CA2035144A1 - Triazolopyridines herbicides - Google Patents
Triazolopyridines herbicidesInfo
- Publication number
- CA2035144A1 CA2035144A1 CA002035144A CA2035144A CA2035144A1 CA 2035144 A1 CA2035144 A1 CA 2035144A1 CA 002035144 A CA002035144 A CA 002035144A CA 2035144 A CA2035144 A CA 2035144A CA 2035144 A1 CA2035144 A1 CA 2035144A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- group
- compound
- pyridine
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000004009 herbicide Substances 0.000 title claims abstract description 8
- 150000008523 triazolopyridines Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 116
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 25
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 19
- 125000005843 halogen group Chemical group 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 9
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000009333 weeding Methods 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005864 Sulphur Substances 0.000 claims abstract description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 3
- OVCXRBARSPBVMC-UHFFFAOYSA-N triazolopyridine Chemical group C=1N2C(C(C)C)=NN=C2C=CC=1C=1OC=NC=1C1=CC=C(F)C=C1 OVCXRBARSPBVMC-UHFFFAOYSA-N 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 171
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- -1 5-thiadiazolyl) group Chemical group 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000013543 active substance Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- NWELCUKYUCBVKK-UHFFFAOYSA-N pyridin-2-ylhydrazine Chemical compound NNC1=CC=CC=N1 NWELCUKYUCBVKK-UHFFFAOYSA-N 0.000 claims description 7
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- 238000006297 dehydration reaction Methods 0.000 claims description 6
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- 230000003647 oxidation Effects 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
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- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 238000005695 dehalogenation reaction Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical group [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005333 aroyloxy group Chemical group 0.000 claims description 2
- 125000004659 aryl alkyl thio group Chemical group 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
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- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 125000000168 pyrrolyl group Chemical group 0.000 claims 1
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- 241000196324 Embryophyta Species 0.000 description 23
- 239000002253 acid Substances 0.000 description 22
- 239000000155 melt Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 19
- 230000000694 effects Effects 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000008187 granular material Substances 0.000 description 15
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- 239000003795 chemical substances by application Substances 0.000 description 14
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- IRZALWDJCUHVNE-UHFFFAOYSA-N (3-methylpyridin-2-yl)hydrazine Chemical compound CC1=CC=CN=C1NN IRZALWDJCUHVNE-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 239000000080 wetting agent Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
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- 239000000945 filler Substances 0.000 description 7
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- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
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- XAYCTBDPZIKHCW-UHFFFAOYSA-N (3-chloropyridin-2-yl)hydrazine Chemical compound NNC1=NC=CC=C1Cl XAYCTBDPZIKHCW-UHFFFAOYSA-N 0.000 description 5
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- 241000219146 Gossypium Species 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
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- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 238000006053 organic reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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- 101150016899 potA gene Proteins 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229940055764 triaz Drugs 0.000 description 1
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
- C07D419/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D419/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
Abstract
Company called: RHONE-POULENC AGROCHIMIE
ABSTRACT
Herbicidal compounds having a triazolopyridine group, the compositions containing them, and their use.
Compounds which can be used as herbicides and have the formula (I) Formula (I) in which:
* X, Y and Z represent a hydrogen atom or a halogen atom or an alkyl group or haloalkyl group or alkoxy group, at least one of the radicals X, Y or Z
having a meaning other than the hydrogen atom, * Ar represents a phenyl group which is optionally mono- or polysubstituted by a lower alkyl group or lower alkoxy group or lower alkylthio group or phenyl group or phenoxy group or a halogen atom, or a heterocycle Het, * Het represents a heterocycle having 5 or 6 ring members and containing one or more hetero atom(s) such as sulphur, nitrogen or oxygen, this heterocycle being optionally mono- or polysubstituted by a lower alkyl or lower alkoxy group or lower alkylthio group or a halogen atom.
The herbicidal compositions which contain the products of the formula (I) and the weeding methods which make use of the compounds of the formula (I) or the compositions containing them.
ABSTRACT
Herbicidal compounds having a triazolopyridine group, the compositions containing them, and their use.
Compounds which can be used as herbicides and have the formula (I) Formula (I) in which:
* X, Y and Z represent a hydrogen atom or a halogen atom or an alkyl group or haloalkyl group or alkoxy group, at least one of the radicals X, Y or Z
having a meaning other than the hydrogen atom, * Ar represents a phenyl group which is optionally mono- or polysubstituted by a lower alkyl group or lower alkoxy group or lower alkylthio group or phenyl group or phenoxy group or a halogen atom, or a heterocycle Het, * Het represents a heterocycle having 5 or 6 ring members and containing one or more hetero atom(s) such as sulphur, nitrogen or oxygen, this heterocycle being optionally mono- or polysubstituted by a lower alkyl or lower alkoxy group or lower alkylthio group or a halogen atom.
The herbicidal compositions which contain the products of the formula (I) and the weeding methods which make use of the compounds of the formula (I) or the compositions containing them.
Description
203~
Herbicidal comPound~ havinq a triazolopyridine qrou~
The present invention thus concerns novel herbicidal compounds from the family of the 1,2,4-triazolol4,3-a]pyridine~, a~ well as processe3 for their preparation, the compo~itions which contain them, and their u~e for combating weeds.
It is therefore an ob~ect of the pre~ent invention to propose compounds which can ~e used as herbicide~ both before emergence (in pre-emergence) and after emergence (in po~t-emergence~.
It is another ob~ect of the present inventicn to propose compound~ which can be used both against weeds of the monocotyledon type and those of the dicotyledon type.
It is another ob~ect of the present invention .
to propo~e compounds which can be u~ed before and~or after emergence as selective herbicide~ in monocotyledon crops (in particular wheat, maize and rice) and dicotyledon crop~ (in particular ~oya, cotton or ~unflower).
It has now been found that all, or some, of the~e aims can be achie~ed by means of the novel compounds according to the i~vention.
In the pra~ent exposition, the expre3~ion lower, qualifying a radical, is under~tood as meaning that this radical can have not more than 4 carbon atom~.
The compounds according to the invention are -.
, characterised by the fact that they have, a~ their formula, the formula (I) which i8 given at the end of . the description, in which:
: * X, Y and Z repre3ent a hydrogen atom or a halogen atom or an alkyl or haloalkyl or alkoxy group, at least one of th~ radical~ X, Y or Z having a méaning other than the hydrogen atom, * Ar repre~ents a phenyl group which is ; optionally mono- or polysubstituted (pref~rably `~ 10 monosubstituted) by a lower alkyl group or lower alkoxy group or lower alkylthio group or phenyl group or phenoxy group or a halogen atom, preferably chlorine or fluorine; or a heterocycle Het, * Het represents a heterocysle having 5 or 6 15 ring Members and containing one or more hetero atom(s) such as sulphur, nitrogen or oxygen, thi~ heterocycle being optionally mono- or polysubstituted (preferably monosubstituted) by a lower alkyl group or lower alkoxy group or lower alkylthio group or a halogen atom, : 20 preferably chlorine or fluorine.
:.- . - :
: .
~ . ". ' ' - ' ' ' ' '
Herbicidal comPound~ havinq a triazolopyridine qrou~
The present invention thus concerns novel herbicidal compounds from the family of the 1,2,4-triazolol4,3-a]pyridine~, a~ well as processe3 for their preparation, the compo~itions which contain them, and their u~e for combating weeds.
It is therefore an ob~ect of the pre~ent invention to propose compounds which can ~e used as herbicide~ both before emergence (in pre-emergence) and after emergence (in po~t-emergence~.
It is another ob~ect of the present inventicn to propose compound~ which can be used both against weeds of the monocotyledon type and those of the dicotyledon type.
It is another ob~ect of the present invention .
to propo~e compounds which can be u~ed before and~or after emergence as selective herbicide~ in monocotyledon crops (in particular wheat, maize and rice) and dicotyledon crop~ (in particular ~oya, cotton or ~unflower).
It has now been found that all, or some, of the~e aims can be achie~ed by means of the novel compounds according to the i~vention.
In the pra~ent exposition, the expre3~ion lower, qualifying a radical, is under~tood as meaning that this radical can have not more than 4 carbon atom~.
The compounds according to the invention are -.
, characterised by the fact that they have, a~ their formula, the formula (I) which i8 given at the end of . the description, in which:
: * X, Y and Z repre3ent a hydrogen atom or a halogen atom or an alkyl or haloalkyl or alkoxy group, at least one of th~ radical~ X, Y or Z having a méaning other than the hydrogen atom, * Ar repre~ents a phenyl group which is ; optionally mono- or polysubstituted (pref~rably `~ 10 monosubstituted) by a lower alkyl group or lower alkoxy group or lower alkylthio group or phenyl group or phenoxy group or a halogen atom, preferably chlorine or fluorine; or a heterocycle Het, * Het represents a heterocysle having 5 or 6 15 ring Members and containing one or more hetero atom(s) such as sulphur, nitrogen or oxygen, thi~ heterocycle being optionally mono- or polysubstituted (preferably monosubstituted) by a lower alkyl group or lower alkoxy group or lower alkylthio group or a halogen atom, : 20 preferably chlorine or fluorine.
:.- . - :
: .
~ . ". ' ' - ' ' ' ' '
2~ 2035~
with the exclusion of compounds wherein, ~ # simultaneously Y represents a methyl group, X and Z represent a hydrogen atom, Ar represents a 3-chloro phenyl or 4-chlorophenyl or 3-pyridyl or 3,4,5-5 trimetho~y phenyl group; or ~ simultaneously X represents a chlorine atom, Y and Z represent a hydrogen atom, Ar represents a 2-pyndyl or 4-pyridyl group.
The invention ~ncludes also the agriculturally 10 acceptable salts, especially acid addition-salts; such acids may be organic or inorganic, for examl)le the chlorhydric sulphuric, acetic, arylsulphonic, and ~e like.
Preferred compounds among~t the compounds accordin~ to the invention are those ha~ing one or the other of the following characteristics:
Only one or two of the three radical~ X, Y or Z represent a radi~al other than the hydrogen atom, when ~, Y or Z are a halogen atom, the atom in que~tion is chlorine or bromine, -:
~ 20 when X, Y or Z are a radical which is at .,. . :
, .
- ~ , . . -. : . .. . ~ . -2~3~4~
least partially hydrocarbon in nature, this radical ha preferably 1 to 4 carbon atoms, 1 carbon atom being even more ~referred.
X is other than a chlonne atom, Z is other than a hydrogen atom, e.g. chlorine or ~ -methyl, .
- X and Y are a hydrogen atom (and Z is other than a hydrogen atom) .
when Ar represents a subs~tituted phenyl group, the substituent(s) is(are) in ortho or para position.
The following Het groups can be mentlonned as especially use~ul in the invention: thienyl (preferably 2- or 3-thienyl), thiazolyl (preferably 2- or 4- thiazolyl), pyridyl (preferably 2-pyridyl), pyITolyl (preferably 2-pyrrolyl), thiadiazolyl (preferably 5-thiadiazolvl).
The following compounds can be mentioned as particular compounds which can be produced according to the invention (for the numbering of the atoms, see note at the end of tho description):
a-ChlOro-3-(3~-methylthien-2~-yl)-s-triazolo[4~3-a]-pyridine, 8-chloro-3-phenyl-s-triazolo[4~3-a]pyridine~
8-methyl-3-(3'-methylthien-2'-yl)-s-triazolot4,3-a]-pyridine, 8-methyl-3-(thien-3~-yl)-~-triazolo[4~3-a]pyridine~
8-methyl-3-(pyrid-2~-yl)-s-triazolo[4~3-a]pyridine~
8-methyl-3-(4'-methylphenyl)-8 -triazolo~4,3-a]pyridine, 8-methyl-3-(4'-fluorophenyl)-s-triazolot4,3-a]pyridine, 8~methyl-3-(2~-chlorophenyl)-s-triazolo[4~3-a]pyridine~
6-methyl-3-phenyl-~-triazolo[4,3-a]pyridine, ... . . . . . .
:: . : , . . . . .
, . -, , .-,: . - , . :-,~ .
3a 2 ~) 3 8-trifluoromethyl-3-phenyl-s-triazolot4,3-a]pyridine, 6-chloro-3-phenyl-~-triazolo[4~3-a]pyridine~
8-methyl-3-~pyrid-3'-yl)-8 -triazolo[4,3-a]pyridine, 8-methyl-3-(pyrid-4'-yl)-s-triazolot4,3-a]p~ridine, 8-methyl-3-(furan-2'-yl)-~-triazolot4,3-a]pyridine, 8-methyl 3-(4'-methoxyphenyl)-s-triazolo[4,3-a]-pyridine, 7-methyl-3-phenyl-~-triazolo~4,3-a]pyridine, 8-methyl-3-(3'-methylphenyl)-8 -triazolot4,3-a]pyridine, 8-methyl-3-(2',4'-dichlorophenyl)-~-triazolo[4,3-a]-~. ., .:
~- ' ' ' ' ~ '~
.
4 203~
pyridine 8-methyl-3-(4~-chlorophenyl)-s-triazolo[4,3-a]pyridine, 8-methyl-3-(4'-phenylphenyl)-s-triazolot4,3-a]pyridine, 8-methoxy-3-phenyl- 8 -tri~zolo~4,3-a]pyridine, 8-me~hyl-3-~thien-2~-yl)-s-triazolo[4~3-a]pyridine~
8-methyl-3-(4'-thiomethylphenyl)-s-triazolo[4,3-a]-pyridine, 8-methyl-3-(2'-fluorophenyl)-s-triazolo[4,3-a]pyridLne, 8-methyl-3-(2'-methylphenyl)-~-trlazolo[4,3-a]pyridine, 10 8-methyl-3-~2~,4~-dimethylphenyl~-~-triazolo[4,3-a]-pyridine, 8-mQthyl-3-phenyl-s-triazolo[4~3-a]pyridin2, 8-promo-3-t3'-methylthien-2'-yl]-~-triazolot4,3-a]-pyridine, 8-trifluoromethyl-3-t3~-methylthien-2~-yl]-s-triazolo-: [4,3-a]pyridine, 8-methyl-3-t2~-methylthien-3~-yl]-s-triazolot4~3-a]
pyridine, 8-bromo-3-phenyl-s-triazolo~4,3-a]pyridine, 20 8-chloro-3-t2'-methylthien-3'-yl]-s-triazolot4,3-a]-pyridine, 8-chloro-3-tthien-3'-yl]-s-triazolot4,3-a]pyridine, 8-methyl-3-tl'-methylpyrrol-2'-yl]-s-triazolot4,3-a]-pyridine, 25 8-~hloro-3-t3',5~-dimethylthien-2'-yl]-~-triazolo-[4,3a]pyridine, 7,8-dimethyl-3-phenyl-~-triazolot4,3-a]pyridine~
8-methyl-3-[3',5'-dimethylthien-2'-yl]-s-triazolo-' ' . ' ' '~ ' .' ' - ~ , ;. :
;' '~ ' ~ . ' , '' " .
~ . ...
` 5 203~14'~
[4l3-a]pyridine~
8-ethyl-3-l3~-methylthien-2~-yl]-s-triazolo[4~3-a]
pyridine, 8-ethyl-3-phenyl-s-trLazolo r 4,3-a]pyridLne, 8-ethyl-3-tl'-methylpyrrol-2'-yl]-s-triazolo[4,3-a~-pyridine, 8-ethyl-3-[thien-3~-yl]-s-triazolo[4,3-a]pyridine, 8-trifluoromethyl-3-[1~-methylpyrrol-2~-yl]-s-triazolo-[4,3-a]pyridine, 8-trifluoromethyl-3-[pyrid-2'-yl]-s-triazolo[4,3-a]-pyridine, 8-chloro-3-[4~-methylthien-2~-yl~-s-triazolo[4~3-a~-pyridine, 7,8-dimethyl-3-t3'-methylthien-2'-yl]-~-triazolo-[4,3-a~pyridine, 8-methyl-3-t4~-methylthien-2~-yl]-s-triazolot4~3-a]
pyridine, 8-trifluoromethyl-3-tthien-3~-yl]-y-triazolo[4~3-a]
pyridine, 8-msthyl-3-[4~-isopropylphenyl]-s-triazolot4~3-a]-pyridine, 8-methyl-3-[4~-bromothien-2~-yl~-s-triazolot4~3-a]
pyridin~, 8-chloro-3-t4'-bromothien-2'-yl]-s-triazolo[4,3-a~-pyridine.
Th~ compounds according to the invention can be prepared by moans of various processes.
According to a first process for the .. . ~, ', ~
: - ,.
203~
preparation of compounds of the formula (I), a compound of the arylidene-2-~pyrid-2'-yl)hydrazine type which has as its formula the formula (II), in which the various substituents have the meanings given above, i8 reacted with an oxidant according to a cycl~ing oxidation reaction. Substance~ which may be mentioned as oxidants are metal cations derived from metal~ which have various degrees of oxidation and which are in the statQ of a higher degree of oxidation, such a~, for example, lead tetraacetate or ferric chloride;
atmospheric oxygen can al80 be u~ed as an oxidant. The reaction i~ advantageou~ly carried out in a liquid organic ~olvent madium, the solvent preferably being ~elected in ~uch a way a~ ~o dissolva tha reactants and the final products as much a~ pos~ible. Suitable solvents are hydrocarbons, halogenated hydrocarbons, acids and alcohol~; solvents of the nitrated aromatic hydrocarbon type can 2180 be used, specifically in tho~e case~ where the oxidant is atmospheric oxygen.
The molar ratio of the amount of oxidant used in relation to the compound of the formula (II) is generAlly between 1 and 5.
According to a first variant, the oxidation reaction for the compound of the formula (II) can also be effected by adding a halogen (preferably in approximately ~toichiometric amount), such a~ bromine, followed by a dehalogenation reaction. These oxidation reactions (according to the general method or according .... .
7 2 0 3 v~
to the variant) are generally effected between 10 and 210C (preferably between 10 and 50C in the case of the variant).
Cyclisinq oxidation is achieved by following this oxidation by means of halogenation by a dehalogenation reaction which is generally effected in the pre~ence of an alkaline agent, for example in the presence of an alkali metal salt of a carboxylic acid such as sodium scetate, in an acetic acid medium. The molar ratio of the amount of alkaline agent used in relation to the halogenated compound of the formula (II) i~ generally between 1 and 5.
According to a second variant, the oxidation reaction for the compound of the formula (II) can al~o be effected by adding an N-halo-N-metallo~ulphonamidate of the formula (IV~:
RSO2~X M where ~ represent~ an alkyl group, or preferably phenyl which i~ optionally monosubstituted in the para position by an alkyl group (for example a p-tolyl group), X represent~ a halogen atom (preferably chlorine or bromine) and M a alkali metal atom (preferably ~odium). A preferred example of an N-halo- :
N-metallo~ulphonamidate i3 chloramine T, of the formula (IVa):
CN~ ~ S0~ N¢l Na-; ' - .. ~;' . ' ' ~
.
.
.
.
8 203~44 The u-~e of an N-halo-N-metallo~ulphonamidate of the preceding formula a~ an oxidant which cycli~e~
a~ylidene-2-(pyrid-2'-yl)hydrazines, which have a~
their formula the general formula (II~ original and S thu~ con~t~tutes a novel preparation proce~ for compound~ of the formula (I).
This cycli~ing oxidation reaction i8 generally effected between 10 and lSO-C (preferably betwaen 20 and 50-C) and is Ædvantageou~ly effected in a liquid organic ~olvent medium, preferably alcohol.
~ he molar ratio of the amount of oxidant used in relation to the compound of the formula (II) i8 preferably approximately stoichiometric.
According to a second preparation method for compounds of the formula (I), a compound of the 2-(aioylhydrazine)pyridine type, which has, as its formula, the formula (I~I) in which the variou~
substituents have the ~ame meaning a~ in formula (I), is dehydrated (cyclising dehydration).
The cyclising dehydration reaction of the compound of the formula (III) is usually carried out by heating at between 100 and 250-C, with el~mination of the water formed as the reaction proceeds. ~he water formed can bs el~minated by simple distillation or, alternatively, by azeotropic distillation, if the heating i8 effected in the presence of an aromatic solvent which i8 capable of dissolving the compound of the formula (III) and forming an azeotrope with water.
. . .
- .. . .. .
.~': ~ . . ' , - .
. .
9 203~144 Azeotropic solvent~ which are suitable for this dehydration method and which may be mentioned are the halogenated or unhalogenated aromatic hydrocarbon , a~
well as the phenols, for example xylene, phenol and 1,2,4-trichlorobenzene.
According to a first ~ariant of the cyclising dehydration of the compound of the formula (III), the proces~ is carried out in the pre~ence of a dehydrating agent, preferably in the presence of an inert solvent, for example an aromatic hydrocarbon such a~ benzene, toluene and xylene. The dehydrating agent i8 advantageously a water scavsnger known per 8e, such as POCl3 or concentrated acetic acid or polypho~phoric acid, the amount of dehydrating agent used being advantageously between 1 and 50 times the molar amount of the compou~d of the formula (III).
According to a second variant, the dehydrating cyclisation of the compounds of the formula (III) i~ effected via a transitory pas~age through an intermediate of the formula ~XI) or ~XII), in which the ~ubstituents have the ~ame meaningQ as in formula (I)~
The intermediates of the formula ~XI) are formed by reac~ion of SOCl2 with a compound of the formula (III) tin an amount of, for exampla, between 1 and 3 moles per mole of compound of the formula (III)], at a temperature between -5-C and 50C, preferably at ambient temperature; the reaction is advantageously effected in the pre~ence of a solvent and/or an acid .7 ,, ,, ,', '' ' ' ' . " ' ', ,. '' ' ' , ., ' ' " " '' ' ' ' ~ ' ' ' ~
''''' ' ' ' ' " . . . .
' ~ ' ~ . ' ' ' ' ' ' ~.
~ ' ' .
.~. ' ' .
' ' . .
lo 2 0 3 ~; 1 4 4 scavenger, in particular pyridine or dimethylformamide (DMF) in the pre~ence of tri~thylamine.
Thermoly~is of the compounds of the formula (XI) to give compounds of the formula (I) i8 accompanied by a liberation of SO2. It i8 preferred for thi~ thermoly~is to be carried out in the pre~e~ce of a solvent such a~ nitrile~ or aromatic hydrocarbons, in particular acetonitrile, toluene, xylenes or naphthalenes, which are optionally alkylated tPreferably methylated).
The cyclising dehydration of compounds of the formula (III) to give compounds of the formula ~I), via intermediates of the formula (XII), is advantaqeously effected by reacting compound~ of the dichlorotriarylphosphorane type with a compound of the formula (III), in the pre~ence of a tertiary base ~uch as triethylamine, and of a ~olvent of the nitrile type.
According to a third preparation method for compoundR of the formula (I3, a cyclising deamination is carried out by heating a compound of the amidrazone type, which hss, a~ it~ formula, (IV) in which the ~arious sub~tituent~ have the same meaning as in formula (I).
The reaction is advantageou~ly effected in the presenca of agents (liquid~) which ~cavenge a onia moleGules, for example in the pre~ence of acids, anhydrides or halides of acids, these acid~ preferably being carboxylic acids. The temperature is generally .
11 203~
between 25 and 220C, preferably between S0 and 180C.
The amount of agent which scaven~es ammonia molecule4 i~ generally between 1 and 30 times the amount (in moles) of the product of the formula (IV).
The deamination can al~o be carried out by simple heating in a liquid medium (thermal deamination), preferably in an inert organic ~olvent medium, for example a halogenated or unhalogenated aromatic hydrocarbon.
According to a fourth preparation proce~ for products of the formula (I), a compound of the hydrazine type of the formula (V) i8 reacted with a compound of the formula ~VI): U~-C(=Wl)-Ar according to the reaction:
~!1 (V) + (VI) _ (I) + UlH + NlH2 the various radicals of the~e formulae (V) and (VI) having the same meanings a~ in the formula (I) and, in addition:
W1 represents an oxygen atom or an NH group, when Wl represents the oxyqen atom, then Ul represents a hydroxyl group [(VI) is thu~ an acid] or alkoxy group t(VI) iB thus an ester] or aroyloxy group t(VI) is thu~ an acid anhydride], or a halogen atom t(VI) i8 thu~ an acid halide], preferably chlorine, when Wl represents an NH group, then U
represents an alkoxy group or alkylthio group or : . . . ~. .: .
- . :
-~5 ' .;
12 ~03~14~
arylalkylthio group.
The preceding reaction i~ effected at a temperature of generally between 20 and 200C, preferably between 50 and 180-C, over a period of 1 to 24 hours. The reactants (V) and (VI) are used in respective molar proportions between 0.8 and 1.2, preferably equal to, or near, 1. The reaction can be effected in the presence or absence of a solvent.
Solvents which can be used, as shown hereinafter in oertain cases, are qolvents which lead to the formation of azeotropic mixtures. Solvents of the alcohol type can also be u~ed when ~he compound of the formula (VI) i8 an imidate, or an aromatic solvent such as a halogenated or unhalogenated hy~rocarbon, or pyridine, when the compound of the formula (VI) is a thioimidate or an acid halide.
~ he light reaction products (U1H and WlH2) are advantageously eliminated a~ the reaction proceeds, generally by distillation when the product in question 20 i8 water or alcohols (U1 thus represent~ a hydroxyl or alkoxy group), and al~o by scavenging wi~h the aid of a tertiary base such a~ triethylamine, when Ul is a halogen ato~, and al80 by scavenging of the ammonia molecule, when Wl i~ NH and Ul is alkoxy (the product of the formula (VI~ is thu an imidate).
The abovementioned di~tillation of the light products can be an azeotropic distillation in the presence of aromatic halogenated or unhalogenated , :~::
" 13 203514~
solvents such a~ pyridine, or the chlorobenzenes, in particular 1,2,4-trichlorobenzene.
The abovementioned ~cavenging of ammonia iR
advantageously effected in the presence of acid~
(preferably carboxylic acids) or of their derivatives such as acid anhydrides or acid halides. These acids or their derivatives are used in a molar amount of generally between 1 and 30 times tha amount of product of the formula (VI) used. These proportions are in the same order of magnitude (mutatis mutandis) when a base i8 used when Ul is a halogen atom.
According to a fifth preparation process for compounds of the formula (I~, a pyridine derivative of the formula (VIII) is reacted with a tetrazole compound of the formula (IX), in which formulae X, Y, Z and Ar have the same meaning as in formula (I) and T
represents a halogen atom, preferably chlorine. The reaction i8 advantageously effected between 20 and l50-C, prsferably in an organic 801vent~ for ex~mple a halogenated or unhalogenated aromatic hydrocarbon such as xylenes, chlorobenzenes or tetralin, or a soivent` of the heterocyclic type such as pyridine.
The invention also relates to novel products which can opt~onelly be u3ed as intermediate~ in the processes according to the invention, characterised in that they have, as their formula, one of th~ formulae (II~ ,- (IV), (VIII), (XI) or (XII) in which the 8ymb01 X~ ~ Z and ~r have the meanings .. . . . . .
: ..... : -i . ... -~ ' ~: ,:- , ., 14 203~
given in the cs~e of the formula (I).
Another ob~ect of the invention is the use of the compound~ of the formu~a (II) as herbiclde~. In what follows, but al~o in the preceding text, the reaction~ which are effected under hot condition~ in a solvent, unless specifically indicated to the contrary, are advantageoucly carried out at the boiling point of the solvent in question.
The preparation of the tetrazoles of the formula (IX) is conveniently effected by reacting an aromatic nitrile of the formula Ar-CN with an alXali metal azide, for example ~odium azide or ammonium azide, at temperature~ between 80 and 130C. Ths molar amount of azide is advantageou~ly between 1 and 3 times (preferably 1.5 and 2 time~) the amount of nitrile.
This reaction is generally effected in a polar solvent such as ~MF or acetic acid or the alcohol~ or their mixtures. Such a reaction i3 described in Advances in Heterocyclic Chemistry, ~ol. 21, page~ 323-435, published in 1977 by Academic Pre~ in an articla by R.N. Butler with the title: Recent advances in tetrazole chemi~try.
The preparation of the arylidene-2-(pyrid-2'-yl)hydrazine~ of the formula (II) is conveniently effected by reacting 2-hydrazinopyridines of the formula (V) with aldehyde~ of the formula Ar-CHO in which the symbol8 X, Y, Z and Ar have the meanings given in the case of the formula (I). The reaction is ,~:'- ' .. ,' .: :
. .
. -:
203~1~4 generally effected at a temperature between 50 and l50~C, preferably in a ~olvent. A lower alcohol such as methanol or ethanol i~ advantagsously used as the solvent. The reaction is promoted by the prei~ence of catalytic amounts of a mineral inorganic or organic acid, for example hydrochloric acid, sulphuric acid, acetic acid, trichloroacetic acid or perchloric acid.
Such a reaction i~ described in Quarterly review, Chemical Society, vol. 23, page~ 37-56, 1969, in an article by J. Buckingham a~ wall a~ in Houben-Weyl, Methoden der organischen Chemie, 4th edition, 1967, vol. X-~, pages 410-487.
The preparation of the 2-(aroylhydrazino)-p~ridine~ of the formula (III) i~ conveni~ntly effected by reacting 2-hydrazinopyridines of the formula (V) with compounds of the formula Ar-CO-U2 in which the ~ymbols X, Y, Z and Ar have the meanings given in the case of the formula (I), and U2 has on~ of the meaning~
given above in the case of Ul. The reaction proceeds in accordance with the equation:
(V~ + Ar-CO-U2 ~ --~(III) + U2H
The reaction i~ generally effected by mixing reactants at a temperature between 0 and 180C, in the pres2nce or absence of a ~olvent. A polar ~olvent i~
advantageously used ai~ solvent.
The following can therefore be cited a~
~- - .. . . , , .
.
.
'~
16 203~
~olvents which can more particularly be u~ed: alcohols when Ar-CO-U2 is not an acid halide; ethers or aliphatic chlorinated or unchlorinated hydrocarbon~ such as methylene chloride, chloroform; ~ol~ents which have acid-scavenging properties, 3uch as pyr~dine, can likewise be used wh~n Ar-CO-U2 repreqent~ an acid halide.
The proportion of the two reactants [that of the formula (V) and that of the formula Ar-CO-U2] can be varied within wide limits around ~toichiometric. When Ar-CO-U2 is an acid ~U2 i~ OH), an excess of the latter derivative i~ u~ed ~n relation to the compound of the formula (Y), for example from 2 to 8 moles per mole of (v). When Ar-CO-U2 i8 an ester (U2 is alkoxy), an approximately sto~chfometric amount of the latter derivative i8 u~ed in relation to the compound of the formula (V), for example from 0.8 to 1.1 moles per mole of (V). When Ar-CO-U2 is an acid halide (U2 is a halogen atom), an exces~ of the compound of the formula (V) i8 used in relation to the compound of the formula Ar-CO-~2, for example from 1 to 5 mole~ per mole of Ar-CO-U2 .
Proces~es which allow tha compounds of the formula (III) to be obtained in accordance with what has ~ust been described are described in the work by Pata~, The chemi~try of carboxylic acids and ester~, ~ol. 5, chapter 9, pages 425-428, publi~hed in 1969 by Interscience/Wiley in an article by Satchell, and also .
- . ' ' .: ~ ' ,~
` ~" 17 203S14~
in Houben-Weyl, Methoden der organischen Chemie, 1952, Vol. VIII, chapter 5, pages 676-680.
The 2-(aroylhydrazino)pyridine~ of the formula (III) can also be prepared conveniently by reacting a pyridine derivative of the formula (VIII) with an aryl hydrazide of the formula Ar-C0-NH-NH2 in which the symbols T, X, Y, Z and Ar have the meanings already given in the case of the formulae (I) and (VIII). The reaction proceed~ in accordance with the e~uation:
(VIII) I Ar-CO-NH-NH2 > (III
,.
This reaction i~ advantageou~ly carried out at a temperature betwoen 50 and 150C, in solvents such a~ alcohols or aromatic solvent~ t for e~ample pyridine or hydrocarbon~ ~uch aY toluen~. The reactants ar~
advantageously in an approximately stoichiometric proportion, for example in a molar ratio ranging from 0.8 to 1.2. The reaction can ~e promoted by the presence o~ a likewi~s approximately stoi~hiometric amount of a basic agent uch aY an alcoholat~ or an alkali metal bicarbonate.
The aryl hydrazide~ of the formula Ar-C0-NH-NH2 can be obtained by reacting hydrazine hydrate with an acid or one of it~ derivative~ such as the e3ters, halide~ or anhydride~. The reaction is advantageou~ly effected at a temperature between 0 and ,, . : ' '''' .; ' , - , . . - , .
18 203S~L4 150~C, preferably in the presence of a ~olvent such as a lower alcohol, the molar proportion of hydrazLne hydrate in relation to the other reactant generally being between 1.01 and 1.5.
Processe~ which allow the aryl hydraz~de~ to be obtained in accordance with what has ~U8t been described are described in the work by Pata~, Th~
chemi~try of amides, vol. 11, chapter 10, pages 515-600, published in 1970 by Interscience/Wiley, in an article by Paulsen and Stoye, and also in Organic Reactions, the Curtius reaction, 1962, Vol. III, chapter 9, pages 366-369 publi~hed by Wiley.
The amidrazone~ of the formula (IV) can be prepared uYing 2-hydrazinopyridin~s of the formula (V) according to the following reaction equations (V) + Ar-C(=NH)-U3 ~ ~ (IV) + U3H~
the various radicals of these reactants and reaction products having the ~ame meaning as in the preceding formulae, and U3 represents a preferably lower alkoxy or alkylthio radical.
~ he reaction is advan~ageously effected a~ a temperature between O and 30~C, preferably in an alcohol-type solvent.
Proce~ses which allow tho amidrazones of the formula (IV) to be obtainsd in accordance with what ha~
~ust been described are described in the work by Pata~, ~' : , . . . .
- : :
-- , . .
.
. . :
.
.~ .. . .
19 203~
The chemi~try of amidines and Lmidates, vol. 20, chapter 10, pages 491-545, published in 1975 by Interscience/Wiley in an article by Watson, a~ well as in an article by Neilson et al., Chemical Review, 1970, Vol. 70, pages 151-170.
The iminoethers of the formula Ar-C(=NH)-U3 in which U3 represents an alkoxy group can be prepared by reacting an aromatic nitrile Ar-CN with a lower alcohol, preferably an alkanol, between -20 and +30C, 10 advantageously in an ether-type solvent, for example ethyl ethsr or 1,2-dimethoxyethane or dioxane, or a halogenated, preferably aliphatic, hydrocarbon such as chloroform. More precisely, the reaction i8 effected in an anhydrous medium in the presence of (gaseous) HCl.
15 Processes which allow these iminoethers of the formula n Ar-C(=NH)-U3 to be obtained are de~cribed in the work by Pata~, The chemistry of amidines and imidates, vol. 20, chapter 9~ page~ 385-489, published in 1975 by Interscience/Wiley in an article by Neilson, as well as : 20 in an article by Roger and ~eilson, Chemical Review, ; 1961, vol. 61, pages 179-211.
~he thioimidates of the formula Ar-Ct=NH)-U3 in which U3 represents an alkylthio group can be prepared by alkylation of arylthiobenzamides by a 25 proc~s such a~ de3cribed by Doyle et al. in Synthesis, 583 (1974). These arylth$obenzamides ~hem~elves can be obtained for example a~ described in the work by Patai, The chemistry of amides, vol. 11, chapter 8, page~
.~ .. . . . .
.
- - ~ ~ .- .. , -. : ~
2r~3s~.~L~ ., 383-475, published in 1970 by Interscience/Wiley, in an article by Walta and Vo~.
The 2-hydrazinopyridine~ of the formula (V) can be obtained by reacting hydrazine hydrate with a 2-halopyridine of the formula (VIII) at a temperaturebetween 0 and 120C, in the presence or absence of a solvent. Solvent~ which may be cited are, in particular, polar ~olvents such as alcohols, pyridine, or dimethyl sulphoxide. The molar amount of hydrazine hydrate is generally between 3 and 15 times the amount of product of the formula (VIII~ used. Processes which allow the compounds of the formula (V) to be obtained in accordance with what has ~u~t been described are described by Enders in Houben-Weyl, Methoden der organischen Chemie, 4th edition, 1967, vol. X-2, chapter 5, pages 252-287.
In particular, the 2-halopyridine~ of the formula (VIII) can be prepared by a proces~ similar to those described by ~linsberg in The Chemistry of Heterocyclic Compounds, Pyridine and its derivative~, part~ I - I~, publi~hed in 1974-1975 by Interscience/Wiley, and by Abramovitch, in The chemistry of ~eterocyclic compounds, Pyridine and its derivatives, supplQments 1 - 5, published in 1960-1964 by Interscience/Wiley.
The following examples, which are given without implied lLmitation, illustrate the invention and show how it can be implemented. In these example~, .~' ' .
2, 203~144 the symbol Ac designates the radical CH3-CO-, the ~ymbol DMF designates dimethylformamide. The word amidrazone de3i~nates compounds which have a group -NH-N= C
Examples 1 to 14 illustrate the preparation of herbic~dal compound~ according to the invan~ion.
Examples I-l to I-10 illustrate the preparation of intermediates of the preceding products.
*Example 1: -Lead tetraacetate (6.7 g; 0.015 mol) are added to phenyl(3'-chloropyrid-2'-yl)hydr~zon~ (3.5 g;
0.015 mol), prepared a~ in Example I-l, in qlacial acetic acid (300 ml) at ambient temp~ratur~ and with stirring. Stirring i~ continued for on~ hour at 60-C.
The medium iB concentrated to dryne~s under reduced presaure. The residua is triturated with water (100 ml), and the mix~ure is filtered, washed with water and dried. 8-Chloro-3-phenyl-s-triazolot4,3-~pyridine ~3.1 g; 0.0135 mol), wh$ch melts at 153-C, iB obtained (yield 90%).
*~xample 2:
A mixture of 3-formylthiophene (2.8 q;
0.025 mol) and 2-hydrazino-3-methylpyridine (3.1 g;
0.025 mol), prepared a~ in Example I-8, in ethanol - : -: . , . ~
22 203~1~4 (30 ml) containing a few drop~ of concentrated HCl, is kept at boiling point for two hours. An ethanolic solution of FeCl3 . 6HzO (70 ml; 0.125 mol) is added gradually, and heating at boiling point is con~i~ued for two hours. The reaction medium i~ concentrated to dryness ur.der reduced pre~sure, the residue is taken up in water (100 ml), the mixture i~ rendered neutral with the aid of gaseou~ NH3 (pH between 8 and 9), and extracted with CH2C12. After the organic phass~ have been concentrated and the residue ha~ been dried and recrystallised u~ing aqueous ethanol, 8-methyl-3-(thien-3'-yl)-~-triazolo[4,3-a]pyridine (6.05 g;
0.02180 mol), which melt~ at 165C, i~ obtained (yield 87%).
*Example 3s Bromine (1.25 ml) in glacial acetic acid (5 ml) i8 added at ambient temperature to a suspen~ion of anhydrou~ sodium acetat2 (6.15 q; 0.075 mol) in : glacial acetic ac$d (50 ml) containing phenyl (3'-20 trifluoromethylpyrid-2'-yl)hydrazone (6.65 g; 0.025 mol) prepared a3 in ~xample I-2. The reaction medium i~
stirred for one hour and poured into an aqueou~
solution of 2N NaOH (300 ml). The precipitate is filtered, wa~hsd with water and dried. 3-Phenyl-8-25 trifluoromethyl-~-triazolot4,3-a]pyridine (4.75 g;
0.018 mol)~ which melts at 197C, is obtained (yield 72%).
,, ' . ~
23 2 o 3 5 1 4 ,~
~ExamPle 4s 2-Formyl-3-methylthiophene (3.15 g;
0.025 mol)~ dissolved in ethanol (20 ml), is added at ambient temperature to a stirred solution of 3-chloro-2-hydrazinopyridine (3.6 g; 0.0~5 mol), prep~red a~ in Example I-7, in ethanol (30 ml) which has been acidified with a little HCl. The mixture i~ heated at boiling point for 2 hour~ and concentrated to dryne~s.
with the exclusion of compounds wherein, ~ # simultaneously Y represents a methyl group, X and Z represent a hydrogen atom, Ar represents a 3-chloro phenyl or 4-chlorophenyl or 3-pyridyl or 3,4,5-5 trimetho~y phenyl group; or ~ simultaneously X represents a chlorine atom, Y and Z represent a hydrogen atom, Ar represents a 2-pyndyl or 4-pyridyl group.
The invention ~ncludes also the agriculturally 10 acceptable salts, especially acid addition-salts; such acids may be organic or inorganic, for examl)le the chlorhydric sulphuric, acetic, arylsulphonic, and ~e like.
Preferred compounds among~t the compounds accordin~ to the invention are those ha~ing one or the other of the following characteristics:
Only one or two of the three radical~ X, Y or Z represent a radi~al other than the hydrogen atom, when ~, Y or Z are a halogen atom, the atom in que~tion is chlorine or bromine, -:
~ 20 when X, Y or Z are a radical which is at .,. . :
, .
- ~ , . . -. : . .. . ~ . -2~3~4~
least partially hydrocarbon in nature, this radical ha preferably 1 to 4 carbon atoms, 1 carbon atom being even more ~referred.
X is other than a chlonne atom, Z is other than a hydrogen atom, e.g. chlorine or ~ -methyl, .
- X and Y are a hydrogen atom (and Z is other than a hydrogen atom) .
when Ar represents a subs~tituted phenyl group, the substituent(s) is(are) in ortho or para position.
The following Het groups can be mentlonned as especially use~ul in the invention: thienyl (preferably 2- or 3-thienyl), thiazolyl (preferably 2- or 4- thiazolyl), pyridyl (preferably 2-pyridyl), pyITolyl (preferably 2-pyrrolyl), thiadiazolyl (preferably 5-thiadiazolvl).
The following compounds can be mentioned as particular compounds which can be produced according to the invention (for the numbering of the atoms, see note at the end of tho description):
a-ChlOro-3-(3~-methylthien-2~-yl)-s-triazolo[4~3-a]-pyridine, 8-chloro-3-phenyl-s-triazolo[4~3-a]pyridine~
8-methyl-3-(3'-methylthien-2'-yl)-s-triazolot4,3-a]-pyridine, 8-methyl-3-(thien-3~-yl)-~-triazolo[4~3-a]pyridine~
8-methyl-3-(pyrid-2~-yl)-s-triazolo[4~3-a]pyridine~
8-methyl-3-(4'-methylphenyl)-8 -triazolo~4,3-a]pyridine, 8-methyl-3-(4'-fluorophenyl)-s-triazolot4,3-a]pyridine, 8~methyl-3-(2~-chlorophenyl)-s-triazolo[4~3-a]pyridine~
6-methyl-3-phenyl-~-triazolo[4,3-a]pyridine, ... . . . . . .
:: . : , . . . . .
, . -, , .-,: . - , . :-,~ .
3a 2 ~) 3 8-trifluoromethyl-3-phenyl-s-triazolot4,3-a]pyridine, 6-chloro-3-phenyl-~-triazolo[4~3-a]pyridine~
8-methyl-3-~pyrid-3'-yl)-8 -triazolo[4,3-a]pyridine, 8-methyl-3-(pyrid-4'-yl)-s-triazolot4,3-a]p~ridine, 8-methyl-3-(furan-2'-yl)-~-triazolot4,3-a]pyridine, 8-methyl 3-(4'-methoxyphenyl)-s-triazolo[4,3-a]-pyridine, 7-methyl-3-phenyl-~-triazolo~4,3-a]pyridine, 8-methyl-3-(3'-methylphenyl)-8 -triazolot4,3-a]pyridine, 8-methyl-3-(2',4'-dichlorophenyl)-~-triazolo[4,3-a]-~. ., .:
~- ' ' ' ' ~ '~
.
4 203~
pyridine 8-methyl-3-(4~-chlorophenyl)-s-triazolo[4,3-a]pyridine, 8-methyl-3-(4'-phenylphenyl)-s-triazolot4,3-a]pyridine, 8-methoxy-3-phenyl- 8 -tri~zolo~4,3-a]pyridine, 8-me~hyl-3-~thien-2~-yl)-s-triazolo[4~3-a]pyridine~
8-methyl-3-(4'-thiomethylphenyl)-s-triazolo[4,3-a]-pyridine, 8-methyl-3-(2'-fluorophenyl)-s-triazolo[4,3-a]pyridLne, 8-methyl-3-(2'-methylphenyl)-~-trlazolo[4,3-a]pyridine, 10 8-methyl-3-~2~,4~-dimethylphenyl~-~-triazolo[4,3-a]-pyridine, 8-mQthyl-3-phenyl-s-triazolo[4~3-a]pyridin2, 8-promo-3-t3'-methylthien-2'-yl]-~-triazolot4,3-a]-pyridine, 8-trifluoromethyl-3-t3~-methylthien-2~-yl]-s-triazolo-: [4,3-a]pyridine, 8-methyl-3-t2~-methylthien-3~-yl]-s-triazolot4~3-a]
pyridine, 8-bromo-3-phenyl-s-triazolo~4,3-a]pyridine, 20 8-chloro-3-t2'-methylthien-3'-yl]-s-triazolot4,3-a]-pyridine, 8-chloro-3-tthien-3'-yl]-s-triazolot4,3-a]pyridine, 8-methyl-3-tl'-methylpyrrol-2'-yl]-s-triazolot4,3-a]-pyridine, 25 8-~hloro-3-t3',5~-dimethylthien-2'-yl]-~-triazolo-[4,3a]pyridine, 7,8-dimethyl-3-phenyl-~-triazolot4,3-a]pyridine~
8-methyl-3-[3',5'-dimethylthien-2'-yl]-s-triazolo-' ' . ' ' '~ ' .' ' - ~ , ;. :
;' '~ ' ~ . ' , '' " .
~ . ...
` 5 203~14'~
[4l3-a]pyridine~
8-ethyl-3-l3~-methylthien-2~-yl]-s-triazolo[4~3-a]
pyridine, 8-ethyl-3-phenyl-s-trLazolo r 4,3-a]pyridLne, 8-ethyl-3-tl'-methylpyrrol-2'-yl]-s-triazolo[4,3-a~-pyridine, 8-ethyl-3-[thien-3~-yl]-s-triazolo[4,3-a]pyridine, 8-trifluoromethyl-3-[1~-methylpyrrol-2~-yl]-s-triazolo-[4,3-a]pyridine, 8-trifluoromethyl-3-[pyrid-2'-yl]-s-triazolo[4,3-a]-pyridine, 8-chloro-3-[4~-methylthien-2~-yl~-s-triazolo[4~3-a~-pyridine, 7,8-dimethyl-3-t3'-methylthien-2'-yl]-~-triazolo-[4,3-a~pyridine, 8-methyl-3-t4~-methylthien-2~-yl]-s-triazolot4~3-a]
pyridine, 8-trifluoromethyl-3-tthien-3~-yl]-y-triazolo[4~3-a]
pyridine, 8-msthyl-3-[4~-isopropylphenyl]-s-triazolot4~3-a]-pyridine, 8-methyl-3-[4~-bromothien-2~-yl~-s-triazolot4~3-a]
pyridin~, 8-chloro-3-t4'-bromothien-2'-yl]-s-triazolo[4,3-a~-pyridine.
Th~ compounds according to the invention can be prepared by moans of various processes.
According to a first process for the .. . ~, ', ~
: - ,.
203~
preparation of compounds of the formula (I), a compound of the arylidene-2-~pyrid-2'-yl)hydrazine type which has as its formula the formula (II), in which the various substituents have the meanings given above, i8 reacted with an oxidant according to a cycl~ing oxidation reaction. Substance~ which may be mentioned as oxidants are metal cations derived from metal~ which have various degrees of oxidation and which are in the statQ of a higher degree of oxidation, such a~, for example, lead tetraacetate or ferric chloride;
atmospheric oxygen can al80 be u~ed as an oxidant. The reaction i~ advantageou~ly carried out in a liquid organic ~olvent madium, the solvent preferably being ~elected in ~uch a way a~ ~o dissolva tha reactants and the final products as much a~ pos~ible. Suitable solvents are hydrocarbons, halogenated hydrocarbons, acids and alcohol~; solvents of the nitrated aromatic hydrocarbon type can 2180 be used, specifically in tho~e case~ where the oxidant is atmospheric oxygen.
The molar ratio of the amount of oxidant used in relation to the compound of the formula (II) is generAlly between 1 and 5.
According to a first variant, the oxidation reaction for the compound of the formula (II) can also be effected by adding a halogen (preferably in approximately ~toichiometric amount), such a~ bromine, followed by a dehalogenation reaction. These oxidation reactions (according to the general method or according .... .
7 2 0 3 v~
to the variant) are generally effected between 10 and 210C (preferably between 10 and 50C in the case of the variant).
Cyclisinq oxidation is achieved by following this oxidation by means of halogenation by a dehalogenation reaction which is generally effected in the pre~ence of an alkaline agent, for example in the presence of an alkali metal salt of a carboxylic acid such as sodium scetate, in an acetic acid medium. The molar ratio of the amount of alkaline agent used in relation to the halogenated compound of the formula (II) i~ generally between 1 and 5.
According to a second variant, the oxidation reaction for the compound of the formula (II) can al~o be effected by adding an N-halo-N-metallo~ulphonamidate of the formula (IV~:
RSO2~X M where ~ represent~ an alkyl group, or preferably phenyl which i~ optionally monosubstituted in the para position by an alkyl group (for example a p-tolyl group), X represent~ a halogen atom (preferably chlorine or bromine) and M a alkali metal atom (preferably ~odium). A preferred example of an N-halo- :
N-metallo~ulphonamidate i3 chloramine T, of the formula (IVa):
CN~ ~ S0~ N¢l Na-; ' - .. ~;' . ' ' ~
.
.
.
.
8 203~44 The u-~e of an N-halo-N-metallo~ulphonamidate of the preceding formula a~ an oxidant which cycli~e~
a~ylidene-2-(pyrid-2'-yl)hydrazines, which have a~
their formula the general formula (II~ original and S thu~ con~t~tutes a novel preparation proce~ for compound~ of the formula (I).
This cycli~ing oxidation reaction i8 generally effected between 10 and lSO-C (preferably betwaen 20 and 50-C) and is Ædvantageou~ly effected in a liquid organic ~olvent medium, preferably alcohol.
~ he molar ratio of the amount of oxidant used in relation to the compound of the formula (II) i8 preferably approximately stoichiometric.
According to a second preparation method for compounds of the formula (I), a compound of the 2-(aioylhydrazine)pyridine type, which has, as its formula, the formula (I~I) in which the variou~
substituents have the ~ame meaning a~ in formula (I), is dehydrated (cyclising dehydration).
The cyclising dehydration reaction of the compound of the formula (III) is usually carried out by heating at between 100 and 250-C, with el~mination of the water formed as the reaction proceeds. ~he water formed can bs el~minated by simple distillation or, alternatively, by azeotropic distillation, if the heating i8 effected in the presence of an aromatic solvent which i8 capable of dissolving the compound of the formula (III) and forming an azeotrope with water.
. . .
- .. . .. .
.~': ~ . . ' , - .
. .
9 203~144 Azeotropic solvent~ which are suitable for this dehydration method and which may be mentioned are the halogenated or unhalogenated aromatic hydrocarbon , a~
well as the phenols, for example xylene, phenol and 1,2,4-trichlorobenzene.
According to a first ~ariant of the cyclising dehydration of the compound of the formula (III), the proces~ is carried out in the pre~ence of a dehydrating agent, preferably in the presence of an inert solvent, for example an aromatic hydrocarbon such a~ benzene, toluene and xylene. The dehydrating agent i8 advantageously a water scavsnger known per 8e, such as POCl3 or concentrated acetic acid or polypho~phoric acid, the amount of dehydrating agent used being advantageously between 1 and 50 times the molar amount of the compou~d of the formula (III).
According to a second variant, the dehydrating cyclisation of the compounds of the formula (III) i~ effected via a transitory pas~age through an intermediate of the formula ~XI) or ~XII), in which the ~ubstituents have the ~ame meaningQ as in formula (I)~
The intermediates of the formula ~XI) are formed by reac~ion of SOCl2 with a compound of the formula (III) tin an amount of, for exampla, between 1 and 3 moles per mole of compound of the formula (III)], at a temperature between -5-C and 50C, preferably at ambient temperature; the reaction is advantageously effected in the pre~ence of a solvent and/or an acid .7 ,, ,, ,', '' ' ' ' . " ' ', ,. '' ' ' , ., ' ' " " '' ' ' ' ~ ' ' ' ~
''''' ' ' ' ' " . . . .
' ~ ' ~ . ' ' ' ' ' ' ~.
~ ' ' .
.~. ' ' .
' ' . .
lo 2 0 3 ~; 1 4 4 scavenger, in particular pyridine or dimethylformamide (DMF) in the pre~ence of tri~thylamine.
Thermoly~is of the compounds of the formula (XI) to give compounds of the formula (I) i8 accompanied by a liberation of SO2. It i8 preferred for thi~ thermoly~is to be carried out in the pre~e~ce of a solvent such a~ nitrile~ or aromatic hydrocarbons, in particular acetonitrile, toluene, xylenes or naphthalenes, which are optionally alkylated tPreferably methylated).
The cyclising dehydration of compounds of the formula (III) to give compounds of the formula ~I), via intermediates of the formula (XII), is advantaqeously effected by reacting compound~ of the dichlorotriarylphosphorane type with a compound of the formula (III), in the pre~ence of a tertiary base ~uch as triethylamine, and of a ~olvent of the nitrile type.
According to a third preparation method for compoundR of the formula (I3, a cyclising deamination is carried out by heating a compound of the amidrazone type, which hss, a~ it~ formula, (IV) in which the ~arious sub~tituent~ have the same meaning as in formula (I).
The reaction is advantageou~ly effected in the presenca of agents (liquid~) which ~cavenge a onia moleGules, for example in the pre~ence of acids, anhydrides or halides of acids, these acid~ preferably being carboxylic acids. The temperature is generally .
11 203~
between 25 and 220C, preferably between S0 and 180C.
The amount of agent which scaven~es ammonia molecule4 i~ generally between 1 and 30 times the amount (in moles) of the product of the formula (IV).
The deamination can al~o be carried out by simple heating in a liquid medium (thermal deamination), preferably in an inert organic ~olvent medium, for example a halogenated or unhalogenated aromatic hydrocarbon.
According to a fourth preparation proce~ for products of the formula (I), a compound of the hydrazine type of the formula (V) i8 reacted with a compound of the formula ~VI): U~-C(=Wl)-Ar according to the reaction:
~!1 (V) + (VI) _ (I) + UlH + NlH2 the various radicals of the~e formulae (V) and (VI) having the same meanings a~ in the formula (I) and, in addition:
W1 represents an oxygen atom or an NH group, when Wl represents the oxyqen atom, then Ul represents a hydroxyl group [(VI) is thu~ an acid] or alkoxy group t(VI) iB thus an ester] or aroyloxy group t(VI) is thu~ an acid anhydride], or a halogen atom t(VI) i8 thu~ an acid halide], preferably chlorine, when Wl represents an NH group, then U
represents an alkoxy group or alkylthio group or : . . . ~. .: .
- . :
-~5 ' .;
12 ~03~14~
arylalkylthio group.
The preceding reaction i~ effected at a temperature of generally between 20 and 200C, preferably between 50 and 180-C, over a period of 1 to 24 hours. The reactants (V) and (VI) are used in respective molar proportions between 0.8 and 1.2, preferably equal to, or near, 1. The reaction can be effected in the presence or absence of a solvent.
Solvents which can be used, as shown hereinafter in oertain cases, are qolvents which lead to the formation of azeotropic mixtures. Solvents of the alcohol type can also be u~ed when ~he compound of the formula (VI) i8 an imidate, or an aromatic solvent such as a halogenated or unhalogenated hy~rocarbon, or pyridine, when the compound of the formula (VI) is a thioimidate or an acid halide.
~ he light reaction products (U1H and WlH2) are advantageously eliminated a~ the reaction proceeds, generally by distillation when the product in question 20 i8 water or alcohols (U1 thus represent~ a hydroxyl or alkoxy group), and al~o by scavenging wi~h the aid of a tertiary base such a~ triethylamine, when Ul is a halogen ato~, and al80 by scavenging of the ammonia molecule, when Wl i~ NH and Ul is alkoxy (the product of the formula (VI~ is thu an imidate).
The abovementioned di~tillation of the light products can be an azeotropic distillation in the presence of aromatic halogenated or unhalogenated , :~::
" 13 203514~
solvents such a~ pyridine, or the chlorobenzenes, in particular 1,2,4-trichlorobenzene.
The abovementioned ~cavenging of ammonia iR
advantageously effected in the presence of acid~
(preferably carboxylic acids) or of their derivatives such as acid anhydrides or acid halides. These acids or their derivatives are used in a molar amount of generally between 1 and 30 times tha amount of product of the formula (VI) used. These proportions are in the same order of magnitude (mutatis mutandis) when a base i8 used when Ul is a halogen atom.
According to a fifth preparation process for compounds of the formula (I~, a pyridine derivative of the formula (VIII) is reacted with a tetrazole compound of the formula (IX), in which formulae X, Y, Z and Ar have the same meaning as in formula (I) and T
represents a halogen atom, preferably chlorine. The reaction i8 advantageously effected between 20 and l50-C, prsferably in an organic 801vent~ for ex~mple a halogenated or unhalogenated aromatic hydrocarbon such as xylenes, chlorobenzenes or tetralin, or a soivent` of the heterocyclic type such as pyridine.
The invention also relates to novel products which can opt~onelly be u3ed as intermediate~ in the processes according to the invention, characterised in that they have, as their formula, one of th~ formulae (II~ ,- (IV), (VIII), (XI) or (XII) in which the 8ymb01 X~ ~ Z and ~r have the meanings .. . . . . .
: ..... : -i . ... -~ ' ~: ,:- , ., 14 203~
given in the cs~e of the formula (I).
Another ob~ect of the invention is the use of the compound~ of the formu~a (II) as herbiclde~. In what follows, but al~o in the preceding text, the reaction~ which are effected under hot condition~ in a solvent, unless specifically indicated to the contrary, are advantageoucly carried out at the boiling point of the solvent in question.
The preparation of the tetrazoles of the formula (IX) is conveniently effected by reacting an aromatic nitrile of the formula Ar-CN with an alXali metal azide, for example ~odium azide or ammonium azide, at temperature~ between 80 and 130C. Ths molar amount of azide is advantageou~ly between 1 and 3 times (preferably 1.5 and 2 time~) the amount of nitrile.
This reaction is generally effected in a polar solvent such as ~MF or acetic acid or the alcohol~ or their mixtures. Such a reaction i3 described in Advances in Heterocyclic Chemistry, ~ol. 21, page~ 323-435, published in 1977 by Academic Pre~ in an articla by R.N. Butler with the title: Recent advances in tetrazole chemi~try.
The preparation of the arylidene-2-(pyrid-2'-yl)hydrazine~ of the formula (II) is conveniently effected by reacting 2-hydrazinopyridines of the formula (V) with aldehyde~ of the formula Ar-CHO in which the symbol8 X, Y, Z and Ar have the meanings given in the case of the formula (I). The reaction is ,~:'- ' .. ,' .: :
. .
. -:
203~1~4 generally effected at a temperature between 50 and l50~C, preferably in a ~olvent. A lower alcohol such as methanol or ethanol i~ advantagsously used as the solvent. The reaction is promoted by the prei~ence of catalytic amounts of a mineral inorganic or organic acid, for example hydrochloric acid, sulphuric acid, acetic acid, trichloroacetic acid or perchloric acid.
Such a reaction i~ described in Quarterly review, Chemical Society, vol. 23, page~ 37-56, 1969, in an article by J. Buckingham a~ wall a~ in Houben-Weyl, Methoden der organischen Chemie, 4th edition, 1967, vol. X-~, pages 410-487.
The preparation of the 2-(aroylhydrazino)-p~ridine~ of the formula (III) i~ conveni~ntly effected by reacting 2-hydrazinopyridines of the formula (V) with compounds of the formula Ar-CO-U2 in which the ~ymbols X, Y, Z and Ar have the meanings given in the case of the formula (I), and U2 has on~ of the meaning~
given above in the case of Ul. The reaction proceeds in accordance with the equation:
(V~ + Ar-CO-U2 ~ --~(III) + U2H
The reaction i~ generally effected by mixing reactants at a temperature between 0 and 180C, in the pres2nce or absence of a ~olvent. A polar ~olvent i~
advantageously used ai~ solvent.
The following can therefore be cited a~
~- - .. . . , , .
.
.
'~
16 203~
~olvents which can more particularly be u~ed: alcohols when Ar-CO-U2 is not an acid halide; ethers or aliphatic chlorinated or unchlorinated hydrocarbon~ such as methylene chloride, chloroform; ~ol~ents which have acid-scavenging properties, 3uch as pyr~dine, can likewise be used wh~n Ar-CO-U2 repreqent~ an acid halide.
The proportion of the two reactants [that of the formula (V) and that of the formula Ar-CO-U2] can be varied within wide limits around ~toichiometric. When Ar-CO-U2 is an acid ~U2 i~ OH), an excess of the latter derivative i~ u~ed ~n relation to the compound of the formula (Y), for example from 2 to 8 moles per mole of (v). When Ar-CO-U2 i8 an ester (U2 is alkoxy), an approximately sto~chfometric amount of the latter derivative i8 u~ed in relation to the compound of the formula (V), for example from 0.8 to 1.1 moles per mole of (V). When Ar-CO-U2 is an acid halide (U2 is a halogen atom), an exces~ of the compound of the formula (V) i8 used in relation to the compound of the formula Ar-CO-~2, for example from 1 to 5 mole~ per mole of Ar-CO-U2 .
Proces~es which allow tha compounds of the formula (III) to be obtained in accordance with what has ~ust been described are described in the work by Pata~, The chemi~try of carboxylic acids and ester~, ~ol. 5, chapter 9, pages 425-428, publi~hed in 1969 by Interscience/Wiley in an article by Satchell, and also .
- . ' ' .: ~ ' ,~
` ~" 17 203S14~
in Houben-Weyl, Methoden der organischen Chemie, 1952, Vol. VIII, chapter 5, pages 676-680.
The 2-(aroylhydrazino)pyridine~ of the formula (III) can also be prepared conveniently by reacting a pyridine derivative of the formula (VIII) with an aryl hydrazide of the formula Ar-C0-NH-NH2 in which the symbols T, X, Y, Z and Ar have the meanings already given in the case of the formulae (I) and (VIII). The reaction proceed~ in accordance with the e~uation:
(VIII) I Ar-CO-NH-NH2 > (III
,.
This reaction i~ advantageou~ly carried out at a temperature betwoen 50 and 150C, in solvents such a~ alcohols or aromatic solvent~ t for e~ample pyridine or hydrocarbon~ ~uch aY toluen~. The reactants ar~
advantageously in an approximately stoichiometric proportion, for example in a molar ratio ranging from 0.8 to 1.2. The reaction can ~e promoted by the presence o~ a likewi~s approximately stoi~hiometric amount of a basic agent uch aY an alcoholat~ or an alkali metal bicarbonate.
The aryl hydrazide~ of the formula Ar-C0-NH-NH2 can be obtained by reacting hydrazine hydrate with an acid or one of it~ derivative~ such as the e3ters, halide~ or anhydride~. The reaction is advantageou~ly effected at a temperature between 0 and ,, . : ' '''' .; ' , - , . . - , .
18 203S~L4 150~C, preferably in the presence of a ~olvent such as a lower alcohol, the molar proportion of hydrazLne hydrate in relation to the other reactant generally being between 1.01 and 1.5.
Processe~ which allow the aryl hydraz~de~ to be obtained in accordance with what has ~U8t been described are described in the work by Pata~, Th~
chemi~try of amides, vol. 11, chapter 10, pages 515-600, published in 1970 by Interscience/Wiley, in an article by Paulsen and Stoye, and also in Organic Reactions, the Curtius reaction, 1962, Vol. III, chapter 9, pages 366-369 publi~hed by Wiley.
The amidrazone~ of the formula (IV) can be prepared uYing 2-hydrazinopyridin~s of the formula (V) according to the following reaction equations (V) + Ar-C(=NH)-U3 ~ ~ (IV) + U3H~
the various radicals of these reactants and reaction products having the ~ame meaning as in the preceding formulae, and U3 represents a preferably lower alkoxy or alkylthio radical.
~ he reaction is advan~ageously effected a~ a temperature between O and 30~C, preferably in an alcohol-type solvent.
Proce~ses which allow tho amidrazones of the formula (IV) to be obtainsd in accordance with what ha~
~ust been described are described in the work by Pata~, ~' : , . . . .
- : :
-- , . .
.
. . :
.
.~ .. . .
19 203~
The chemi~try of amidines and Lmidates, vol. 20, chapter 10, pages 491-545, published in 1975 by Interscience/Wiley in an article by Watson, a~ well as in an article by Neilson et al., Chemical Review, 1970, Vol. 70, pages 151-170.
The iminoethers of the formula Ar-C(=NH)-U3 in which U3 represents an alkoxy group can be prepared by reacting an aromatic nitrile Ar-CN with a lower alcohol, preferably an alkanol, between -20 and +30C, 10 advantageously in an ether-type solvent, for example ethyl ethsr or 1,2-dimethoxyethane or dioxane, or a halogenated, preferably aliphatic, hydrocarbon such as chloroform. More precisely, the reaction i8 effected in an anhydrous medium in the presence of (gaseous) HCl.
15 Processes which allow these iminoethers of the formula n Ar-C(=NH)-U3 to be obtained are de~cribed in the work by Pata~, The chemistry of amidines and imidates, vol. 20, chapter 9~ page~ 385-489, published in 1975 by Interscience/Wiley in an article by Neilson, as well as : 20 in an article by Roger and ~eilson, Chemical Review, ; 1961, vol. 61, pages 179-211.
~he thioimidates of the formula Ar-Ct=NH)-U3 in which U3 represents an alkylthio group can be prepared by alkylation of arylthiobenzamides by a 25 proc~s such a~ de3cribed by Doyle et al. in Synthesis, 583 (1974). These arylth$obenzamides ~hem~elves can be obtained for example a~ described in the work by Patai, The chemistry of amides, vol. 11, chapter 8, page~
.~ .. . . . .
.
- - ~ ~ .- .. , -. : ~
2r~3s~.~L~ ., 383-475, published in 1970 by Interscience/Wiley, in an article by Walta and Vo~.
The 2-hydrazinopyridine~ of the formula (V) can be obtained by reacting hydrazine hydrate with a 2-halopyridine of the formula (VIII) at a temperaturebetween 0 and 120C, in the presence or absence of a solvent. Solvent~ which may be cited are, in particular, polar ~olvents such as alcohols, pyridine, or dimethyl sulphoxide. The molar amount of hydrazine hydrate is generally between 3 and 15 times the amount of product of the formula (VIII~ used. Processes which allow the compounds of the formula (V) to be obtained in accordance with what has ~u~t been described are described by Enders in Houben-Weyl, Methoden der organischen Chemie, 4th edition, 1967, vol. X-2, chapter 5, pages 252-287.
In particular, the 2-halopyridine~ of the formula (VIII) can be prepared by a proces~ similar to those described by ~linsberg in The Chemistry of Heterocyclic Compounds, Pyridine and its derivative~, part~ I - I~, publi~hed in 1974-1975 by Interscience/Wiley, and by Abramovitch, in The chemistry of ~eterocyclic compounds, Pyridine and its derivatives, supplQments 1 - 5, published in 1960-1964 by Interscience/Wiley.
The following examples, which are given without implied lLmitation, illustrate the invention and show how it can be implemented. In these example~, .~' ' .
2, 203~144 the symbol Ac designates the radical CH3-CO-, the ~ymbol DMF designates dimethylformamide. The word amidrazone de3i~nates compounds which have a group -NH-N= C
Examples 1 to 14 illustrate the preparation of herbic~dal compound~ according to the invan~ion.
Examples I-l to I-10 illustrate the preparation of intermediates of the preceding products.
*Example 1: -Lead tetraacetate (6.7 g; 0.015 mol) are added to phenyl(3'-chloropyrid-2'-yl)hydr~zon~ (3.5 g;
0.015 mol), prepared a~ in Example I-l, in qlacial acetic acid (300 ml) at ambient temp~ratur~ and with stirring. Stirring i~ continued for on~ hour at 60-C.
The medium iB concentrated to dryne~s under reduced presaure. The residua is triturated with water (100 ml), and the mix~ure is filtered, washed with water and dried. 8-Chloro-3-phenyl-s-triazolot4,3-~pyridine ~3.1 g; 0.0135 mol), wh$ch melts at 153-C, iB obtained (yield 90%).
*~xample 2:
A mixture of 3-formylthiophene (2.8 q;
0.025 mol) and 2-hydrazino-3-methylpyridine (3.1 g;
0.025 mol), prepared a~ in Example I-8, in ethanol - : -: . , . ~
22 203~1~4 (30 ml) containing a few drop~ of concentrated HCl, is kept at boiling point for two hours. An ethanolic solution of FeCl3 . 6HzO (70 ml; 0.125 mol) is added gradually, and heating at boiling point is con~i~ued for two hours. The reaction medium i~ concentrated to dryness ur.der reduced pre~sure, the residue is taken up in water (100 ml), the mixture i~ rendered neutral with the aid of gaseou~ NH3 (pH between 8 and 9), and extracted with CH2C12. After the organic phass~ have been concentrated and the residue ha~ been dried and recrystallised u~ing aqueous ethanol, 8-methyl-3-(thien-3'-yl)-~-triazolo[4,3-a]pyridine (6.05 g;
0.02180 mol), which melt~ at 165C, i~ obtained (yield 87%).
*Example 3s Bromine (1.25 ml) in glacial acetic acid (5 ml) i8 added at ambient temperature to a suspen~ion of anhydrou~ sodium acetat2 (6.15 q; 0.075 mol) in : glacial acetic ac$d (50 ml) containing phenyl (3'-20 trifluoromethylpyrid-2'-yl)hydrazone (6.65 g; 0.025 mol) prepared a3 in ~xample I-2. The reaction medium i~
stirred for one hour and poured into an aqueou~
solution of 2N NaOH (300 ml). The precipitate is filtered, wa~hsd with water and dried. 3-Phenyl-8-25 trifluoromethyl-~-triazolot4,3-a]pyridine (4.75 g;
0.018 mol)~ which melts at 197C, is obtained (yield 72%).
,, ' . ~
23 2 o 3 5 1 4 ,~
~ExamPle 4s 2-Formyl-3-methylthiophene (3.15 g;
0.025 mol)~ dissolved in ethanol (20 ml), is added at ambient temperature to a stirred solution of 3-chloro-2-hydrazinopyridine (3.6 g; 0.0~5 mol), prep~red a~ in Example I-7, in ethanol (30 ml) which has been acidified with a little HCl. The mixture i~ heated at boiling point for 2 hour~ and concentrated to dryne~s.
3-Methylthien-2-yl(3'-chloropyrid-2'-yl)hydrazone i8 obtained. This substance i 8 dis301ved in nitrobenzene (50 ml) and oxidi~sd in air by heating at boiling point for 4 hours. The solution i8 concentrated under reduced preQsure. The solid, which ha~ been collected by cooling, i3 solubilised in N HCl (20 ml), and then reprecipitated by neutrali~ation with an ammoniacal solution. 3-(3~-Methylthien-2'-yl)-8-chloro-3-triazolot4,3-a]pyridine (4.45 g; 0.017B mol), which melts at 135DC, is obtained (yield 71%).
*Exam~le 5:
A mixture of 3-methyl-2-(3'-methylthien-2'-oylhydrazino)pyridine (1.25 g; 0.005 mol), prepared as in ~ample I-5, and POC13 (7.65 g) in toluene (25 ml) i~
refluxed for two hours. The reaction medium i8 concentrated, the concentrate i~ taken up in iced water (50 ml), the mixture i~ rendered alkaline (pH betw~en 8 and 9) with thQ aid of an aquQous KHC03 solution, and then extracted with CH2C12. The organic solution is dried o~er NgS0~ and then concentrated. The residue i8 :: ' ,~ ' , . ' ' . ' ': " ' ,~- .
:: . .
~ ~ 3 ~
washed with isopropanol and then dried. 8-Methyl-3-(3'-methylthien-2'-yl)-s-triazolo[4,3-a]pyridino (0.8 g;
0.0035 mol~, which melts at 94C, iR obtained (yield 70%).
*Example_6:
SOCl2 (4.2 g; 0.0425 mol) i8 added dropwise at 0C to a solution of 2-(2'-chlorobenzoylhydrazino)-3-methylpyridine (13.1 ~; 0.05 mol), prepared a~ in Example I-3, in anhydrous pyridine (50 ml). The reaction mixture i~ stirred for one hour at 0UC and thén fil$ered. The in~oluble portion is heated at boiling point for 3 hours in acetonitrile (50 ml~. The 301ution i9 concentrated and the re~idue i~
recryQtallised. 8-Methyl-3-(2'-chlorophenyl)-8-triazolo[4,3-a]pyridine (5.75 g; 0.0235 mol), which melts at 72C, i~ obtained (yield 47%).
*Example 7:
2-(2',4'-DLmethylbenzoylhydrazino)-3-methylpyridine (3.85 g; 0.015 mol), prepared as in Example I-4, is dissolved at ambient temperature in 30 ml of glacial acetic acid.
The reaction mixture i8 kept at boiling point for 12 hours and then evaporated to dryne~s. The residua i~ washed with water and then with pentane and recrystallised from absolut~ ethanol. 8-Nethyl-3-(2',4' dLmethylphenyl)-s-triazolo[4,3-a]pyridine (1.65 g; 0.007 mol), which melts at 106C, is obtained (yield 47%).
' ~ ' - . . , :
- ~
;
25 203~4 ~Example 8:
Nl-(5~-methylpyrid-2~-yl)phenylamidrazone (6.8 ~; 0.03 mol), prepared as in Example I-6, i~
dissolved in formic acid (25 ml). The batch i~ refluxed 5 for one hour, cooled and poured into water (200 ml).
The precipitate is recovered by filtration, washed with water and dried. 3-Phenyl-6-methyl-~-triazolo~4,3-a]-pyridine (4.7 g; 0.0225 mol), which melts at 160CC, is obtained (yield 75%).
10 *Exam~le 9:
A mixture of 2-hydrazino-3-methylpyridine (3.1 g; 0.025 mol), prepared as in Example I-8, and 4-fluorobenzoic acid (3.5 g; 0.025 mol) i~ heated at 180C for 3 hour~ and then cooled and mixed with 15 boiling chloroform (80 ml). The solution is filtered t and the filtrate is concentrated to dryne~. The residue i~ tr~ated with an aqueous ~olution of Na2CO3, filtered, washed with wat~r, dried and recrystallised from methanol. 3-(4'-Fluorophenyl)-8-methyl-~-triazolo-t4,3-a]pyridine (2.3 g; 0.01 mol), which melt~ at 166-C, i~ obtained (yield 40%).
*~xample 10: `
A mixture of 2-hydrazino-3-methylpyTidine (3.1 g; 0.025 mol), prepared as in Example I-8, and -~
picolinic acid (3.1 g; 0.025 mol~ is heated for 4 hours at 180-C, cooled, diluted with the aid of aqueouY
ethanol (100 ml) and rendered alkaline (pH
approximately 8-9) with a solution of dilute NaOH. The .
' .
~ , .
26 203~
precipitate i~ recovered by filtration, wa~hed with water, dried and recry~tallised uslng aqueous ethanol.
8-Methyl-3-(pyrid-2'-yl)-~-triazolo[4,3-a]pyridine (1.0 g; 0.00475 mol), which melt~ at 141C, is obtained (yield 19%).
*Exam~ple 11:
Example 9 i~ repeated but 4-fluorobenzoic acid i~ r~placed by 2-fluorobenzoic acid. 3-(2'-Fluorophenyl)-8-methyl-s-triazolot4,3-a]pyridine (4.1 g; 0.018 mol), which melt~ at 130C, is obtained (yield 72~).
*Example 12s Triethylamine (5.05 g; 0.05 mol) and 2-hydrazino-3-methylpyridine (3.1 g; 0.025 mol), prepared as in Exa~ple I-8, ara added ~ucc2ssively at ambient temperature to a su~p~nsion of ethyl 4-methylbenzimidate chlorohydrate (5 g; 0.025 mol) in ethanol (50 ml). The reaction medium i~ kept at boiling point for one hour and then concentrated, cooled and poured into cold water (250 ml). The mixture i8 extracted with the aid of HCCl3. The organic solution i~ dried and concentrated to dryness. 3-(4'-Ethylphenyl)-8-methyl-s-triazolo[4,3-a]pyridine (3 g; 0.0135 mol), which melts at 145C, i8 obtained (yield 54%).
*Example 13:
Example 2 i~ repeated but the 3-formylthiophene ~2.8 g) is replaced by 4-phenylbenzaldehyde (4.6 g;
0.025 mol). 8-Methyl-3-(4'-phenylphenyl)-s-triazolo-, .
- .;
. ' '-'' ' ' 203~
[4,3-a]pyridine (2.3 g; 0.008 mol), which melts at 156-C, is obtained (yield 32%).
*Example 14:
Example 12 i8 repeated, replacing the ethyl
*Exam~le 5:
A mixture of 3-methyl-2-(3'-methylthien-2'-oylhydrazino)pyridine (1.25 g; 0.005 mol), prepared as in ~ample I-5, and POC13 (7.65 g) in toluene (25 ml) i~
refluxed for two hours. The reaction medium i8 concentrated, the concentrate i~ taken up in iced water (50 ml), the mixture i~ rendered alkaline (pH betw~en 8 and 9) with thQ aid of an aquQous KHC03 solution, and then extracted with CH2C12. The organic solution is dried o~er NgS0~ and then concentrated. The residue i8 :: ' ,~ ' , . ' ' . ' ': " ' ,~- .
:: . .
~ ~ 3 ~
washed with isopropanol and then dried. 8-Methyl-3-(3'-methylthien-2'-yl)-s-triazolo[4,3-a]pyridino (0.8 g;
0.0035 mol~, which melts at 94C, iR obtained (yield 70%).
*Example_6:
SOCl2 (4.2 g; 0.0425 mol) i8 added dropwise at 0C to a solution of 2-(2'-chlorobenzoylhydrazino)-3-methylpyridine (13.1 ~; 0.05 mol), prepared a~ in Example I-3, in anhydrous pyridine (50 ml). The reaction mixture i~ stirred for one hour at 0UC and thén fil$ered. The in~oluble portion is heated at boiling point for 3 hours in acetonitrile (50 ml~. The 301ution i9 concentrated and the re~idue i~
recryQtallised. 8-Methyl-3-(2'-chlorophenyl)-8-triazolo[4,3-a]pyridine (5.75 g; 0.0235 mol), which melts at 72C, i~ obtained (yield 47%).
*Example 7:
2-(2',4'-DLmethylbenzoylhydrazino)-3-methylpyridine (3.85 g; 0.015 mol), prepared as in Example I-4, is dissolved at ambient temperature in 30 ml of glacial acetic acid.
The reaction mixture i8 kept at boiling point for 12 hours and then evaporated to dryne~s. The residua i~ washed with water and then with pentane and recrystallised from absolut~ ethanol. 8-Nethyl-3-(2',4' dLmethylphenyl)-s-triazolo[4,3-a]pyridine (1.65 g; 0.007 mol), which melts at 106C, is obtained (yield 47%).
' ~ ' - . . , :
- ~
;
25 203~4 ~Example 8:
Nl-(5~-methylpyrid-2~-yl)phenylamidrazone (6.8 ~; 0.03 mol), prepared as in Example I-6, i~
dissolved in formic acid (25 ml). The batch i~ refluxed 5 for one hour, cooled and poured into water (200 ml).
The precipitate is recovered by filtration, washed with water and dried. 3-Phenyl-6-methyl-~-triazolo~4,3-a]-pyridine (4.7 g; 0.0225 mol), which melts at 160CC, is obtained (yield 75%).
10 *Exam~le 9:
A mixture of 2-hydrazino-3-methylpyridine (3.1 g; 0.025 mol), prepared as in Example I-8, and 4-fluorobenzoic acid (3.5 g; 0.025 mol) i~ heated at 180C for 3 hour~ and then cooled and mixed with 15 boiling chloroform (80 ml). The solution is filtered t and the filtrate is concentrated to dryne~. The residue i~ tr~ated with an aqueous ~olution of Na2CO3, filtered, washed with wat~r, dried and recrystallised from methanol. 3-(4'-Fluorophenyl)-8-methyl-~-triazolo-t4,3-a]pyridine (2.3 g; 0.01 mol), which melt~ at 166-C, i~ obtained (yield 40%).
*~xample 10: `
A mixture of 2-hydrazino-3-methylpyTidine (3.1 g; 0.025 mol), prepared as in Example I-8, and -~
picolinic acid (3.1 g; 0.025 mol~ is heated for 4 hours at 180-C, cooled, diluted with the aid of aqueouY
ethanol (100 ml) and rendered alkaline (pH
approximately 8-9) with a solution of dilute NaOH. The .
' .
~ , .
26 203~
precipitate i~ recovered by filtration, wa~hed with water, dried and recry~tallised uslng aqueous ethanol.
8-Methyl-3-(pyrid-2'-yl)-~-triazolo[4,3-a]pyridine (1.0 g; 0.00475 mol), which melt~ at 141C, is obtained (yield 19%).
*Exam~ple 11:
Example 9 i~ repeated but 4-fluorobenzoic acid i~ r~placed by 2-fluorobenzoic acid. 3-(2'-Fluorophenyl)-8-methyl-s-triazolot4,3-a]pyridine (4.1 g; 0.018 mol), which melt~ at 130C, is obtained (yield 72~).
*Example 12s Triethylamine (5.05 g; 0.05 mol) and 2-hydrazino-3-methylpyridine (3.1 g; 0.025 mol), prepared as in Exa~ple I-8, ara added ~ucc2ssively at ambient temperature to a su~p~nsion of ethyl 4-methylbenzimidate chlorohydrate (5 g; 0.025 mol) in ethanol (50 ml). The reaction medium i~ kept at boiling point for one hour and then concentrated, cooled and poured into cold water (250 ml). The mixture i8 extracted with the aid of HCCl3. The organic solution i~ dried and concentrated to dryness. 3-(4'-Ethylphenyl)-8-methyl-s-triazolo[4,3-a]pyridine (3 g; 0.0135 mol), which melts at 145C, i8 obtained (yield 54%).
*Example 13:
Example 2 i~ repeated but the 3-formylthiophene ~2.8 g) is replaced by 4-phenylbenzaldehyde (4.6 g;
0.025 mol). 8-Methyl-3-(4'-phenylphenyl)-s-triazolo-, .
- .;
. ' '-'' ' ' 203~
[4,3-a]pyridine (2.3 g; 0.008 mol), which melts at 156-C, is obtained (yield 32%).
*Example 14:
Example 12 i8 repeated, replacing the ethyl
4-methylbenzimidate chlorohydrate by methyl benzimidate chlorohydrate. 3-Phenyl-8-methyl-s-triazolo[4,3-a]-pyridine (3.5 g; 0.0168 mol), which melts at 118C, is obtained (yield 67%).
*Example 15:
Example 4 i8 repeated but replacings 1) the 2-formyl-3-methylthiophene (3.15 g) by 4-methylthiobenzaldehyde (4.00 g; 0.025 mol), and 2) 3-chloro-2-hydrazinopyridine (3.6 g) by 2-hydrazino-3-methylpyridine (3.1 g; 0.0~5 mol ) . 4-Methylthiophenyl (3'-methylpyrid-2'-yl)hydrazone ~8 obtained and dissolved in nitrobenzene (50 ml), and then treated as in Example 4. 3'-(4'-Methylth~ophenyl)-8-methyl ~-triazolot4,3-a]pyridine (4.60 g; 0.018 mol), which melts at 137C, i~ obtzined (yield~ 72%).
*Ex~mpl~ 16~
2-Foxmylthiazole (2.0 g; 0.018 mol) di~301ved ; in ethanol (20 ml) is added with stirring at ambient temperature to a solution of 3-chloro~2-hydrazinopyridine (2.4 g; 0.018 mol), prepared as in ~xamplo I-~, in ethanol (30 ml) which contdins p-toluenesulphonic acid (0.2 g). The mixture iB heated at boiling point for 2 hours and evaporated to drynes~.
Thiazol-2-yl(3'-chloropyrld-2'-yl)hydrazone is ....... .
. : ~
- :. .
- - ' ' :' .
203~
obtained. This substance is dixsolved in ethanol (50 ml). Chloramine T (5.1 g; 0.018 mol) i~ added rapidly at ambient temperature to the preceding ethanolic solution. The reaction medium i8 stirred for 30 minute~. After the ~olvent ha~ been evaporated, the re~idue i~ chromatographed (eluent heptane/ethyl acetste 40J60). 3-(Thiazol-2~-yl)-8-chloro-s-triaz~lo[4,3-a]pyridine (1.50 g; 0.0063 mol), which melts at 218C, i3 obtained (yield 36~).
~Example 17:
Example 16 i8 repeated but the 3-chloro-2-hydrazinopyridine i~ replaced by 2-hydrazino-3-methylpyridine (prepared a~ in Example I-8).
3-(Thiazol-2'-yl)-8-methyl-s-triazolo~4,3-a]pyridine (1.26 g; 0.0058 mol), which melts at 140C, i8 obtained (yield 32%).
*Example 18:
Example 17 i3 repeated but the 2-formylthiaZOlQ i8 replaced by 4-phenoxybenzaldehyde.
3-(4'-Phenoxyphenyl)-8-methyl-~-triazolo[4,3-a]pyridine (4.7 g; 0.0156 mol), which melts at 132~C, i~ obtained ~yield 87%).
*Example 19:
Example 16 i8 repeated but the 2-formylthiazole i~ replaced by 4-phenoxybenzaldehyde. 3-(4'-Phenoxyphenyl)-8-chloro-s-triazolo[4,3-a]pyridine (5.0 g; 0.0155 mol), which melts at 145-C, is obtained (yield 86%).
. . ~ ,. ................................... .
- ' ` 203~144 ~Example 20:
Example 5 i~ repeated but the 3-methyl-2-(3'-methylthien~2~-oylhydrazino)pyridine i8 replaced by 3-methyl-2-(4~-methy~ 2~3~-thiadiazol-5~-oylhydrazino)pyridine. 3-(4'-Methyl-1',2',3'-thiadiazol-5-yl)-8-methyl-~-triazolot4,3-a]pyridine (0.3 g; 0.0013 mol), which melt~ at lBO~C, i~ obtained (yield 26%).
To obtain the compounds of the following sxample~, one of Examples 4 or 5 i8 repeateds *Example ?l 8-Bromo-3-(3'-methylthien-2'-yl)-8-triazolo[4,3-a]pyridine, ~ :
*Example 22 8-trifluoromethyl-3-~3'-methylthien-2'-yl)-s- ~ `
triazolot4,3-a]pyridine, xample ?3 8-methyl-3-(2'-methylthien-2'-yl~
triazolol4,3-a]pyridine~
*Ex2mple_23 8-methyl-3-(2-methylthien-2'-yl) 8-triazolo[4,3,-a~pyridine, *Example 24 8-bromo-3-phenyl-s-triazolo[4,3-a]pyridine, .
*Example 25 B-chloro-3-(2'-methylthien-3'-yl)-~-triazolot4,3-a]pyridine, - ~ .
203~
Example 26 8-chloro-3-(thien-3'-yl)-s-triazolo[4,3-a]-pyridine, *Example 27 8-methyl-3-(1'-methylpyrrol-2~-yl)-8-triazolo[4,3-a]pyridine, Example 28 8-chloro-3-(3~,5'-dLmethylthien-2'-yl)-~-triazolo[4,3-a]pyridine, ~Example 29 7,8-dimethyl-3-phenyl-s-triazolo[4r3-a]
pyridino, Example 30 8-methyl-3-(3',5'-dimethylthièn-2~-yl)-s-triazolot4,3-a]pyridine, *Example 31 8-ethyl-3-(3~-methylthien-2~-yl)-s-triazolot4,3-a]pyridine, .-*Example 32 8-ethyl-3-phenyl-s-triazolo[4,3-a]pyridine, *Example 33 8-ethyl-3-(1'-methylpyrrol-2~-yl) -8-triazolot4,3-a]pyridine, *~xampla.34 8-ethyl-3-(thien-3~-yl)-~-triazolo[4~3-a]
pyridine, *Example 35 8-trifluoromethyl-3~ -methylpyrrol-2~-yl)-.:., . :., .; ,:: . ~
.~ . i ., . : . - ~ .
_ 31 ~0 3 ~14 ~
s-triazolo[4,3-a]pyridine, Example 36 8-trifluoromethyl-3-(pyrrol-2'-yl~-8-triazolo[4,3-a~pyridine, *Example 37 8-chloro-3-(4~-methylthien-2~-yl)-s-triazolo[4,3-a]pyridine, *Example 38 7,8-dLmethyl-3-(3'-methylthien-2'-yl)-s-triazolot4,3-a]pyridine, ,i *Example ~9 ;
8-methyl-3-(4'-methylthien-2'-yl)~
triazolot4,3-a]pyridine, ~: -*ExamplQ 40 8-trifluoromethyl-3-(thien-3'-yl)-s- t triazolot4,3-a~pyridine~
*Example 41 8-methyl-3-(4~ opropylphenyl) triazolot4,3-a]pyridine, *Example 42 ~ 8-methyl-3-(4'-bromothien-2'-yl)-8-triazolot4,3-a]pyridine, *Example 43 8-chloro-3-(4~-bromothien-2~-yl)-~-triazolot4,3-a]pyridine, Example 44 8-methyl-3-(3'-chlorothien-2'-yl)-8-triazolot4,3-alpyridine, .
- .
' ' ' ~ , ' ~ . ' :. "'" ' : -: - -.
: . .
32 203~
~_xample 45 8-chloro-3-(3~-chlorothien-2'-yl)-8-triazolo[4,3-a]pyridine, ~Example 46 8-methyl-3-~3'-bromothien-2'yl)-~-triazolo[4,3-a]pyridine, xample 4?
8-chloro-3-(3'-bromothien-2'-yl)-s-triazolo[4,3-alpyridine, The above products are obtained in accordance with the methods described in ~xamples 4 and 5.
Example I-1:
Banzaldehyde (5.35 g; 0.05 mol) in ethanol (29 ml) is added with stirring and at ambient temperature to a solut~on of 3-chloro-2-hydrazinopyridine (7.2 g; 0.05 mol~ in ethanol (30 ml which contains a few drops of concentrated HCl. The batch is refluxed for two hours and then concentrated.
After the mixturs ha cooled, the solid re~idue i8 recovered by filtxation, dried and recrystalli~ed from ~hanol. Phenyl (3'-chloropyrid-2'-yl)hydrazone (10.45 g; 0.045 mol), which malt~ at l51~C, i~ obtained (yield 91%~.
*Example I-2s Benzaldehyde (5.35 g; 0.05 mol) in ethanol (20 ml) i8 added to a 301ution of 3rtrifluoromethyl-2-hydrazinopyridine (13.25 g; 0.05 mol~, prepared as in Example I-9, in ethanol (30 ml) which contain~ acetic . . .
.: ~ . - '' . . , . - ~ . .
. .
203~
acid (0.3 ml). The mixtur~ i~ refluxed for 2 hours, concentrated, cooled and diluted with water (S ml). The precipitste i~ recovered by filtration and dried.
Phenyl (3'-trifluoromethylpyrid-2'-yl)-hydrazone (11.15 g; 0.04~ mol), which metl~ at 119C, is obtained (yield 84%).
*Example I-3:
2-Chlorobenzoyl chloride (8.75 g; 0.05 mol) are added 810wly and at the temperature of the ico-bath to 3-methyl-2-hydrazinopyridine (6.15 g; 0.05 mol), prepared a3 in Example 1-8, in anhydrous pyridine (50 ml). The reaction mixture is stirred for 4 hours at ambient temperature and then poured into iced-water (100 ml). After ths mixture ha~ been allowed to stand 15 for 12 hours at O~C, it is filtered and the precipitate `~
is washed with water, dried and recrystallised using aqueous ethanol. 2-(2'-Chlorobenzoylhydrazino)-3-methylpyr~dine tlO.45 g; 0.04 mol), which melts at ; 115C, is obtainQd (yield 80%).
*Example I-4s 2,4-Dimethylbenzoyl chloride (8.45 g;
0.05 mol) are added slowly at O-C to 3-methyl-2-hydrazinopyridine (6.15 g; 0.05 mol), prepared as in Example I-8, in CH2~12 (200 ml) containing triethylamine (5.5 g; 0.055 mol). The reaction mixture is refluxed for 3 hour~, cooled, and filtered, and the filtrate is concentrated. Tha residu~ i~ wa~hed with water, dried and recry~tallised u~ing aqueous ethanol. 2-(2',4'-. . .
. :
34 20351~
and recrystalli~ed u~ing aqueou~ ethanol. 2-(2~,4~-Dimethylbenzoylhydrazino)-3-methylpyridine (9.45 g;
0.037 mol~, which melts at 120C, i8 ohtained (yield 74%).
*Example_I-5:
A mixture of methyl 3-methylthien-2-yl carboxylate t3.9 g; 0.025 mol) and 2-hydrazino-3-methylpyridine (3.1 g; 0.025 mol), prepared as in Example I-8, is heated in n-butanol ~30 ml) for 6 hours at boiling point. ~he mixture is concentrated to drynes~ and recrystallised from tolusne. 3-Methyl-2-(3'-methylthien-2'-oylhydrazino)pyridine (5.7 g;
0.023 mol), which melts at 196-C, is obtained (yield *Example I-6:
Methyl benzimidate chlorohydrate (12 g;
0.07 mol) i8 added at ambient temperature to a solution of 2-hydrazino-5-methylpyridine (8.65 g; 0.07 mol), prepared a in Example I-10, in a mixture of absolute ethanol (150 ml) and triethylamine (7.1 g; 0.07 mol).
The batch i8 ~tirred for 24 hour~ at ambient temperature. The precipitate is recovered by f~ltration, washad with ethanol and ~hen dried. Nl-(5'-methylpyrid-2'-yl)phenylamidrazone (9.95 g; 0.044 mol), which melts at a temperaturs around 166C, i~ obtained (yield 63%).
*Example I-7:
85% hydrazine (125 ml) is added 510wly and a~
., - , ~ , , , ,~
.~ . . : . . , .
203~44 ambient temperature to a solution of 2,3-dichloropyridine (74 g; 0.5 mol) in ethanol (400 ml). The reaction mixture i8 kept at boiling point for 24 hours and then cooled to O~C. The ~olid precipitate i~ recovered by filtration and recry~talli~ed us;ng ethanol.
2-Hydrazino-3-chloropyridine (66.05 g; 0.46 mol), which melt~ at 16~C, i~ obtained (yield 92%).
Example I-8:
A mixtur~ of 2-bromo-3-methylpyridine (51.6 g; 0.3 mol) and 85% hydrazine (110 ml) is kept at boilin~ point for 20 hour~. After the mixture ha~
returned to ambient temperature, the precipitate i8 recovered by filtration, washed with i~opropyl ether and solubilised in CH2Cl2. The organic ~olution i~
filtered and evaporated to dryne~. 2-Hydrazino-3-methylpyridine (26.45 g; 0.215 mol), which melts at ; 122-C, i~ obtained (yield 71%J.
*Example I-5:
Example I-8 is repeated, but the 2-bromo-3-methylpyridine (51.6 g) is replaced by 2-chloro-3 trifluoromethylpyridine (54.45 g), and the mixture i~
heated for 24 hours. 2-Hydrazino-3-trifluoromethyl-pyridine (34.55 g; O.l9S mol), which melts at 63~C, i8 obtained (yield 65%).
*Example I-lOs Exampla I-8 i~ repeated, but the 2-bromo-3-methylpyridine i~ replaced by the ~ame amount of 2-bromo-5-methylpyridine. 2-Hydrazino-5-methylpyridine ,. , , . . ~ . -.
~ - . - ~. . ' ' :
~ , . . .
36 203~4 (yield 58~).
The example~ hereinafter, which are givan without implied lLmitation, illu~trate the use of the products according to the invention and their application in weeding. In these examples, the following abbreviations are used:
: . . . . . ~ . . , ' . ' ."' -' ;' ' ' 20351~4 ~ _ Abbrevia- Engli~h name of Latin name tions weed~
~ .. _
*Example 15:
Example 4 i8 repeated but replacings 1) the 2-formyl-3-methylthiophene (3.15 g) by 4-methylthiobenzaldehyde (4.00 g; 0.025 mol), and 2) 3-chloro-2-hydrazinopyridine (3.6 g) by 2-hydrazino-3-methylpyridine (3.1 g; 0.0~5 mol ) . 4-Methylthiophenyl (3'-methylpyrid-2'-yl)hydrazone ~8 obtained and dissolved in nitrobenzene (50 ml), and then treated as in Example 4. 3'-(4'-Methylth~ophenyl)-8-methyl ~-triazolot4,3-a]pyridine (4.60 g; 0.018 mol), which melts at 137C, i~ obtzined (yield~ 72%).
*Ex~mpl~ 16~
2-Foxmylthiazole (2.0 g; 0.018 mol) di~301ved ; in ethanol (20 ml) is added with stirring at ambient temperature to a solution of 3-chloro~2-hydrazinopyridine (2.4 g; 0.018 mol), prepared as in ~xamplo I-~, in ethanol (30 ml) which contdins p-toluenesulphonic acid (0.2 g). The mixture iB heated at boiling point for 2 hours and evaporated to drynes~.
Thiazol-2-yl(3'-chloropyrld-2'-yl)hydrazone is ....... .
. : ~
- :. .
- - ' ' :' .
203~
obtained. This substance is dixsolved in ethanol (50 ml). Chloramine T (5.1 g; 0.018 mol) i~ added rapidly at ambient temperature to the preceding ethanolic solution. The reaction medium i8 stirred for 30 minute~. After the ~olvent ha~ been evaporated, the re~idue i~ chromatographed (eluent heptane/ethyl acetste 40J60). 3-(Thiazol-2~-yl)-8-chloro-s-triaz~lo[4,3-a]pyridine (1.50 g; 0.0063 mol), which melts at 218C, i3 obtained (yield 36~).
~Example 17:
Example 16 i8 repeated but the 3-chloro-2-hydrazinopyridine i~ replaced by 2-hydrazino-3-methylpyridine (prepared a~ in Example I-8).
3-(Thiazol-2'-yl)-8-methyl-s-triazolo~4,3-a]pyridine (1.26 g; 0.0058 mol), which melts at 140C, i8 obtained (yield 32%).
*Example 18:
Example 17 i3 repeated but the 2-formylthiaZOlQ i8 replaced by 4-phenoxybenzaldehyde.
3-(4'-Phenoxyphenyl)-8-methyl-~-triazolo[4,3-a]pyridine (4.7 g; 0.0156 mol), which melts at 132~C, i~ obtained ~yield 87%).
*Example 19:
Example 16 i8 repeated but the 2-formylthiazole i~ replaced by 4-phenoxybenzaldehyde. 3-(4'-Phenoxyphenyl)-8-chloro-s-triazolo[4,3-a]pyridine (5.0 g; 0.0155 mol), which melts at 145-C, is obtained (yield 86%).
. . ~ ,. ................................... .
- ' ` 203~144 ~Example 20:
Example 5 i~ repeated but the 3-methyl-2-(3'-methylthien~2~-oylhydrazino)pyridine i8 replaced by 3-methyl-2-(4~-methy~ 2~3~-thiadiazol-5~-oylhydrazino)pyridine. 3-(4'-Methyl-1',2',3'-thiadiazol-5-yl)-8-methyl-~-triazolot4,3-a]pyridine (0.3 g; 0.0013 mol), which melt~ at lBO~C, i~ obtained (yield 26%).
To obtain the compounds of the following sxample~, one of Examples 4 or 5 i8 repeateds *Example ?l 8-Bromo-3-(3'-methylthien-2'-yl)-8-triazolo[4,3-a]pyridine, ~ :
*Example 22 8-trifluoromethyl-3-~3'-methylthien-2'-yl)-s- ~ `
triazolot4,3-a]pyridine, xample ?3 8-methyl-3-(2'-methylthien-2'-yl~
triazolol4,3-a]pyridine~
*Ex2mple_23 8-methyl-3-(2-methylthien-2'-yl) 8-triazolo[4,3,-a~pyridine, *Example 24 8-bromo-3-phenyl-s-triazolo[4,3-a]pyridine, .
*Example 25 B-chloro-3-(2'-methylthien-3'-yl)-~-triazolot4,3-a]pyridine, - ~ .
203~
Example 26 8-chloro-3-(thien-3'-yl)-s-triazolo[4,3-a]-pyridine, *Example 27 8-methyl-3-(1'-methylpyrrol-2~-yl)-8-triazolo[4,3-a]pyridine, Example 28 8-chloro-3-(3~,5'-dLmethylthien-2'-yl)-~-triazolo[4,3-a]pyridine, ~Example 29 7,8-dimethyl-3-phenyl-s-triazolo[4r3-a]
pyridino, Example 30 8-methyl-3-(3',5'-dimethylthièn-2~-yl)-s-triazolot4,3-a]pyridine, *Example 31 8-ethyl-3-(3~-methylthien-2~-yl)-s-triazolot4,3-a]pyridine, .-*Example 32 8-ethyl-3-phenyl-s-triazolo[4,3-a]pyridine, *Example 33 8-ethyl-3-(1'-methylpyrrol-2~-yl) -8-triazolot4,3-a]pyridine, *~xampla.34 8-ethyl-3-(thien-3~-yl)-~-triazolo[4~3-a]
pyridine, *Example 35 8-trifluoromethyl-3~ -methylpyrrol-2~-yl)-.:., . :., .; ,:: . ~
.~ . i ., . : . - ~ .
_ 31 ~0 3 ~14 ~
s-triazolo[4,3-a]pyridine, Example 36 8-trifluoromethyl-3-(pyrrol-2'-yl~-8-triazolo[4,3-a~pyridine, *Example 37 8-chloro-3-(4~-methylthien-2~-yl)-s-triazolo[4,3-a]pyridine, *Example 38 7,8-dLmethyl-3-(3'-methylthien-2'-yl)-s-triazolot4,3-a]pyridine, ,i *Example ~9 ;
8-methyl-3-(4'-methylthien-2'-yl)~
triazolot4,3-a]pyridine, ~: -*ExamplQ 40 8-trifluoromethyl-3-(thien-3'-yl)-s- t triazolot4,3-a~pyridine~
*Example 41 8-methyl-3-(4~ opropylphenyl) triazolot4,3-a]pyridine, *Example 42 ~ 8-methyl-3-(4'-bromothien-2'-yl)-8-triazolot4,3-a]pyridine, *Example 43 8-chloro-3-(4~-bromothien-2~-yl)-~-triazolot4,3-a]pyridine, Example 44 8-methyl-3-(3'-chlorothien-2'-yl)-8-triazolot4,3-alpyridine, .
- .
' ' ' ~ , ' ~ . ' :. "'" ' : -: - -.
: . .
32 203~
~_xample 45 8-chloro-3-(3~-chlorothien-2'-yl)-8-triazolo[4,3-a]pyridine, ~Example 46 8-methyl-3-~3'-bromothien-2'yl)-~-triazolo[4,3-a]pyridine, xample 4?
8-chloro-3-(3'-bromothien-2'-yl)-s-triazolo[4,3-alpyridine, The above products are obtained in accordance with the methods described in ~xamples 4 and 5.
Example I-1:
Banzaldehyde (5.35 g; 0.05 mol) in ethanol (29 ml) is added with stirring and at ambient temperature to a solut~on of 3-chloro-2-hydrazinopyridine (7.2 g; 0.05 mol~ in ethanol (30 ml which contains a few drops of concentrated HCl. The batch is refluxed for two hours and then concentrated.
After the mixturs ha cooled, the solid re~idue i8 recovered by filtxation, dried and recrystalli~ed from ~hanol. Phenyl (3'-chloropyrid-2'-yl)hydrazone (10.45 g; 0.045 mol), which malt~ at l51~C, i~ obtained (yield 91%~.
*Example I-2s Benzaldehyde (5.35 g; 0.05 mol) in ethanol (20 ml) i8 added to a 301ution of 3rtrifluoromethyl-2-hydrazinopyridine (13.25 g; 0.05 mol~, prepared as in Example I-9, in ethanol (30 ml) which contain~ acetic . . .
.: ~ . - '' . . , . - ~ . .
. .
203~
acid (0.3 ml). The mixtur~ i~ refluxed for 2 hours, concentrated, cooled and diluted with water (S ml). The precipitste i~ recovered by filtration and dried.
Phenyl (3'-trifluoromethylpyrid-2'-yl)-hydrazone (11.15 g; 0.04~ mol), which metl~ at 119C, is obtained (yield 84%).
*Example I-3:
2-Chlorobenzoyl chloride (8.75 g; 0.05 mol) are added 810wly and at the temperature of the ico-bath to 3-methyl-2-hydrazinopyridine (6.15 g; 0.05 mol), prepared a3 in Example 1-8, in anhydrous pyridine (50 ml). The reaction mixture is stirred for 4 hours at ambient temperature and then poured into iced-water (100 ml). After ths mixture ha~ been allowed to stand 15 for 12 hours at O~C, it is filtered and the precipitate `~
is washed with water, dried and recrystallised using aqueous ethanol. 2-(2'-Chlorobenzoylhydrazino)-3-methylpyr~dine tlO.45 g; 0.04 mol), which melts at ; 115C, is obtainQd (yield 80%).
*Example I-4s 2,4-Dimethylbenzoyl chloride (8.45 g;
0.05 mol) are added slowly at O-C to 3-methyl-2-hydrazinopyridine (6.15 g; 0.05 mol), prepared as in Example I-8, in CH2~12 (200 ml) containing triethylamine (5.5 g; 0.055 mol). The reaction mixture is refluxed for 3 hour~, cooled, and filtered, and the filtrate is concentrated. Tha residu~ i~ wa~hed with water, dried and recry~tallised u~ing aqueous ethanol. 2-(2',4'-. . .
. :
34 20351~
and recrystalli~ed u~ing aqueou~ ethanol. 2-(2~,4~-Dimethylbenzoylhydrazino)-3-methylpyridine (9.45 g;
0.037 mol~, which melts at 120C, i8 ohtained (yield 74%).
*Example_I-5:
A mixture of methyl 3-methylthien-2-yl carboxylate t3.9 g; 0.025 mol) and 2-hydrazino-3-methylpyridine (3.1 g; 0.025 mol), prepared as in Example I-8, is heated in n-butanol ~30 ml) for 6 hours at boiling point. ~he mixture is concentrated to drynes~ and recrystallised from tolusne. 3-Methyl-2-(3'-methylthien-2'-oylhydrazino)pyridine (5.7 g;
0.023 mol), which melts at 196-C, is obtained (yield *Example I-6:
Methyl benzimidate chlorohydrate (12 g;
0.07 mol) i8 added at ambient temperature to a solution of 2-hydrazino-5-methylpyridine (8.65 g; 0.07 mol), prepared a in Example I-10, in a mixture of absolute ethanol (150 ml) and triethylamine (7.1 g; 0.07 mol).
The batch i8 ~tirred for 24 hour~ at ambient temperature. The precipitate is recovered by f~ltration, washad with ethanol and ~hen dried. Nl-(5'-methylpyrid-2'-yl)phenylamidrazone (9.95 g; 0.044 mol), which melts at a temperaturs around 166C, i~ obtained (yield 63%).
*Example I-7:
85% hydrazine (125 ml) is added 510wly and a~
., - , ~ , , , ,~
.~ . . : . . , .
203~44 ambient temperature to a solution of 2,3-dichloropyridine (74 g; 0.5 mol) in ethanol (400 ml). The reaction mixture i8 kept at boiling point for 24 hours and then cooled to O~C. The ~olid precipitate i~ recovered by filtration and recry~talli~ed us;ng ethanol.
2-Hydrazino-3-chloropyridine (66.05 g; 0.46 mol), which melt~ at 16~C, i~ obtained (yield 92%).
Example I-8:
A mixtur~ of 2-bromo-3-methylpyridine (51.6 g; 0.3 mol) and 85% hydrazine (110 ml) is kept at boilin~ point for 20 hour~. After the mixture ha~
returned to ambient temperature, the precipitate i8 recovered by filtration, washed with i~opropyl ether and solubilised in CH2Cl2. The organic ~olution i~
filtered and evaporated to dryne~. 2-Hydrazino-3-methylpyridine (26.45 g; 0.215 mol), which melts at ; 122-C, i~ obtained (yield 71%J.
*Example I-5:
Example I-8 is repeated, but the 2-bromo-3-methylpyridine (51.6 g) is replaced by 2-chloro-3 trifluoromethylpyridine (54.45 g), and the mixture i~
heated for 24 hours. 2-Hydrazino-3-trifluoromethyl-pyridine (34.55 g; O.l9S mol), which melts at 63~C, i8 obtained (yield 65%).
*Example I-lOs Exampla I-8 i~ repeated, but the 2-bromo-3-methylpyridine i~ replaced by the ~ame amount of 2-bromo-5-methylpyridine. 2-Hydrazino-5-methylpyridine ,. , , . . ~ . -.
~ - . - ~. . ' ' :
~ , . . .
36 203~4 (yield 58~).
The example~ hereinafter, which are givan without implied lLmitation, illu~trate the use of the products according to the invention and their application in weeding. In these examples, the following abbreviations are used:
: . . . . . ~ . . , ' . ' ."' -' ;' ' ' 20351~4 ~ _ Abbrevia- Engli~h name of Latin name tions weed~
~ .. _
5 AVE Wild oat Avena fatua . _ _ ECH Japanese millet Echinochloa cru~-galli ._ .
CHR Corn marigold Chrysanthemum 3egetum 10 POR Common purslane Portulaca oleracea . _ . _ .
DIG Hairy finger gra~s Digitaria sanguinali~
SIN Nhite mustard Sinapi3 alba . _ . I
ALO Black grass Alopecuru~
~yo~uroide~
. , . .
IPO China ~ute Ipomea purpurea .
ABU Black nightshade Abutilon theophrasti SOL Common chickweed Solanum nigrum .. , 20 STE Stitchwort Stellaria media, .
CEN Cornflower Centaurea cyanu3 . _ .. .__ . -SES Hemp ~esbania Sesbania exaltata SET Faber's foxtail Setaria faberii CHY - Corn marLgold Chrysanthemum . segetum ,~ , , : - . .
' 203~14~
3~
. ____. ~ .. . _ Abbrevia- Engli~h name of Latin name tions weeds . _ _ _ ... ... __ . ., S RZ Wheat Triti~um ae~tivum ZEA Maize Zea May~
.. _ _ I
ORY Rice Oryza sativa _ Soya Glycine maximum GOS Cotton Gossypium hlr~utum 10 HE~ Sunflower Helianthu~ annuus BRS Oilsaed rape Brassica napus Example Vl:
Herbicidal application before emergence of the plant t 15 species.
A number of eeds selected as a function of the plant specie~ and the ~ize of the seed is sown in 7 x 7 x 8 cm pots filled with light agricultural 80il.
The pot~ are treated by spraying them with a 20 mixture in an amount which corresponds to an application rata of 500 l/ha and which contains the active ingredient at the desired concentration.
The seeds which are not covered by 80il are thus treated with the mixture tthe term mixture is used 25 to designate generally compositions which ar~ diluted with water, such as are applied to the plants).
The mixture used for the treatment i5 a ,. . . . .
- :~
. . - ., . : ,. .
,.~ ;. :
.~ , 203~
solution or suspension of the active in~redient in an acetone/water mixture in the ratio of 50/50, in the presencQ of 0.05% by weight of Cemul~ol NP 10 (surfactant) which is composed of a polyethoxyl~ted S alkylphenol, in particular 8 polyethoxylated nonylphenol) and 0.04% by weight of Tween 20 (surfactant composed of an oleate of a derivatiYe of a polycondensate of ethylene oxide with sorbitol).
In the case of a suspen~ion~ the latter is obtained by mixing and grinding the ingredients in a microniser in such a way a~ to obtain an averags particle ~ize of less than 40 micron~.
After the treatment, the ~eed~ are covered by a layer of soil about 3 mm in thicknes3.
The pot8 are then placed in containers for receiving the watering water, by way of ~ubirrigation, and maintained for 24 hour~ at ambient temperature and 60% relative humidity.
After 24 days, a de3truction percentage (D) of the plants in the treated pot is determined in relation to the number of plants in the untreated pots (controls). On the remaining treated plants, the size reduction percentage (SR) i8 measured in relation to the control plants.
The percentage of foliar volume destroyed and reduced by the product i8 therefore given by the formula ~ ~ 3 ~
D + SR (100 - D) = A
This value A i~ transformed into a key from O
to 5 ac~ording to the following gradations Rey O ~ A < 10 0 no effect 10 < A < 30 30 ~ A ~ 50 2 50 < A < 70 3 70 ~ A < 90 4 90 < A ~ 100 5 complete de~truction.
.
~ : : ?
.:
.. : ~ .
... : , . .. .
:: ~ , , ': ..
~. ~ : . - -: :
20351~
The result~ obtained are given hereinafter:
Compound accor- 6 2 10 3 5 1 ding to Ex.No. . ¦ .
5 (applied at a .
dosage rate of 4 kg/ha) ~ ~ - _ _ _ Pre-emergence .
activity A
_ _ _ _ _ DIG 5 5 5 3 5 5 5 5 5 5 ff~-_ _ __ A~U 4 5 5 5 5 4 3 5 5 5 ,. . .
, ^" 203S1 ~4 PRE-EMERGENCE ACTIVITY
EXAMPLES ¦ ECH ¦ ALO ¦ DIG SIN ABU j SOL ¦ STE ¦
._-- 1- l _ _ ~i 1 1 65 - 5 ---- -5 5 -- 5 5 5 ~ .... . _ 20 4 5 5_ 5 5 5 5 I
23 3 4 5 1 _5_ __5 _ l~i 33 5 5 5 5 5 5 5 34 5 5 ' 5 5 5 . _ . _ . .
39 3 5 5 1 0 5 ~i , -I
..... _ 1- -' i -- , 2a . .
'' , . :- . ~ : ..
~ ~' ' . . . -.
.
.:. . . : : . .
203~
_ .. _ PRE-EMERGENCE ACTIVITIES
CROPS
EXAY- DOS- _ . _ _ _ PLES ARGEE
Xg/ha E~RS GOS GLX S SL TRZ Z SA ORY
27 2 ~ 0 0 1 0 0 .
. .:
- : -, ~ -, .:: , 2 0 3 ~ ~ 4 '~
_~ PRE-EMERGENCE ACTIVITIES
WEEDS
S E~ DOS-PLES ARAEE
kg/h~ STE CHY SOL DIG SET
~. . -, :
. ' ~' . ~ ' ' 20351~
_ . .
PRE-EMERGENCE ACTIVITIES
CROPS WEEDS
, . .. .. . __ EXAM- DOS- i 5 ¦ PL S ¦ RA rE
kg~ha GLX TRZ ZEA STE AE~U SOL DIG
. _ l _ 32 2 O t) O O 5 1 4 4 . 43 4 1 O 1 _ 5 5 5I 5 - - . - . . :
~: . - .:- ....... - , - :
-: - - ~
:
203~144 Compound according to Ex.No 5 1 12 Applied at a dosage rate of 5 (kg/ha) 2 1 4 Pre-emergence activity A
_ _ GOS 0 _ HE~ 0 3 2 __ , ..
ORY 1 0 0 ;
E amples which follow:
These examples show that, pre-emergence, the products according to the invention have a good general activity against the weed~ and a good ~electivity toward~ one or more crops ~uch as wheat, maize, rice, cotton, ~unflower, ~oya and oilseed rape.
, .~ . . .~ .
:. . .
47 20351~
Examp~~ U2 Herbiçidal apDlication after emer ence of the ~lant species A number of seeds selected as a function of the plant specie~ and the size of the seed i8 sown in 7 x 7 x 8 cm pots filled w~th light agricultural soil.
The seeds are then covered by a layer of 80il of about 3 mm in thickness and the seed i8 allowed to germinate until it give~ ri~e to a plantlet in a suitable stage. In the case of tha Gramineae, the treatment st~ge is the ~formation of second leaf~
stags. In the case of the dicotyledon3, the treatment StagQ i8 the "cotyledons unfolded, first true leaf being developed~ stage.
The pota are then treated by spraying ~hem with a mixture in an amount which corresponds to an application rate cf 500 l~h~ and which contain~ the active ingredient at the desired ~oncentration.
The mixtuxe used for the treatment is prepared a~ in Example Ul.
After the treatment, the seeds are covered by a soil layer of about 3 mm in thickness.
The potA are then placed in containers for receiving the watering water, by way of subirrigation, and maintained for 24 days at ambient tempera~ure and 60% relative humidity.
A (pexcentage of destroyed foliage volume) is measured as in Example U~.
. ,: - ,. : : -48 2V351~4 The resul~s obta:Lned are given hereinafters _ 6 1~ 4~ 3 1 5~ 13--Compound in accordance 5 with Ex.No.
(applied at a dosage rate of 1 , 4 kg/ha) . 1 ~ ¦
. . _ . _ _ . i i 10 Post-emergence activity AVE 2 3 ] ~ - 4 2 5 _ 3 2 . 1 ECN 3 4 c ~ ' 4 3 5 c _ 5 , ALO 2 4 4 5 2 4 5 4 .
. _ _ _ _ _ , . DIG 2 3 ~ q -c 4 4 3 5 4 4 5 IPO 2 4 4 . 4 3 5 5 5 , _ _ _ SIN 5 5 c c c c 5 5 5 c 5 5 ABU 3 4 ~ q ~ ~ 4 l 5 . 3 5 SOL 4 4 c i c ~ 5 5 ~ 6 _ 3 5 ,~
.
~. ': , : ` - ~ : , : . , `:
2~35144 _ ~XAMPLES j POST-EMERGENCE ACTIVITIES
, , - I ECI~ ALO ¦ DIC ¦ SIN ABU j SOL ! STE
. _ l _j 16 4 5 4 5 3 5 ~ I
_ . ... . ~
18 3 _ 5 5 5 _ _ _ _ ~ 26 4 1 4 4 5 5 4 ! _ 5 .
1~ 295 2 ~ 5 5 4 4 . , .
335 55 1 5 ~ 1 5 L 5 l . I I ~ I .
~0 355 1 5 5 1 5 5 1 -4 1 5 38 ~ 13 4 1 2 5 1 5 1 5 . 39 1 5 15 j 5 1 5 1 3 1 4 1 5 ~5 ' - 41 ~ 5! 5 1 5 1 5 1 5 1 5 1 5 ----1 1 l I I
43 1 5 j5 1 1 1 5 1 5 1 5 , . , .: , ~ .
: ` `
:' . -. ' ' .:
: ~, . ' .
20351~
Compound accor~
ding to Ex.No. l lj 2 l 10 12 9 Applied at a dosage rate of (kg/ha) l l l ¦ ¦
-- '1~ 21 1 21 1 ---~ 2 Post-emergence l l i activity A ~ l l ¦
! I l ~
weeds ,;
POR 5 5~ 5 41 Z ¦ 3 1 4 crops ¦ ¦ .
T~Z 0 2 0 1 0 0 2 . _ 1 1 1 1 . O 1 ~ .
. ,. ~
' ,: , . , . .. . : ' . ~ ' 51 203~4 POST-E~ERGENCE ACTIVITIE:S
¦ WEEDS
1: ~C~ Rl~TE ~ n I
PLE:S ¦ Kg/h~- GOS j TRZ ! ZEA ! ORY GLX
38 l ~ 2 O l O
:~1 0,5 O I 1 1 1 0 10 28 2 l O l 1~ 16 1 2 O O 1 211 2 O 0 ~ O
~>o 26 2 O O
333 0;5 3 0 ~ 1 O O I
¦ WEEDS
EXAN- DOSaG~
PLES Kg /h STE CHY SES CEN SET
. , ._.
1 31 0,5 5 5 1 3 - 5 3 : -, . : . -.
~ ~, , , ' 52 203~
WSAGE I POST-EME~GENCE ACTIVITIE5 PLES j ~g/ha WEEDS
ABU ¦ IPO ¦ CHY ¦ SOL ¦ POL ¦ STE
37 1 2 1 3 1 4 1 5 ll 4 43~ 5 1 ~ 5 j i ¦POST-~MERGENCE ~CTIVITIES
WEEDS
1 005 GE I i ! l PLES ~/ha STE ~ I SOL ! SET
21 22 55 3 4 44 , :
17_ 2 5 5 3 5 . ,: - :, .: . , . , : -, . . . .
203all~
POST-EMERGENCE ACTIVITIES
WEEDS
DOSAGE; ! I _ EXAM~ 'rE ln l I l ¦ PLES ! Kg~h~ STE A}IU IPO SOL ECH ¦ DIG ~ SET
39 1, 2! 5 1 5 1 4, 5 ~ 5~' ~i5 25 ! 2 ~1 5 ! 4 1 5 5 ! 5 1 ~ j 5 262 ~ 4 1 5 ' 4 4 1 5 1 4 4 lC 350.5~ 5 ! 5 1 4 ~ l 51 3 5 33ll 5 5 5 5 l 51 3 5 28l 1 5 5 5 5 1 l 1 5 1 4 - Moreover, the compound of Example 14 has shown the following activities A at a dosag~ rate of 2 kg/ha:
IPC¦ 501~ SE~ STE¦ CHY¦ GL~ NEI¦ TRZ¦ ZEA OBY
4 1 5 1 3 1 4 ~ O
These example~ ~how that, post-emer~ence, the compound~ according to the invention have a good general activity against waed~ and a good selectivity in one or more crop~, such a~ wheat, maize, rice, sunflower, cotton and soya.
~ he trials which hav~ been carried out show therefore the advantageou~ propertie~ of the compounds according to the invention as herbicide3, in particular herbicides which have a broad spectrum of activity and ., ,~ . . , ~ , 203~i4~
which can be active pre-emergence and post-emergence.
For their use in practice, the compounds according to the invention are rarely utilised by themselves. Most frequently, these compounds are part S of compositions. These compositions, which can be used as herbicidal agent~, contain, a4 the active ingredient, a compound according to the invention such as has been de~cribed above, in a mixture with at least one ~olid or liquid carrier which iB agriculturally acceptable and, if appropriate, at least one agent with surface activity i~ likewiso agriculturally acceptable.
By agent with surface activity, there is to bs under~tood, in the present ~tatement, an agent known in the English language under the term ~surfactant n ~ which embraces principally the surfa~e-active agents, wetting agent or di~persants.
These compo~itions are likewise part of the invention. ~hey can also contain a large range of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agent~, penetrants, ~tabili~ers, sequestering agents, etc. More generally, the compounds used in the invention can be combined with all solid or liquid additives which ~orrespond to techniques cu~tomary in the art of formulation.
Generally ~peaking, the compounds according to the invention cu~tomarily contain approximately from 0.05 to 95% (by weight) of a compound according to the invention, one or more ~olid or liquid carriers and, if ,. - , . ~ , . .
-: .: . . .
203514~
desired, one or mor~ surface-active agent ~ he term 'carrier~ designate~, in the pre~ent statement, an organic or inorganic natural or 6ynthetic material, with which the compound is combined far S facilitating it~ application to the plant, to the seeds or ~o the soil. This carrier is thus generally inert and it must be agriculturally acceptable, in particular to the treated plant.
The carrier can be of any customary type. In particular, it can be solid (clays, natural or synthetic silicate~, ~ilica, re~ins, waxes, ~olid fertilizers, etc....) or liguid (water; alcohol~, especially butanol etc...).
The agent with surface activity, or the ~urface-active a~ent, can al~o be of any customary type. It can be an emul~ifier, di~persant or wetting agent of the ionic or non-ionic type, or a mixture of such surface-active agent~. Examples which may be mentioned are 6alts of polyacrylic acids, ~alts of lignosulfonic acid~, salt~ of phenolsulfonic acids or naphthalenesulfonic acids, or polycondensates of ethylene oxide with fatty Alcohols or with fatty acid~
or with fatty amines, or substituted phenols ~especially alkylphenols or arylphenols), ~alt~ of esters of ~ulfosuccinic acids, derivatiYes of taurine (especially alkyltaurates), phosphoric e~ters of alcohol~ or of polycondensates of ethylene oxide with phenols, of fatty acid esters and of polyols, or ~, . .
,, ' ' 56 20351~
derivstivQ~ of the preceding compounds which have sulfate, qulfonate and phoqphste functions.
The presence of at least one surface-active agent is generally indispensable when the compound and/or inert carrier are not water-soluble and the veetor agent for the application i8 water.
Thus, the compounds for agricultural use aeeording to th~ invention can contain the active ingredients aeeording to the invention within very wide limits, from 0.05% to 95% (by weight). Their content of ~urface-acti~e agent is advantageouYly between 0.1% and 50~ by weight.
As regards the eomposition~ which are adapted to storage and transport, they contain more advantageously from 0.5 to 95~-(by weight) of active substance, the eompositions as they are applied to the plant~ being generally markedly more diluted than the eompositions which are adapted to storage and transport, which are more eoncentrated.
The compo3itions aceording to the invention themselves eome in a very wide range of forms, solid or liquid.
Solid e~mposition forms whieh may be mentioned are the dusts for dusting (having a compound content whieh ean reaeh 100~); the wettable powders; the granules, specially those obtained by extrusion, by compacting, by impregnating a granulated ~upport, by granulation using a dust (the eompound content in these ...... . . .
- , .. . . . .
.- . ~
.. . .
- , , , ,, , , , , :: : . . .
. : , ' . : . ' . ,' . ' ' ~ - :
57 203~
granules being between 0.5 and 80% in the la~t-mentioned ca~es).
The wettable powders (or sprayable powder) are customarily prepared in such a way that they contain 20 to 95~ of active compound, and they cu~tomarily contain, in addition to the solid carrier, from 0 to 30% of a wetting agent, from 3 to 20~ of a disperYant and, if neces~ary, from 0 to 10% of one or more stabilisers and/or other additlves, such as penetrant~, adhesive~, or anticaking agents, colourants, QtC.
To obtain the ~prayable powders, or wettable powders, the active substances are mixed intimately in suitable mixer~ with the additional substances, and the mixture is ground by mea~s of mills or other suitable grinders. In thi~ way, powder~ for spraying are obtained whose wettabil~ty and su~pension properties are advantageous; they can be suspended in water at any desired concentration, and the suspension3 can ba used very advantageously, in particular for application to the leaves of the plants.
In place of the wettable powders, pastes can be rQalised. The conditions and detail~ of production and utili~ation of th~se pa~te~ are similar to tho~e in the case of the wettable powdars or sprayable powder~.
What follow~ now by way of example are various compositions of wettable powders ~or sprayable powders):
:
; .
, .., 58 20351~4 Example F 1:
Active compound (compound No.1) 50 ~ Ethoxylated fatty alcohol (wetting agent) 2.5 5 ~ Condensate of ethylene oxide with phenyl-ethylphenol (dispersant) 5%
~ Chalk (inert carr~er) 42.5%
Example F 2:
* Active compound (compound No.l) 10%
10 * Synthetic oxo Cl3 alcohol of the branched type, ethoxylated with 8 to 10 ethylene oxide unit~
(wetting agent) 0.75%
* Neutral calcium ligno~ulfonate (dispersant) 12%
* Calcium carbonate (inert filler) q.s. 100 Example F 3: this wettable powder contains the ~ame ingredients as in the preceding example, in the following proportions: -* Active compound 75 20 * Wetting agent 1.50%
* Disper~ant 8%
* Calcium carbonate (inert filler~ q.s. 100%
Example F 4: .
* Active compound (compound No.1) 90%
25 * Ethoxylated fat~y alcohol (wetting agent) 4%
* Ethoxylated phenylethylphenol (di~persant) 6%
. ' -,:' .. -- , '' .
,:~ . -. . . :
` -`` 203~i44 Exam~e F5s * Active compound (compound No.1) 50%
~ Mixture of anionic and non-ionic curfactants ~wetting agent) 2.5%
~ Sodium lignosulfonate (di~persant) 5~
* Raolin-type clay (inert carrier) 42.5%
The compounds according to the invention which can be formulated in the form of water-dispexsible granule~ sre likewi~e comprised in the Rcope of the invention.
These di~persible granule~, whose apparent density is generally between about 0.3 and 0.6, have a particle s~ze of generally between about 0.15 and 2 mm and preferably between 0.3 and 1.5 mm.
The active ~ubstance eontent of the3e granules is generally between about 1% and 90%, and preferably between 25~ and 90%.
The remainder of the granule is es entially composed of a solid filler and, if appropriate, of surface-active ad~uvants which impart to the granule properties of water dispersibility. ~hese granules can esaentially be of two type which are distinguished a~cording to whether the filler carried i8 water-soluble o~ not. When the filler i5 water-soluble, it can be inorganic or, preferably, organic. Excellent re~ulta have been obtained using urea. In the casQ of ~
an insoluble filler, the latter is preferably inorganic, ~uch as, for example, kaolin or bentonite.
; , :.
. ~
-., : . . ' :
. .; ' ~: , 2 f3 3 ~
It i8 therefore advantageou~ly accompanied by surface-active agents (ln a ratio of 2 to 20~ by weight of the granule) of which more than half iB, for example, composed by least one, e~sentially anionic, dispersant such as an alkali metal polynaphthalene~ulfonate or alkaline earth metal polynaphthalenesulfonate or an alkali metal lignosulfonatQ or an alkaline earth metal lignosulfonate, the remainder being composed of non-ionic or anionic wettinq agent~ ~uch a~ an alkali metal alkylnaphthalenesulfonate or alkaline earth metal alkylnaphthalenesulfonate.
Moreover, other ad~uvants such as antifoam agents can be added, even though this is not indispensable.
The ~ranules accordin~ to the invention can be prepared by mixing the necessary ingredient~ followed by granulation according to various techniques known per se (coating apparatus, fluidised bed, atomiser, extrus~on, etc.). The proces~ i8 generally fini~hed by 20 a cxushing step followed by a sieving step at the ~;.
particle d~men~ion selected within the above lLmits mentioned.
It ~ preferably obtained by extrusion, proceeding a8 shown in the example~ hereinafter.
xam~le F 6: Disper~ible aranules 90% by weight of active ~ubstance tcompound No.l) and 10% of urea in bead form are mixed in a ' ~ -- 2 0 3 ~
mixer. The mixture i~ ~ub~equently ground in a pin mill. Thi~ giVQ8 8 powder which i~ moistened wlth about 8% by weight of water. The moi~t powder i~ extruded ln a perforated-roll extruder. This g~ves granule~ which are dried, then cru~hed and ~eved, in such a way as to retain only the granules of a size between 0.15 and 2 mm.
Exam~le F 7: Disper~ible granules The following components are mlxed in a mixer:
* Active sub~tance (compound No.l) 75~
* Wetting agent ~sodium alkylnaphthalene~ulfonate) 2%
* Disper~ant (sodium polynaphthalene~ulfonats) 8 ~ Inert water-insoluble filler (kaolin) 15~
Thi~ mixture is granul~ted in a fluidised bed in the presence of water, and then dried, cru~hed and sie~ed in such a way as to obtain granules of a size between 0.15 and 0.80 mm.
The~e granule~ can be used on their own, or in solution or dispersion in water in ~uch a way as to obtain the de~ired dosage rate. They ~an also be u~ed for preparing combination~ with other active substances, e~pec~ally herbicides, the latter being in th~ form of wettable pcwders or of granules or aqeuou~
~uspensions.
~ he compoundY of the formula (I) can also be used in the form of dusts for dusting; it is also possible to use a composition containing 50 g of actiYe :, . ~ . . ~.
' ~" - ~' ' ' .
203~
substanc~ and 9S0 g of talc; it i~ also pos~ible to use a composition containing 20 g of active substance, 10 g of finely-divided silica and 970 g of talc; the components are mixed and ground, and the mixture i5 applied by dusting.
Liquid forms of compo~itions, or forms of compositions intended for making up liquid composit~ons at the time of application, which may be mentioned are ~olutions, in particular wa~er-soluble concantrate~, emulsifiable concRntrates, emulsion~, flowable~ and aerosols; wettabl~ powders (or sprayable powder) and pastes are solid compo~itions but intended for making up liquid compo3itions at the time of application.
~he emulsifiable concentrates or soluble concentrates most frequently c~mprise 10 to 80% of active substance, while the ready-to-use emulsion~ or solutions, for their partl contain 0.001 to 20% of active substance.
Besides th~ solvent, the emulsifiable concentrates can contain, if necessary, 2 to 20% of suitabla additive~ such as ~tabilisers, surface-active agent~, penGtrants, corrosion inhibitors, colourants or adhesives, a3 mentioned above.
Using these concentrate~, d~lution with water can givo emulsions of any desired concentration, which i~ particulsrly convenient for application to crops.
What now follow~ by way of example is the composition of some emulsifiable concentrate~:
. . .. .
..
: -.: , .~ .
203~
Exam~le F 8:
~ Active substance 400 g/l * Alkali metal dodecylbenzene sulfonate 24 g~l * Nonylphenol with oxyethylated 10 molecules 5 of ethylene oxide 16 g/l * Cyclohexan~ne 200 g/l Aromatic solvent q.s. 1 litre According to another formula for an emulsifiable concentrate, the following are used:
10 Example F 9:
* Active ~ubstance 250 g * Epoxidised vegetable oil 25 g * Nlxture of alkylarylsulfonate and an ether of polyglycol with fatty alcohols100 g 15 * DLmethylformamide - 50 g * Xylene 575 g The flowables, which can likewi~e be applied by spraying, are prepared in 3uch a way as to obtain a fluid stable produc~ which does not sattle out, and they customarily contain from 10 to 75% of active substance, from 0.5 to 15% of surface-active agents, from 0.1 to 10% of thixotropi~ agents, from 0 to 10~ of suitable additive~ such as antifo2ms~ corrosion inhibiters, ~tabiliser3, penetrants and adhesive , and, as a carrier, water or an organic l~quid in which the active substance i~ sparingly soluble, or insolubles certain ~olid organic material~ or mineral ~alt~ can be :
203~14~
dissolved in the carrier for helping prevent sedimentation, or as antigels in the casQ of water.
What now follows by way of example is a composition of a flowable:
Example F 102 Compound 500 g * Polyconden~ate of ethylene oxide with tri~tyrylphenol phosphate 50 g * Polyethoxylated alkylphenol 50 g 10 ~ Sodium polycarboxylate 20 g ~ ~thylene glycol 50 g * Organopoly~iloxane-type oil (antifoam) 1 g * Polysaccharide 1.5 g :~
* Water 327.5 g The aqueous di~persion~ and emulsions, for example the compositions obtained by dilutin~ a wettable powder or an emul~ifiabla concentrate according to the invention with the aid of water, are Qncompassed within the general ~cope of th~ present invention. The emulsions can be of ths water-in-oil type or oil-in-water type, and they can have a thick consistency like that of a ~mayonnaise.
The pre3ent invention also relates to a weeding method (e~pecially in area~ of dicotyledon or monocotyledon crop~), which consists of applying, to the area to be weeded, and/or on the plants to be destroyed, an effective amount of a compound according , 20 3 51 ~1 to the invention, especially a compound of the formula (I), it being possible for the plants (or weeds) which are to be destroyed, or whose growth it is desired to prevent, to bs of the monocotyledon or dicotyledon type.
The product~ and compositions according to the invention are conveniently applied to tha vegetation and especially to the weed~ to be eliminated when they have a green foliage (post-emergence application).
It is also po~ible to use a weeding method which consists of applying an effective quantity of a compound of the formula (I) to the areas or terrains where it i~ desired to prevent the germination or the development of plant~ which have not yet germinated ~pre-emergence application). In thi~ case, it i5 possible for which the crop to be sown before or after the treatment.
The application rate of active sub~tance i~
generally between 0.05 and 8 kg!ha, preferably between 0.4 and 4 kg/ha.
.
66 203~
~umbe r i ng ~NFormul a (1) 7 ~N
N ~ ` 6 Ar Y~,NH-N-CH-Ar Y~5,T
Forrr~.~J~ a (Il) Fr.~m~la ~\1111) Y~NH-NH-CO-Ar ~ ~--C//
N ~ ;
Formula (111), Forrnula (IX) X~ Ar ~
For~ a (IV) Formub (Xl) , Z Z
Y~NH-NH2 Y~N--N=C-At X~N X N
Fom~la (V) Fom~la(XII) , ~ : . : , . ~
- . . .. :
CHR Corn marigold Chrysanthemum 3egetum 10 POR Common purslane Portulaca oleracea . _ . _ .
DIG Hairy finger gra~s Digitaria sanguinali~
SIN Nhite mustard Sinapi3 alba . _ . I
ALO Black grass Alopecuru~
~yo~uroide~
. , . .
IPO China ~ute Ipomea purpurea .
ABU Black nightshade Abutilon theophrasti SOL Common chickweed Solanum nigrum .. , 20 STE Stitchwort Stellaria media, .
CEN Cornflower Centaurea cyanu3 . _ .. .__ . -SES Hemp ~esbania Sesbania exaltata SET Faber's foxtail Setaria faberii CHY - Corn marLgold Chrysanthemum . segetum ,~ , , : - . .
' 203~14~
3~
. ____. ~ .. . _ Abbrevia- Engli~h name of Latin name tions weeds . _ _ _ ... ... __ . ., S RZ Wheat Triti~um ae~tivum ZEA Maize Zea May~
.. _ _ I
ORY Rice Oryza sativa _ Soya Glycine maximum GOS Cotton Gossypium hlr~utum 10 HE~ Sunflower Helianthu~ annuus BRS Oilsaed rape Brassica napus Example Vl:
Herbicidal application before emergence of the plant t 15 species.
A number of eeds selected as a function of the plant specie~ and the ~ize of the seed is sown in 7 x 7 x 8 cm pots filled with light agricultural 80il.
The pot~ are treated by spraying them with a 20 mixture in an amount which corresponds to an application rata of 500 l/ha and which contains the active ingredient at the desired concentration.
The seeds which are not covered by 80il are thus treated with the mixture tthe term mixture is used 25 to designate generally compositions which ar~ diluted with water, such as are applied to the plants).
The mixture used for the treatment i5 a ,. . . . .
- :~
. . - ., . : ,. .
,.~ ;. :
.~ , 203~
solution or suspension of the active in~redient in an acetone/water mixture in the ratio of 50/50, in the presencQ of 0.05% by weight of Cemul~ol NP 10 (surfactant) which is composed of a polyethoxyl~ted S alkylphenol, in particular 8 polyethoxylated nonylphenol) and 0.04% by weight of Tween 20 (surfactant composed of an oleate of a derivatiYe of a polycondensate of ethylene oxide with sorbitol).
In the case of a suspen~ion~ the latter is obtained by mixing and grinding the ingredients in a microniser in such a way a~ to obtain an averags particle ~ize of less than 40 micron~.
After the treatment, the ~eed~ are covered by a layer of soil about 3 mm in thicknes3.
The pot8 are then placed in containers for receiving the watering water, by way of ~ubirrigation, and maintained for 24 hour~ at ambient temperature and 60% relative humidity.
After 24 days, a de3truction percentage (D) of the plants in the treated pot is determined in relation to the number of plants in the untreated pots (controls). On the remaining treated plants, the size reduction percentage (SR) i8 measured in relation to the control plants.
The percentage of foliar volume destroyed and reduced by the product i8 therefore given by the formula ~ ~ 3 ~
D + SR (100 - D) = A
This value A i~ transformed into a key from O
to 5 ac~ording to the following gradations Rey O ~ A < 10 0 no effect 10 < A < 30 30 ~ A ~ 50 2 50 < A < 70 3 70 ~ A < 90 4 90 < A ~ 100 5 complete de~truction.
.
~ : : ?
.:
.. : ~ .
... : , . .. .
:: ~ , , ': ..
~. ~ : . - -: :
20351~
The result~ obtained are given hereinafter:
Compound accor- 6 2 10 3 5 1 ding to Ex.No. . ¦ .
5 (applied at a .
dosage rate of 4 kg/ha) ~ ~ - _ _ _ Pre-emergence .
activity A
_ _ _ _ _ DIG 5 5 5 3 5 5 5 5 5 5 ff~-_ _ __ A~U 4 5 5 5 5 4 3 5 5 5 ,. . .
, ^" 203S1 ~4 PRE-EMERGENCE ACTIVITY
EXAMPLES ¦ ECH ¦ ALO ¦ DIG SIN ABU j SOL ¦ STE ¦
._-- 1- l _ _ ~i 1 1 65 - 5 ---- -5 5 -- 5 5 5 ~ .... . _ 20 4 5 5_ 5 5 5 5 I
23 3 4 5 1 _5_ __5 _ l~i 33 5 5 5 5 5 5 5 34 5 5 ' 5 5 5 . _ . _ . .
39 3 5 5 1 0 5 ~i , -I
..... _ 1- -' i -- , 2a . .
'' , . :- . ~ : ..
~ ~' ' . . . -.
.
.:. . . : : . .
203~
_ .. _ PRE-EMERGENCE ACTIVITIES
CROPS
EXAY- DOS- _ . _ _ _ PLES ARGEE
Xg/ha E~RS GOS GLX S SL TRZ Z SA ORY
27 2 ~ 0 0 1 0 0 .
. .:
- : -, ~ -, .:: , 2 0 3 ~ ~ 4 '~
_~ PRE-EMERGENCE ACTIVITIES
WEEDS
S E~ DOS-PLES ARAEE
kg/h~ STE CHY SOL DIG SET
~. . -, :
. ' ~' . ~ ' ' 20351~
_ . .
PRE-EMERGENCE ACTIVITIES
CROPS WEEDS
, . .. .. . __ EXAM- DOS- i 5 ¦ PL S ¦ RA rE
kg~ha GLX TRZ ZEA STE AE~U SOL DIG
. _ l _ 32 2 O t) O O 5 1 4 4 . 43 4 1 O 1 _ 5 5 5I 5 - - . - . . :
~: . - .:- ....... - , - :
-: - - ~
:
203~144 Compound according to Ex.No 5 1 12 Applied at a dosage rate of 5 (kg/ha) 2 1 4 Pre-emergence activity A
_ _ GOS 0 _ HE~ 0 3 2 __ , ..
ORY 1 0 0 ;
E amples which follow:
These examples show that, pre-emergence, the products according to the invention have a good general activity against the weed~ and a good ~electivity toward~ one or more crops ~uch as wheat, maize, rice, cotton, ~unflower, ~oya and oilseed rape.
, .~ . . .~ .
:. . .
47 20351~
Examp~~ U2 Herbiçidal apDlication after emer ence of the ~lant species A number of seeds selected as a function of the plant specie~ and the size of the seed i8 sown in 7 x 7 x 8 cm pots filled w~th light agricultural soil.
The seeds are then covered by a layer of 80il of about 3 mm in thickness and the seed i8 allowed to germinate until it give~ ri~e to a plantlet in a suitable stage. In the case of tha Gramineae, the treatment st~ge is the ~formation of second leaf~
stags. In the case of the dicotyledon3, the treatment StagQ i8 the "cotyledons unfolded, first true leaf being developed~ stage.
The pota are then treated by spraying ~hem with a mixture in an amount which corresponds to an application rate cf 500 l~h~ and which contain~ the active ingredient at the desired ~oncentration.
The mixtuxe used for the treatment is prepared a~ in Example Ul.
After the treatment, the seeds are covered by a soil layer of about 3 mm in thickness.
The potA are then placed in containers for receiving the watering water, by way of subirrigation, and maintained for 24 days at ambient tempera~ure and 60% relative humidity.
A (pexcentage of destroyed foliage volume) is measured as in Example U~.
. ,: - ,. : : -48 2V351~4 The resul~s obta:Lned are given hereinafters _ 6 1~ 4~ 3 1 5~ 13--Compound in accordance 5 with Ex.No.
(applied at a dosage rate of 1 , 4 kg/ha) . 1 ~ ¦
. . _ . _ _ . i i 10 Post-emergence activity AVE 2 3 ] ~ - 4 2 5 _ 3 2 . 1 ECN 3 4 c ~ ' 4 3 5 c _ 5 , ALO 2 4 4 5 2 4 5 4 .
. _ _ _ _ _ , . DIG 2 3 ~ q -c 4 4 3 5 4 4 5 IPO 2 4 4 . 4 3 5 5 5 , _ _ _ SIN 5 5 c c c c 5 5 5 c 5 5 ABU 3 4 ~ q ~ ~ 4 l 5 . 3 5 SOL 4 4 c i c ~ 5 5 ~ 6 _ 3 5 ,~
.
~. ': , : ` - ~ : , : . , `:
2~35144 _ ~XAMPLES j POST-EMERGENCE ACTIVITIES
, , - I ECI~ ALO ¦ DIC ¦ SIN ABU j SOL ! STE
. _ l _j 16 4 5 4 5 3 5 ~ I
_ . ... . ~
18 3 _ 5 5 5 _ _ _ _ ~ 26 4 1 4 4 5 5 4 ! _ 5 .
1~ 295 2 ~ 5 5 4 4 . , .
335 55 1 5 ~ 1 5 L 5 l . I I ~ I .
~0 355 1 5 5 1 5 5 1 -4 1 5 38 ~ 13 4 1 2 5 1 5 1 5 . 39 1 5 15 j 5 1 5 1 3 1 4 1 5 ~5 ' - 41 ~ 5! 5 1 5 1 5 1 5 1 5 1 5 ----1 1 l I I
43 1 5 j5 1 1 1 5 1 5 1 5 , . , .: , ~ .
: ` `
:' . -. ' ' .:
: ~, . ' .
20351~
Compound accor~
ding to Ex.No. l lj 2 l 10 12 9 Applied at a dosage rate of (kg/ha) l l l ¦ ¦
-- '1~ 21 1 21 1 ---~ 2 Post-emergence l l i activity A ~ l l ¦
! I l ~
weeds ,;
POR 5 5~ 5 41 Z ¦ 3 1 4 crops ¦ ¦ .
T~Z 0 2 0 1 0 0 2 . _ 1 1 1 1 . O 1 ~ .
. ,. ~
' ,: , . , . .. . : ' . ~ ' 51 203~4 POST-E~ERGENCE ACTIVITIE:S
¦ WEEDS
1: ~C~ Rl~TE ~ n I
PLE:S ¦ Kg/h~- GOS j TRZ ! ZEA ! ORY GLX
38 l ~ 2 O l O
:~1 0,5 O I 1 1 1 0 10 28 2 l O l 1~ 16 1 2 O O 1 211 2 O 0 ~ O
~>o 26 2 O O
333 0;5 3 0 ~ 1 O O I
¦ WEEDS
EXAN- DOSaG~
PLES Kg /h STE CHY SES CEN SET
. , ._.
1 31 0,5 5 5 1 3 - 5 3 : -, . : . -.
~ ~, , , ' 52 203~
WSAGE I POST-EME~GENCE ACTIVITIE5 PLES j ~g/ha WEEDS
ABU ¦ IPO ¦ CHY ¦ SOL ¦ POL ¦ STE
37 1 2 1 3 1 4 1 5 ll 4 43~ 5 1 ~ 5 j i ¦POST-~MERGENCE ~CTIVITIES
WEEDS
1 005 GE I i ! l PLES ~/ha STE ~ I SOL ! SET
21 22 55 3 4 44 , :
17_ 2 5 5 3 5 . ,: - :, .: . , . , : -, . . . .
203all~
POST-EMERGENCE ACTIVITIES
WEEDS
DOSAGE; ! I _ EXAM~ 'rE ln l I l ¦ PLES ! Kg~h~ STE A}IU IPO SOL ECH ¦ DIG ~ SET
39 1, 2! 5 1 5 1 4, 5 ~ 5~' ~i5 25 ! 2 ~1 5 ! 4 1 5 5 ! 5 1 ~ j 5 262 ~ 4 1 5 ' 4 4 1 5 1 4 4 lC 350.5~ 5 ! 5 1 4 ~ l 51 3 5 33ll 5 5 5 5 l 51 3 5 28l 1 5 5 5 5 1 l 1 5 1 4 - Moreover, the compound of Example 14 has shown the following activities A at a dosag~ rate of 2 kg/ha:
IPC¦ 501~ SE~ STE¦ CHY¦ GL~ NEI¦ TRZ¦ ZEA OBY
4 1 5 1 3 1 4 ~ O
These example~ ~how that, post-emer~ence, the compound~ according to the invention have a good general activity against waed~ and a good selectivity in one or more crop~, such a~ wheat, maize, rice, sunflower, cotton and soya.
~ he trials which hav~ been carried out show therefore the advantageou~ propertie~ of the compounds according to the invention as herbicide3, in particular herbicides which have a broad spectrum of activity and ., ,~ . . , ~ , 203~i4~
which can be active pre-emergence and post-emergence.
For their use in practice, the compounds according to the invention are rarely utilised by themselves. Most frequently, these compounds are part S of compositions. These compositions, which can be used as herbicidal agent~, contain, a4 the active ingredient, a compound according to the invention such as has been de~cribed above, in a mixture with at least one ~olid or liquid carrier which iB agriculturally acceptable and, if appropriate, at least one agent with surface activity i~ likewiso agriculturally acceptable.
By agent with surface activity, there is to bs under~tood, in the present ~tatement, an agent known in the English language under the term ~surfactant n ~ which embraces principally the surfa~e-active agents, wetting agent or di~persants.
These compo~itions are likewise part of the invention. ~hey can also contain a large range of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agent~, penetrants, ~tabili~ers, sequestering agents, etc. More generally, the compounds used in the invention can be combined with all solid or liquid additives which ~orrespond to techniques cu~tomary in the art of formulation.
Generally ~peaking, the compounds according to the invention cu~tomarily contain approximately from 0.05 to 95% (by weight) of a compound according to the invention, one or more ~olid or liquid carriers and, if ,. - , . ~ , . .
-: .: . . .
203514~
desired, one or mor~ surface-active agent ~ he term 'carrier~ designate~, in the pre~ent statement, an organic or inorganic natural or 6ynthetic material, with which the compound is combined far S facilitating it~ application to the plant, to the seeds or ~o the soil. This carrier is thus generally inert and it must be agriculturally acceptable, in particular to the treated plant.
The carrier can be of any customary type. In particular, it can be solid (clays, natural or synthetic silicate~, ~ilica, re~ins, waxes, ~olid fertilizers, etc....) or liguid (water; alcohol~, especially butanol etc...).
The agent with surface activity, or the ~urface-active a~ent, can al~o be of any customary type. It can be an emul~ifier, di~persant or wetting agent of the ionic or non-ionic type, or a mixture of such surface-active agent~. Examples which may be mentioned are 6alts of polyacrylic acids, ~alts of lignosulfonic acid~, salt~ of phenolsulfonic acids or naphthalenesulfonic acids, or polycondensates of ethylene oxide with fatty Alcohols or with fatty acid~
or with fatty amines, or substituted phenols ~especially alkylphenols or arylphenols), ~alt~ of esters of ~ulfosuccinic acids, derivatiYes of taurine (especially alkyltaurates), phosphoric e~ters of alcohol~ or of polycondensates of ethylene oxide with phenols, of fatty acid esters and of polyols, or ~, . .
,, ' ' 56 20351~
derivstivQ~ of the preceding compounds which have sulfate, qulfonate and phoqphste functions.
The presence of at least one surface-active agent is generally indispensable when the compound and/or inert carrier are not water-soluble and the veetor agent for the application i8 water.
Thus, the compounds for agricultural use aeeording to th~ invention can contain the active ingredients aeeording to the invention within very wide limits, from 0.05% to 95% (by weight). Their content of ~urface-acti~e agent is advantageouYly between 0.1% and 50~ by weight.
As regards the eomposition~ which are adapted to storage and transport, they contain more advantageously from 0.5 to 95~-(by weight) of active substance, the eompositions as they are applied to the plant~ being generally markedly more diluted than the eompositions which are adapted to storage and transport, which are more eoncentrated.
The compo3itions aceording to the invention themselves eome in a very wide range of forms, solid or liquid.
Solid e~mposition forms whieh may be mentioned are the dusts for dusting (having a compound content whieh ean reaeh 100~); the wettable powders; the granules, specially those obtained by extrusion, by compacting, by impregnating a granulated ~upport, by granulation using a dust (the eompound content in these ...... . . .
- , .. . . . .
.- . ~
.. . .
- , , , ,, , , , , :: : . . .
. : , ' . : . ' . ,' . ' ' ~ - :
57 203~
granules being between 0.5 and 80% in the la~t-mentioned ca~es).
The wettable powders (or sprayable powder) are customarily prepared in such a way that they contain 20 to 95~ of active compound, and they cu~tomarily contain, in addition to the solid carrier, from 0 to 30% of a wetting agent, from 3 to 20~ of a disperYant and, if neces~ary, from 0 to 10% of one or more stabilisers and/or other additlves, such as penetrant~, adhesive~, or anticaking agents, colourants, QtC.
To obtain the ~prayable powders, or wettable powders, the active substances are mixed intimately in suitable mixer~ with the additional substances, and the mixture is ground by mea~s of mills or other suitable grinders. In thi~ way, powder~ for spraying are obtained whose wettabil~ty and su~pension properties are advantageous; they can be suspended in water at any desired concentration, and the suspension3 can ba used very advantageously, in particular for application to the leaves of the plants.
In place of the wettable powders, pastes can be rQalised. The conditions and detail~ of production and utili~ation of th~se pa~te~ are similar to tho~e in the case of the wettable powdars or sprayable powder~.
What follow~ now by way of example are various compositions of wettable powders ~or sprayable powders):
:
; .
, .., 58 20351~4 Example F 1:
Active compound (compound No.1) 50 ~ Ethoxylated fatty alcohol (wetting agent) 2.5 5 ~ Condensate of ethylene oxide with phenyl-ethylphenol (dispersant) 5%
~ Chalk (inert carr~er) 42.5%
Example F 2:
* Active compound (compound No.l) 10%
10 * Synthetic oxo Cl3 alcohol of the branched type, ethoxylated with 8 to 10 ethylene oxide unit~
(wetting agent) 0.75%
* Neutral calcium ligno~ulfonate (dispersant) 12%
* Calcium carbonate (inert filler) q.s. 100 Example F 3: this wettable powder contains the ~ame ingredients as in the preceding example, in the following proportions: -* Active compound 75 20 * Wetting agent 1.50%
* Disper~ant 8%
* Calcium carbonate (inert filler~ q.s. 100%
Example F 4: .
* Active compound (compound No.1) 90%
25 * Ethoxylated fat~y alcohol (wetting agent) 4%
* Ethoxylated phenylethylphenol (di~persant) 6%
. ' -,:' .. -- , '' .
,:~ . -. . . :
` -`` 203~i44 Exam~e F5s * Active compound (compound No.1) 50%
~ Mixture of anionic and non-ionic curfactants ~wetting agent) 2.5%
~ Sodium lignosulfonate (di~persant) 5~
* Raolin-type clay (inert carrier) 42.5%
The compounds according to the invention which can be formulated in the form of water-dispexsible granule~ sre likewi~e comprised in the Rcope of the invention.
These di~persible granule~, whose apparent density is generally between about 0.3 and 0.6, have a particle s~ze of generally between about 0.15 and 2 mm and preferably between 0.3 and 1.5 mm.
The active ~ubstance eontent of the3e granules is generally between about 1% and 90%, and preferably between 25~ and 90%.
The remainder of the granule is es entially composed of a solid filler and, if appropriate, of surface-active ad~uvants which impart to the granule properties of water dispersibility. ~hese granules can esaentially be of two type which are distinguished a~cording to whether the filler carried i8 water-soluble o~ not. When the filler i5 water-soluble, it can be inorganic or, preferably, organic. Excellent re~ulta have been obtained using urea. In the casQ of ~
an insoluble filler, the latter is preferably inorganic, ~uch as, for example, kaolin or bentonite.
; , :.
. ~
-., : . . ' :
. .; ' ~: , 2 f3 3 ~
It i8 therefore advantageou~ly accompanied by surface-active agents (ln a ratio of 2 to 20~ by weight of the granule) of which more than half iB, for example, composed by least one, e~sentially anionic, dispersant such as an alkali metal polynaphthalene~ulfonate or alkaline earth metal polynaphthalenesulfonate or an alkali metal lignosulfonatQ or an alkaline earth metal lignosulfonate, the remainder being composed of non-ionic or anionic wettinq agent~ ~uch a~ an alkali metal alkylnaphthalenesulfonate or alkaline earth metal alkylnaphthalenesulfonate.
Moreover, other ad~uvants such as antifoam agents can be added, even though this is not indispensable.
The ~ranules accordin~ to the invention can be prepared by mixing the necessary ingredient~ followed by granulation according to various techniques known per se (coating apparatus, fluidised bed, atomiser, extrus~on, etc.). The proces~ i8 generally fini~hed by 20 a cxushing step followed by a sieving step at the ~;.
particle d~men~ion selected within the above lLmits mentioned.
It ~ preferably obtained by extrusion, proceeding a8 shown in the example~ hereinafter.
xam~le F 6: Disper~ible aranules 90% by weight of active ~ubstance tcompound No.l) and 10% of urea in bead form are mixed in a ' ~ -- 2 0 3 ~
mixer. The mixture i~ ~ub~equently ground in a pin mill. Thi~ giVQ8 8 powder which i~ moistened wlth about 8% by weight of water. The moi~t powder i~ extruded ln a perforated-roll extruder. This g~ves granule~ which are dried, then cru~hed and ~eved, in such a way as to retain only the granules of a size between 0.15 and 2 mm.
Exam~le F 7: Disper~ible granules The following components are mlxed in a mixer:
* Active sub~tance (compound No.l) 75~
* Wetting agent ~sodium alkylnaphthalene~ulfonate) 2%
* Disper~ant (sodium polynaphthalene~ulfonats) 8 ~ Inert water-insoluble filler (kaolin) 15~
Thi~ mixture is granul~ted in a fluidised bed in the presence of water, and then dried, cru~hed and sie~ed in such a way as to obtain granules of a size between 0.15 and 0.80 mm.
The~e granule~ can be used on their own, or in solution or dispersion in water in ~uch a way as to obtain the de~ired dosage rate. They ~an also be u~ed for preparing combination~ with other active substances, e~pec~ally herbicides, the latter being in th~ form of wettable pcwders or of granules or aqeuou~
~uspensions.
~ he compoundY of the formula (I) can also be used in the form of dusts for dusting; it is also possible to use a composition containing 50 g of actiYe :, . ~ . . ~.
' ~" - ~' ' ' .
203~
substanc~ and 9S0 g of talc; it i~ also pos~ible to use a composition containing 20 g of active substance, 10 g of finely-divided silica and 970 g of talc; the components are mixed and ground, and the mixture i5 applied by dusting.
Liquid forms of compo~itions, or forms of compositions intended for making up liquid composit~ons at the time of application, which may be mentioned are ~olutions, in particular wa~er-soluble concantrate~, emulsifiable concRntrates, emulsion~, flowable~ and aerosols; wettabl~ powders (or sprayable powder) and pastes are solid compo~itions but intended for making up liquid compo3itions at the time of application.
~he emulsifiable concentrates or soluble concentrates most frequently c~mprise 10 to 80% of active substance, while the ready-to-use emulsion~ or solutions, for their partl contain 0.001 to 20% of active substance.
Besides th~ solvent, the emulsifiable concentrates can contain, if necessary, 2 to 20% of suitabla additive~ such as ~tabilisers, surface-active agent~, penGtrants, corrosion inhibitors, colourants or adhesives, a3 mentioned above.
Using these concentrate~, d~lution with water can givo emulsions of any desired concentration, which i~ particulsrly convenient for application to crops.
What now follow~ by way of example is the composition of some emulsifiable concentrate~:
. . .. .
..
: -.: , .~ .
203~
Exam~le F 8:
~ Active substance 400 g/l * Alkali metal dodecylbenzene sulfonate 24 g~l * Nonylphenol with oxyethylated 10 molecules 5 of ethylene oxide 16 g/l * Cyclohexan~ne 200 g/l Aromatic solvent q.s. 1 litre According to another formula for an emulsifiable concentrate, the following are used:
10 Example F 9:
* Active ~ubstance 250 g * Epoxidised vegetable oil 25 g * Nlxture of alkylarylsulfonate and an ether of polyglycol with fatty alcohols100 g 15 * DLmethylformamide - 50 g * Xylene 575 g The flowables, which can likewi~e be applied by spraying, are prepared in 3uch a way as to obtain a fluid stable produc~ which does not sattle out, and they customarily contain from 10 to 75% of active substance, from 0.5 to 15% of surface-active agents, from 0.1 to 10% of thixotropi~ agents, from 0 to 10~ of suitable additive~ such as antifo2ms~ corrosion inhibiters, ~tabiliser3, penetrants and adhesive , and, as a carrier, water or an organic l~quid in which the active substance i~ sparingly soluble, or insolubles certain ~olid organic material~ or mineral ~alt~ can be :
203~14~
dissolved in the carrier for helping prevent sedimentation, or as antigels in the casQ of water.
What now follows by way of example is a composition of a flowable:
Example F 102 Compound 500 g * Polyconden~ate of ethylene oxide with tri~tyrylphenol phosphate 50 g * Polyethoxylated alkylphenol 50 g 10 ~ Sodium polycarboxylate 20 g ~ ~thylene glycol 50 g * Organopoly~iloxane-type oil (antifoam) 1 g * Polysaccharide 1.5 g :~
* Water 327.5 g The aqueous di~persion~ and emulsions, for example the compositions obtained by dilutin~ a wettable powder or an emul~ifiabla concentrate according to the invention with the aid of water, are Qncompassed within the general ~cope of th~ present invention. The emulsions can be of ths water-in-oil type or oil-in-water type, and they can have a thick consistency like that of a ~mayonnaise.
The pre3ent invention also relates to a weeding method (e~pecially in area~ of dicotyledon or monocotyledon crop~), which consists of applying, to the area to be weeded, and/or on the plants to be destroyed, an effective amount of a compound according , 20 3 51 ~1 to the invention, especially a compound of the formula (I), it being possible for the plants (or weeds) which are to be destroyed, or whose growth it is desired to prevent, to bs of the monocotyledon or dicotyledon type.
The product~ and compositions according to the invention are conveniently applied to tha vegetation and especially to the weed~ to be eliminated when they have a green foliage (post-emergence application).
It is also po~ible to use a weeding method which consists of applying an effective quantity of a compound of the formula (I) to the areas or terrains where it i~ desired to prevent the germination or the development of plant~ which have not yet germinated ~pre-emergence application). In thi~ case, it i5 possible for which the crop to be sown before or after the treatment.
The application rate of active sub~tance i~
generally between 0.05 and 8 kg!ha, preferably between 0.4 and 4 kg/ha.
.
66 203~
~umbe r i ng ~NFormul a (1) 7 ~N
N ~ ` 6 Ar Y~,NH-N-CH-Ar Y~5,T
Forrr~.~J~ a (Il) Fr.~m~la ~\1111) Y~NH-NH-CO-Ar ~ ~--C//
N ~ ;
Formula (111), Forrnula (IX) X~ Ar ~
For~ a (IV) Formub (Xl) , Z Z
Y~NH-NH2 Y~N--N=C-At X~N X N
Fom~la (V) Fom~la(XII) , ~ : . : , . ~
- . . .. :
Claims (23)
- A compound of the triazolopyridine type, which has the formula (I) in which:
* X, Y and Z represent a halogen atom or a halogen atom or an alkyl group or haloalkyl group or alkoxy group, at least one of the radicals X, Y or Z having a meaning other than the hydrogen atom, * Ar represents a phenyl group which is optionally mono- or polysubstituted by a lower alkyl group or lower alkoxy group or lower alkylthio group or phenyl group or phenoxy group or a halogen atom, preferably chlorine or fluorine; or a heterocycle Het, * Het represents a heterocycle having 5 or 6 ring members and containing one or more hetero atom(s) such as sulphur, nitrogen or oxygen, this heterocycle being optionally mono- or polysubstituted by a lower alkyl group or lower alkoxy group or lower alkylthio group or a halogen atom, preferably chlorine or fluorine, and agriculturally acceptable salts therof, * with the exclusion of compounds wherein, ** simultaneously Y represents a methyl group, X and Z represent a hydrogen atom, Ar represents a 3-chloro phenyl or 4-chlorophenyl or 3-pyridyl or 3,4,5-trimethoxy phenyl group; or ** simultaneously X represents a chlorine atom, Y and Z represent a hydrogen atom, Ar represents a 2-pyridyl or 4-pyridyl group. - 2. A compound according to claim 1, in which X is other than chlorine, and/or, when Ar represents a substituted phenyl group, its substituent(s) is(are) in the ortho or para position.
- 3. A compound according to claim 1 or 2, in which Het is selected in the group consisting of thienyl (preferably 2-or 3- thienyl), thiazolyl (preferably 2- or 4- thiazolyl), pyridyl (preferably 2-pyridyl), pyrrolyl (preferably 2-pyrrolyl), thiadiazolyl (preferably 5-thiadiazolyl) group.
- 4. A compound according to anyone of claims 1 to 3, in which Ar is monosubstituted and Het represents a thienyl radical.
- 5. A compound according to anyone of claims 1 to 4, in which:
only one, or two of the three radicals X, Y or Z
represent a radical other than the hydrogen atom, and/or when Z, Y or Z are a halogen atom, the atom in question is chlorine or bromine, and/or when X, Y or Z are a radical which is at least partially hydrocarbon in nature, this radical has preferably 1 to 4 carbon atoms, and 1 carbon atom being even more preferred - 6. A compound according to anyone of claims 1 to 5, in which Z is other than the hydrogen atom.
- 7. A compound according to anyone of claims 1 to 6, in which X and Y are the hydrogen atom.
- 8. A compound according to anyone of claims 1 to 7, in which Z is a chlorine atom or a methyl group.
- 9. A herbicidal composition which contains 0.05 to 95% by weight of an active substance according to anyone of claims 1 to 8 in combination with one or more solid or liquid carriers which are agriculturally acceptable, and/or surfactants which are agriculturally acceptable.
- 10. A weeding method which consists in applying, to the zone to be weeded and/or to the plants to be destroyed, an effective amount of a compound according to one of claims 1 to 8 or of a composition according to claim 9.
- 11. A compound which can be used especially as an intermediate for the preparation of a compound according to claim 1, this compound having one of the formulae (II), (IV), (VIII), (XI) or (XII) Fomule (II) Formule (IV) Formule (XI) Formule (XII) Formule (VIII) in which the various symbols have the meanings given in any of claims 1 to 8.
- 12. The process for the preparation of a compound according to one of claims 1 to 8, in which a compound of the arylidene-2-(pyrid-2'-yl)hydrazine type, which has, as its formula, the formula (II) according to claim 11, is reacted with an oxidant in accordance with a cyclising oxidation reaction.
- 13. The process according to claim 12, in which the oxidant is selected from amongst the metal cations derived from metals which have various degrees of oxidation and are at a higher degree of oxidation, or atmospheric oxygen.
- 14. The process according to claim 12, in which the oxidation reaction of the compound of the formula (II) is effected by adding a halogen, followed by a dehalogenation.
- 15. The process according to claim 12, in which the oxidation reaction of the compound of the formula (II) is effected by adding an N-halo-N-metallosulphonamidate (preferably chloramine T).
- 16. The process for the preparation of a compound according to one of claims 1 to 8, in which a compound of the 2-(aroylhydrazino)pyridine type which has, as its formula, the formula (III), is dehydrated (cyclising dehydration), in which the various substituents have the same meaning as in any of claims 1 to 8.
- 17. The process according to claim 16, which is carried out in the presence of a dehydrating agent.
- 18. The process for the preparation of a compound according to one of claims 1 to 8, in which a cyclising deamination is effected by heating a compound of the amidrazone type which has, as its formula, (IV) according to claim 11, in which the various substituents have the same meaning as in any of claims 1 to 8.
- 19. The process for the preparation of a compound according to one of claims 1 to 8, in which a compound of the hydrazine type of the formula (V) is reacted with a compound of the formula (VI): U1-C(=W1)-Ar according to the reaction:
(V) + (VI)-----> (I) + U1H + W1H2 the various radicals of these formulae (V) and (VI) having the same meanings as in any of claims 1 to 8, W1 represents an oxygen atom or an NH group, when W1 represents the oxygen atom, then U1 represents a hydroxyl group or alkoxy group or aroyloxy group, or a halogen atom, when W1 represents an NH group, then U1 represents an alkoxy group or alkylthio group or arylalkylthio group. - 20. The process for the preparation of a compound according to one of claims 1 to 8, in which a pyridine-type derivative of the formula (VIII) Formula (VIII) is reacted with a tetrazole-type compound of the formula (IX) X, Y, Z and Ar in these formulae having the same meaning as in any of claims 1 to 6, and T representing a halogen atom, preferably chlorine.
- 21. The process for the preparation of arylidene-2-(pyrid-2'-yl)hydrazines of the formula (II) according to claim 11, in which a 2-hydrazinopyridine of the formula (V) according to claim 11 is reacted with aldehydes of the formula Ar-CHO in which the symbols X, Y, Z and Ar have the meanings given in any of claims 1 to 8.
- 22. The process for the preparation of amidrazones of the formula (IV) according to claim 11, in which a 2-hydrazinopyridine derivative of the formula (V) according to claim 11 is reacted according to the equation:
(V) + Ar-C(=NH)-U3 ------> (IV) + U3H
the various radicals of these reactants and reaction products having the same meaning as in any of claims 1 to 8, and U3 is an alkoxy or alkylthio radical. - 23. The use of compounds of the formula (II) as herbicides.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9001267A FR2657610A1 (en) | 1990-01-29 | 1990-01-29 | TRIAZOLOPYRIDINES HERBICIDES. |
| FR9001267 | 1990-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2035144A1 true CA2035144A1 (en) | 1991-07-30 |
Family
ID=9393365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002035144A Abandoned CA2035144A1 (en) | 1990-01-29 | 1991-01-29 | Triazolopyridines herbicides |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0441718A1 (en) |
| JP (1) | JPH04234881A (en) |
| KR (1) | KR910014379A (en) |
| CN (1) | CN1053792A (en) |
| AU (1) | AU6997791A (en) |
| BR (1) | BR9100441A (en) |
| CA (1) | CA2035144A1 (en) |
| CS (1) | CS18491A2 (en) |
| FI (1) | FI910408A (en) |
| FR (1) | FR2657610A1 (en) |
| HU (1) | HUT56697A (en) |
| IE (1) | IE910200A1 (en) |
| IL (1) | IL97037A0 (en) |
| MA (1) | MA22046A1 (en) |
| OA (1) | OA09479A (en) |
| PT (1) | PT96586A (en) |
| YU (1) | YU13691A (en) |
| ZA (1) | ZA91643B (en) |
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| US8722894B2 (en) | 2007-09-14 | 2014-05-13 | Janssen Pharmaceuticals, Inc. | 1,3-disubstituted-4-phenyl-1H-pyridin-2-ones |
| US8748621B2 (en) | 2007-09-14 | 2014-06-10 | Janssen Pharmaceuticals, Inc. | 1,3-disubstituted 4-(aryl-X-phenyl)-1H-pyridin-2-ones |
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| US8841323B2 (en) | 2006-03-15 | 2014-09-23 | Janssen Pharmaceuticals, Inc. | 1, 4-disubstituted 3-cyano-pyridone derivatives and their use as positive allosteric modulators of MGLUR2-receptors |
| US8906939B2 (en) | 2007-03-07 | 2014-12-09 | Janssen Pharmaceuticals, Inc. | 3-cyano-4-(4-tetrahydropyran-phenyl)-pyridin-2-one derivatives |
| US8937060B2 (en) | 2009-05-12 | 2015-01-20 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo [4,3-A] pyridine derivatives and their use for the treatment of prevention of neurological and psychiatric disorders |
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| US10106542B2 (en) | 2013-06-04 | 2018-10-23 | Janssen Pharmaceutica Nv | Substituted 6,7-dihydropyrazolo[1,5-a]pyrazines as negative allosteric modulators of mGluR2 receptors |
| US10537573B2 (en) | 2014-01-21 | 2020-01-21 | Janssen Pharmaceutica Nv | Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use |
| US11369606B2 (en) | 2014-01-21 | 2022-06-28 | Janssen Pharmaceutica Nv | Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL96432A0 (en) * | 1989-11-30 | 1991-08-16 | Schering Ag | Pesticidal compositions containing pyridine derivatives and novel pyridine derivatives |
| DE4204816A1 (en) * | 1992-02-18 | 1993-08-19 | Bayer Ag | TRIAZOLO-PYRIDINE DERIVATIVES |
| DE4326758A1 (en) * | 1993-08-10 | 1995-02-16 | Basf Ag | [1,3,4] triazolo [1,5-a] pyridines |
| WO1995007275A1 (en) * | 1993-09-10 | 1995-03-16 | Ciba-Geigy Ag | Photochromic compounds, methods and intermediates for producing them and their use |
| EP0891334A1 (en) | 1996-04-03 | 1999-01-20 | Merck & Co., Inc. | Inhibitors of farnesyl-protein transferase |
| AU720199B2 (en) | 1996-09-30 | 2000-05-25 | Nihon Nohyaku Co., Ltd. | Bis-thiadiazole derivatives or salts thereof and agrohorticultural disease controller and method for using the same |
| AU725138B2 (en) | 1996-09-30 | 2000-10-05 | Nihon Nohyaku Co., Ltd. | 1,2,3-thiadiazole derivatives and salts thereof, disease controlling agents for agricultural and horticultural use, and method for the use thereof |
| WO1999040090A1 (en) * | 1998-02-04 | 1999-08-12 | Nissan Chemical Industries, Ltd. | Pyridine derivatives fused with azole and herbicide |
| DE10038019A1 (en) * | 2000-08-04 | 2002-02-14 | Bayer Ag | Substituted triazolopyride (az) ine |
| US20090215817A1 (en) * | 2004-08-18 | 2009-08-27 | Pfizer Inc | Novel Triazolopyridine Compounds for the Treatment of Inflammation |
| CA2722178C (en) * | 2008-04-25 | 2014-01-07 | Nippon Soda Co., Ltd. | Granular agrochemical composition and method of producing the same |
| CN112239467B (en) * | 2019-07-18 | 2023-06-02 | 青岛清原化合物有限公司 | Substituted 1,2, 4-triazolo [4,3-a ] pyridine derivatives, preparation method thereof, weeding composition and application |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1163355A (en) * | 1966-05-17 | 1969-09-04 | Borg Warner | Preparation of 5-Substituted Tetrazoles |
| DE1670139A1 (en) * | 1966-08-31 | 1970-10-29 | Boehringer Mannheim Gmbh | Process for the preparation of 3- (5-nitrofuryl-2) -s-triazolo [4.3-a] pyridine derivatives |
| ES400725A1 (en) * | 1972-03-13 | 1975-01-01 | Gallardo Antonio Sa | A procedure for the obtaining of derivatives of s-triazo - (4,3, -a) -piridine. (Machine-translation by Google Translate, not legally binding) |
| DE2720416A1 (en) * | 1976-05-21 | 1977-12-01 | Fisons Ltd | HETEROCYCLIC COMPOUNDS AND METHODS FOR THEIR PRODUCTION |
| US4347251A (en) * | 1981-07-13 | 1982-08-31 | American Cyanamid Company | Novel 3-substituted amino-1-substituted heteroaryl-2-pyrazolines |
| PT79024A (en) * | 1983-08-09 | 1984-09-01 | Ciba Geigy Ag | Process for the manufacture of novel acylated hydrazine compounds |
| JPS611665A (en) * | 1984-06-15 | 1986-01-07 | Ishihara Sangyo Kaisha Ltd | Pyridylhydrazine and pesticide containing the same |
| US4650872A (en) * | 1985-08-01 | 1987-03-17 | Merrell Dow Pharmaceuticals Inc. | 5-chloro-s-triazolo[4,3-a]-pyridine-7-carboxylic acids, useful as antiallergic agents |
-
1990
- 1990-01-29 FR FR9001267A patent/FR2657610A1/en not_active Withdrawn
-
1991
- 1991-01-18 MA MA22319A patent/MA22046A1/en unknown
- 1991-01-21 IE IE020091A patent/IE910200A1/en unknown
- 1991-01-24 IL IL97037A patent/IL97037A0/en unknown
- 1991-01-25 AU AU69977/91A patent/AU6997791A/en not_active Abandoned
- 1991-01-28 YU YU13691A patent/YU13691A/en unknown
- 1991-01-28 EP EP91420024A patent/EP0441718A1/en not_active Withdrawn
- 1991-01-28 HU HU91288A patent/HUT56697A/en unknown
- 1991-01-28 FI FI910408A patent/FI910408A/en not_active Application Discontinuation
- 1991-01-28 PT PT96586A patent/PT96586A/en not_active Application Discontinuation
- 1991-01-28 CS CS91184A patent/CS18491A2/en unknown
- 1991-01-29 CN CN91100658A patent/CN1053792A/en active Pending
- 1991-01-29 CA CA002035144A patent/CA2035144A1/en not_active Abandoned
- 1991-01-29 KR KR1019910001480A patent/KR910014379A/en not_active Application Discontinuation
- 1991-01-29 OA OA59941A patent/OA09479A/en unknown
- 1991-01-29 JP JP3094660A patent/JPH04234881A/en active Pending
- 1991-01-29 BR BR919100441A patent/BR9100441A/en unknown
- 1991-01-29 ZA ZA91643A patent/ZA91643B/en unknown
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| US8841323B2 (en) | 2006-03-15 | 2014-09-23 | Janssen Pharmaceuticals, Inc. | 1, 4-disubstituted 3-cyano-pyridone derivatives and their use as positive allosteric modulators of MGLUR2-receptors |
| US9266834B2 (en) | 2006-03-15 | 2016-02-23 | Janssen Pharmaceuticals, Inc. | 1, 4-disubstituted 3-cyano-pyridone derivatives and their use as positive allosteric modulators of MGLUR2-receptors |
| US8906939B2 (en) | 2007-03-07 | 2014-12-09 | Janssen Pharmaceuticals, Inc. | 3-cyano-4-(4-tetrahydropyran-phenyl)-pyridin-2-one derivatives |
| US9067891B2 (en) | 2007-03-07 | 2015-06-30 | Janssen Pharmaceuticals, Inc. | 1,4-disubstituted 3-cyano-pyridone derivatives and their use as positive allosteric modulators of mGluR2-receptors |
| US11071729B2 (en) | 2007-09-14 | 2021-07-27 | Addex Pharmaceuticals S.A. | 1′,3′-disubstituted-4-phenyl-3,4,5,6-tetrahydro-2H,1′H-[1,4′]bipyridinyl-2′-ones |
| US8748621B2 (en) | 2007-09-14 | 2014-06-10 | Janssen Pharmaceuticals, Inc. | 1,3-disubstituted 4-(aryl-X-phenyl)-1H-pyridin-2-ones |
| US8722894B2 (en) | 2007-09-14 | 2014-05-13 | Janssen Pharmaceuticals, Inc. | 1,3-disubstituted-4-phenyl-1H-pyridin-2-ones |
| US9132122B2 (en) | 2007-09-14 | 2015-09-15 | Janssen Pharmaceuticals, Inc. | 1′,3′-disubstituted-4-phenyl-3,4,5,6-tetrahydro-2H,1′H-[1,4′]bipyridinyl-2′-ones |
| US9114138B2 (en) | 2007-09-14 | 2015-08-25 | Janssen Pharmaceuticals, Inc. | 1′,3′-disubstituted-4-phenyl-3,4,5,6-tetrahydro-2H,1′H-[1,4′] bipyridinyl-2′-ones |
| US8785486B2 (en) | 2007-11-14 | 2014-07-22 | Janssen Pharmaceuticals, Inc. | Imidazo[1,2-A]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors |
| US8691849B2 (en) | 2008-09-02 | 2014-04-08 | Janssen Pharmaceuticals, Inc. | 3-azabicyclo[3.1.0]hexyl derivatives as modulators of metabotropic glutamate receptors |
| US8697689B2 (en) | 2008-10-16 | 2014-04-15 | Janssen Pharmaceuticals, Inc. | Indole and benzomorpholine derivatives as modulators of metabotropic glutamate receptors |
| US8691813B2 (en) | 2008-11-28 | 2014-04-08 | Janssen Pharmaceuticals, Inc. | Indole and benzoxazine derivatives as modulators of metabotropic glutamate receptors |
| US9085577B2 (en) | 2009-05-12 | 2015-07-21 | Janssen Pharmaceuticals, Inc. | 7-aryl-1,2,4-triazolo[4,3-A]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors |
| US10071095B2 (en) | 2009-05-12 | 2018-09-11 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo [4,3-A] pyridine derivatives and their use for the treatment of neurological and psychiatric disorders |
| US8716480B2 (en) | 2009-05-12 | 2014-05-06 | Janssen Pharmaceuticals, Inc. | 7-aryl-1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors |
| US8946205B2 (en) | 2009-05-12 | 2015-02-03 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors |
| US9226930B2 (en) | 2009-05-12 | 2016-01-05 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo [4,3-a] pyridine derivatives and their use for the treatment of prevention of neurological and psychiatric disorders |
| US8937060B2 (en) | 2009-05-12 | 2015-01-20 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo [4,3-A] pyridine derivatives and their use for the treatment of prevention of neurological and psychiatric disorders |
| US9737533B2 (en) | 2009-05-12 | 2017-08-22 | Janssen Pharmaceuticals. Inc. | 1,2,4-triazolo [4,3-A] pyridine derivatives and their use for the treatment of prevention of neurological and psychiatric disorders |
| US9271967B2 (en) | 2010-11-08 | 2016-03-01 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors |
| US9012448B2 (en) | 2010-11-08 | 2015-04-21 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of MGLUR2 receptors |
| US8993591B2 (en) | 2010-11-08 | 2015-03-31 | Janssen Pharmaceuticals, Inc. | 1,2,4-triazolo[4,3-a] pyridine derivatives and their use as positive allosteric modulators of MGLUR2 receptors |
| US10106542B2 (en) | 2013-06-04 | 2018-10-23 | Janssen Pharmaceutica Nv | Substituted 6,7-dihydropyrazolo[1,5-a]pyrazines as negative allosteric modulators of mGluR2 receptors |
| US10584129B2 (en) | 2013-06-04 | 2020-03-10 | Janssen Pharmaceuticals Nv | Substituted 6,7-dihydropyrazolo[1,5-a]pyrazines as negative allosteric modulators of mGluR2 receptors |
| US9708315B2 (en) | 2013-09-06 | 2017-07-18 | Janssen Pharmaceutica Nv | 1,2,4-triazolo[4,3-a]pyridine compounds and their use as positive allosteric modulators of MGLUR2 receptors |
| US10537573B2 (en) | 2014-01-21 | 2020-01-21 | Janssen Pharmaceutica Nv | Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use |
| US11103506B2 (en) | 2014-01-21 | 2021-08-31 | Janssen Pharmaceutica Nv | Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use |
| US11369606B2 (en) | 2014-01-21 | 2022-06-28 | Janssen Pharmaceutica Nv | Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use |
| US12048696B2 (en) | 2014-01-21 | 2024-07-30 | Janssen Pharmaceutica Nv | Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| MA22046A1 (en) | 1991-10-01 |
| CN1053792A (en) | 1991-08-14 |
| KR910014379A (en) | 1991-08-31 |
| CS18491A2 (en) | 1991-09-15 |
| HUT56697A (en) | 1991-10-28 |
| YU13691A (en) | 1994-01-20 |
| FR2657610A1 (en) | 1991-08-02 |
| OA09479A (en) | 1992-11-15 |
| JPH04234881A (en) | 1992-08-24 |
| IE910200A1 (en) | 1991-07-31 |
| FI910408A0 (en) | 1991-01-28 |
| EP0441718A1 (en) | 1991-08-14 |
| HU910288D0 (en) | 1991-08-28 |
| ZA91643B (en) | 1991-11-27 |
| AU6997791A (en) | 1991-08-01 |
| FI910408A (en) | 1991-07-30 |
| BR9100441A (en) | 1991-10-22 |
| IL97037A0 (en) | 1992-03-29 |
| PT96586A (en) | 1991-10-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |
