CH655312A5 - CHLORACETAMIDE. - Google Patents

Description

The present invention relates to new 5-membered heteroaromatic compounds which carry an N-substituted chloroacetamido group on a ring carbon atom, their use as a herbicide, preparations to facilitate this use in agriculture and the preparation of the new compounds .

Some herbicidal N-substituted a-haloacetanilides are known. US Pat. No. 4,282,028 describes N-substituted N-2,5-dialkyl-pyrrole-1-yl) haloacetamides which have a herbicidal action and regulates plant growth. There is a need for more effective herbicides. The new 5-membered heteroaromatic compounds are particularly effective herbicides with a suitable soil persistence.

The present invention relates to compounds of the formula I.

^ COCH2Cl

Ar-N <^ I

wherein

Ar is a 5-membered heteroaromatic ring which contains 1 or 2 ring heteroatoms selected from O, S and N and is bonded to the N atom of the N (Y) COCH2Cl group by a ring carbon atom, where, if Ar is pyrazolyl, the N (Y) COCH2Cl group is in the 4-position, and

Y Allenyl, CH2-CH = C = CH2, a hydrocarbon is selected from the series Q gAlkyl, C3 gAlkenyl, C3 gAlkinyl, C3 gcycloalkyl, C5 8cycloalkenyl, C3_8cycloalkyl-C1_5alkyl, the hydrocarbon being unsubstituted or by halogen, selected from the series F , Cl or Br, is substituted; or a group CHR, -COY], in which R, represents H or C) 5-alkyl, and Y] together with the CO group to which Y1 is bonded forms an ester or amide function; or represents a group R2-Az in which

R2 stands for CH2 or CH2-CH2 which is unsubstituted or substituted by Q 5, and

Az denotes a heteroaromatic ring selected from a di- or triazole bonded to R2 with a ring nitrogen atom, a 5-membered hetero ring containing 1 to 3 heteroatoms bonded to R2 with a ring carbon atom, selected from O, S and N, and a pyrimidine group; or a 2-oxo-l-pyrrolidinyl group in which a CH2 group can be replaced by O, S or NCH3 and 5-oxo and / or bicyclic benz [c] linked derivatives of such 2-oxo-l-pyrrolidinyl -Group, or a group A-OR3, in which R3 is H or a hydrocarbon which is selected from the series consisting of C 1-8 alkyl, C38 alkenyl, C3_8 alkynyl, C3 8cycloalkyl, C5..gcycloalkenyl and C3_8Cy-cloalkyl-Q 5- alkyl, which hydrocarbon is unsubstituted or substituted; or for a group

N = C;

-R4

'R4' stands

in which

R4 represents a hydrocarbon selected from the series consisting of C] _5alkyl, C3_5alkenyl, C3_5alkynyl, C3_8cycloalkyl, C3_gcycloalkenyl and C ^ gcycloalkyl-C ^ alkyl, the hydrocarbon being unsubstituted or substituted by halogen selected from F, Cl and Br; or allenyl means

R4 'H or one of the meanings given for R4, and

A represents a hydrocarbon radical which can be linked to R3 to form a hetero ring containing 1 or 2 O-heteroatoms, the N and O atoms connected by A being separated from one another by up to 3 carbon atoms; or a group CHR5-CHR5 '= = NOR} means wherein

R4 has the above meaning,

R5 and R5 'independently of one another are H or CH3 or together are (CH2) 3 or (CH2) 4, or a group CHR6-N (CH3) COCH3 in which R6 is H or Q_3 alkyl.

The Ar group can be unsubstituted or substituted. If Ar is substituted, it can carry substituents in any possible position: preferred positions of such substituents are in the o-position, in particular in the o, o'-position of the

3,655,312

Chloroacetamide group, where additional substituents may be present. Examples of suitable substituents of Ar are halogen selected from F, Cl and Br; CMAlkyl, unsubstituted or substituted by halogen (F, Cl, Br), C ^ alkoxy or Q_6 5 cycloalkyl; C2 4 alkenyl unsubstituted or substituted by C [4 alkoxy; C3 6cycloalkyl; CHO or C2 4 alkanoyl and functional derivatives thereof such as oximes, acetals, ketals (e.g. C (= NOCwAlkyl) -CI_3alkyl; C (OC, _4Al-alkyl) 2-C, _3alkyl; CH (OC, 4Alkyl) 2 etc. ); C ^ alkyl-S, C, ^ A1-iokyl-SO, Ci 4alkyl-S02, C, _5alkoxy-carbonyl; C ^ alkoxy, unsubstituted or substituted by halogen or C ^ alkoxy; C2 4 alkenyloxy, C2_4 alkynyloxy; HO and CH2OH and esters thereof (e.g. esters with organic carboxylic acids such as formic acid, C2_5alkanecarboxylic acid or a halogenated derivative thereof, e.g. acetic acid or chloroacetic acid).

Any substituents of Ar that are not in the o-position of the chloroacetamide group are preferably selected from the series C ^ alkyl (e.g. CH3), halogen (e.g. Cl, Br) and C] _4alkoxy-carbonyl (e.g. COOCH3).

20 If Ar contains 2 heteroatoms, one of them is N; the other is preferably O or S.

A preferred subgroup of compounds of the formula I are compounds in which Ar has either one hetero ring atom (as in pyrrolyl, thienyl, furanyl) or 2 adjacent 25 hetero ring atoms (as in isoxazolyl, isothiazolyl, pyrazolyl). The chloroacetamide group is preferably attached to the ring carbon atom which is in the β-position of the hetero ring atom (s); accordingly in the 3-position if Ar is pyrrole, thiophene or furan and in the 4-position if Ar 30 is isoxazole, isothiazole or pyrazole. A preferred subgroup of the latter group are the compounds in which the Ar group is in the ortho-more preferred ortho-ortho 'position of the acetamide group, in particular if the substituents are selected from the previously defined group. Each -35 of the ring N atom with a free valence can be unsubstituted (i.e. stand for NH) or substituted; if it is substituted, it is preferably substituted by C 1-4 alkyl, in particular by CH3 or C2-5. Ar stands in particular for a thiophene, isothiazole or isoxazole, preferably for an isothiazole or thiophene ring. A particularly preferred subgroup of the compounds of the formula I are compounds in which Ar denotes thiophene, in particular that in which Ar denotes at least 2,4-position-substituted 3-thienyl, more particularly the 3-thienyl compounds 45 in which the substituents in 2- and 4 Position are selected from C] _4alkyl and C ^ alkoxy.

If Y, R3, R4 and / or R4 'is a halogen-substituted hydrocarbon, halogen is in particular Cl or Br; such a substituted hydrocarbon is in particular monosubstituted. If Y is a halogen-substituted hydrocarbon, the halogen substitution is generally preferably not in the 1-position if the use as a herbicide is intended (such 1-halogenated compounds are generally not stable, but they are valuable intermediates for the preparation of those in which Y Is alkoxyalkyl or pyrazolyl-methyl); a suitable example of such a meaning of Y is 2-Cl-ethyl.

If Y, R3, R4 and / or R4 'is Ci_8alkyl, C3_8alkenyl or 60 C3_8alkynyl, they have in particular up to 5 carbon atoms. If Y, R3, R4 and / or R / mean cycloalkyl or cycloalkenyl or contain such a group, this cycloaliphatic group preferably contains up to 6 carbon atoms.

If Rj is Cj 5 alkyl, it is in particular CH3 65 or C2H5, preferably CH3. The term ester or amide function in connection with the meaning of Yj encompasses any function which is obtained by reacting a COOH group of an acid with an organic compound.

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4th

acts with elimination of water, e.g. by reaction with an alcohol, an amine, a mercaptan, an oxime, a hydrazine, hydrazide or hydrazone. Examples of such ester meanings of Y] are C ^ alkoxy-CO, C3 5alkynyl-0-C0 etc. Examples of suitable amide function meanings of Yj are Ci ^ alkylamino-CO, di (Ci ^ alkyl) -amino-CO, CONHNH2 and CONH-N = C (C, _3 alkyl) 2.

If R2 is CH2, it can carry 1 or 2, in particular 1, Q_5alkyl. If R2 is CH2CH2, it can carry up to 4 Q_4 alkyl groups and is preferably mono- or disubstituted. If CH2CH2 is disubstituted, the substituents are expediently on different carbon atoms.

Preferred C1-4 alkyl substituents of R2 are CH3 and C2H5, in particular CH3. If R2 is substituted by C ^ 5 alkyl, it is preferably monosubstituted. R2 means in particular CH2 or CH (CH3).

If Az represents one of the aromatic hetero rings defined above, this ring can be unsubstituted or substituted; suitable substituents of such Az meanings are e.g. one or more Ci_5 alkyl groups (such as CH3, C2H5); such substituted aromatic hetero rings are in particular mono- or disubstituted.

If Az represents a di- or triazole radical, this is in particular unsubstituted or substituted 1-pyrazolyl,

1-imidazolyl, 1,2,3-triazol-l-yl or 1,2,4-triazol-l-yl, preferably 1-pyrazolyl or 3,5-di-CH3-l-pyrazolyl.

If Az represents one of the 5-membered hetero-rings defined by a ring C atom attached to R2, this is e.g. a furyl, thienyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, 1,2,4 or 1,2,3-thia or oxadiazolyl, or a 1,3,4-triazolyl group, the Heteroring can be unsubstituted or substituted, e.g. by one or two substituents selected from the series CMAlkyl, Ci ^ alkylthio and C ^ alkoxy; suitable examples of such meanings are 2-furyl, 2-thienyl, 2-CH3-4-thiazolyl,

3-CH3-5-isoxazolyl, 2-C2H5-l, 3,4-oxadiazol-5-yl, 3-CH3-l, 2,4-oxadiazol-5-yl, l-CH3-2-CH3S-l, 3,4-triazol-5-ylund

2-CH3-1,3,4-triazol-5-yl.

If Az represents a pyrimidine group, this can be bonded to R2 through its 2-, 4- or 5-position, and is e.g. for 2-pyrimidinyl.

If Az represents one of the bicyclic 2-oxo-1-pyrolidinyl groups defined above, this can be unsubstituted or, e.g. be substituted by halogen; an example of such a meaning is 2-oxo-l, 3-benzothiazol-3-yl and that

4-chloro derivative thereof.

If R3 is one of the hydrocarbon radicals defined above, this can be unsubstituted or e.g. be substituted by halogen, CN, an azole group such as 1-pyrazolyl and / or C14alkoxy; such substituted hydrocarbon meanings of R3 are CH2CH2C1, (l-pyrazolyl) -CH2, CH2CH2CN and 3,5-dimethyl-l-pyrazolyl.

Suitable meanings of A-0-R3 if A is linked to R3 to form a ring are e.g. l, 3-dioxolan-4-yl-C, 3alkylene, l, 3-dioxolan-2-yl-C ^ 3alkylene and 2- or 3-tetrahydro-furyl-Ci_3alkylene.

If A is not linked to R3 to form a ring, A means in particular a non-aromatic, in particular a Ci_8alkylene group which separates the O and N atoms to which it is attached with 1 to 3, in particular 1 to 2, carbon atoms. A suitable meaning of A is e.g. the CH2 or CH2-CH2 group and monomethylated derivatives thereof, in particular CH2, CH (CH3), CH2CH2, CH (CH3) CH2; R3 is then in particular Q 3 alkyl such as CH3, C2H5 and nC3H7.

Group A is unsubstituted or substituted, e.g. by Q 5 alkoxy. Substituted meanings of A are preferably monosubstituted.

The compounds of formula I are prepared by a) in a compound of formula II

Ar-N

CO-CH2OH ■ Y

II

wherein Ar and Y have the above meaning, the HO group io of the N-hydroxyacetyl group is substituted by Cl,

b) a compound of formula III

AR-NH-COCH2Cl

III

is wherein Ar has the above meaning, with a compound of formula IV

LY

IV

20 where

Y has the above meaning and L represents a group which can be split off under the conditions of an N-alkylation reaction,

c) for the preparation of a compound of formula Ia

25th

^ COCH2Cl

AR-N <

~ CH-Y2 Ia

30th

R '

wherein R 'is H or C ^ alkyl,

Y2 denotes Az ', OR3 or N (CH3) COCH3,

Az 'is a di- or 35-triazole bonded to CHR' with its N atom, and Ar and R3 are as defined above, means a compound of the formula V.

AR-N

-COCH2Cl

CH-Cl

I.

R '

45

wherein Ar and R 'have the above meaning, with a reactive derivative of a compound of formula VI

HY,

where Y2 has the above meaning,

d) a compound of formula VII

50

AR-NH-Y

VII

wherein Ar and Y are as defined above, with chlorace-55 tyl chloride, or a reactive functional derivative thereof, N-acetylated.

Process a) can be carried out analogously to the methods known for the substitution of the OH group by chlorine.

Such a substitution can e.g. by treating a compound of formula II with a chlorinating agent, e.g. with thionyl chloride, under the reaction conditions known for analogous reactions.

According to a variant of this chlorination process, the compounds of the formula II can first be converted into a corresponding sulfonyloxy derivative, e.g. by O-sulfonation with the aid of a sulfonyl halide, and this then by nucleophilic substitution of the sulfonyloxy

Group can be converted by chlorine into the desired compounds of formula I.

Reactants which provide the Cl anion required for the nucleophilic substitution are, for example, alkali metal chlorides such as NaCl, quaternary tetrabutylammonium chloride and 4-dimethylaminopyridine hydrochloride. Such substitution is expediently in CH2C12 or in an aqueous organic two-phase system in which the organic phase is, for example, a hydrocarbon such as a hydrocarbon is carried out in the presence of a suitable phase transfer catalyst, preferably with heating to 40 ° to 120 ° C.

Process b) can be carried out analogously to known processes using methods known for the N-alkylation of amides. The reaction is conveniently carried out in a solvent which is inert under the reaction conditions, e.g. Dimethoxyäthan or acetonitrile, or in an aqueous / organic two-phase system in the presence of a phase transfer catalyst.

Suitable meanings of L (in formula IV) are Cl, Br or the sulfonyloxy radical of an organic sulfonic acid such as mesyloxy or p-tosyloxy.

The compounds of formula III are used in particular in salt form, preferably in alkali metal salt form, e.g. used in Na salt form. Such salts can be obtained in a known manner by reacting a compound of formula III with a base such as an alkali metal amide, hydride, hydroxide or alcoholate.

For the preparation of the compounds of formula Ia according to process c), the compounds of formula V are expediently used as an alkali metal salt, e.g. used as Na salt. If Y2 is a diazole or triazole, the compounds of the formula V can also be used as an N-trialkylsilyl (e.g. N-trimethylsilyl) compound. The implementation is analogous to known methods.

The reaction according to process d) can also be carried out analogously to known methods, under conditions known for the N-chloroacetylation of amines. If C1C0CH2C1 is used as the N-chloroacetylating agent, it is expedient to work in the presence of an acid-binding agent such as K2C03.

The compounds of the formula I can be isolated from the reaction mixture and worked up in a known manner.

The conversion of a compound of formula I into another compound of formula I, e.g. Conversion of an acid into an ester, a carbonyl compound into an oxime, a haloalkyl compound into an ether compound (or vice versa) etc. can also be carried out analogously to known methods. The compounds according to the invention have one or more asymmetric centers and can therefore exist in optically active, diastereomeric, racemic or geometric isomeric forms. In general, such compounds are used as a mixture in the herbicidal processes and preparations according to the invention, although the separation can also be carried out analogously to known methods.

The compounds of formula II, III, V and VII are new.

The compounds of the formula II can be obtained by ammonolysis of the esters of the compounds of the formula VIII

ARNH,

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IX

AR-NHCOCH2OH

VIII

wherein Ar has the above meaning, with a carboxylic acid, and then introducing a group Y (as defined above) in compounds of the formula VIII, by N-alkylation.

Such esters are obtained e.g. by N-acylation of the corresponding compounds of the formula IX.

where Ar has the above meaning with a suitable ester of HOCH2COCl, e.g. with CH3CO-OCH2COC1. 5 The compounds of formula III are obtained by N-acylation of a compound of formula IX with chloroacetylchloride.

Compounds of formula V (a subset of compounds of formula I) are obtained e.g. by reacting 10 a compound of formula IX with an aldehyde and reacting the Schiff thus obtained see base with chloroacetyl chloride.

Compounds of formula VII can be obtained by N-alkylation of compounds of formula IX. Solls che alkylation can be carried out by known methods, with the aid of suitable alkylating agents (e.g. halides), or else, where appropriate, reductively using a Schiff base or an amide.

Many of the compounds of Formula IX are new. 20 A particularly valuable group of new compounds of the formula IX are 3-aminothiophenes which carry substituents from the series C] _4alkyl and C ^ alkoxy in the 2- and 4-position; they are referred to below as compounds of the formula IXa. The compounds of formula IXa are also the subject of the invention.

The compounds of formula IX can be obtained by reduction of the corresponding NO 2 compounds, e.g. by catalytic hydrogenation under hydrogen pressure in the presence of palladium. Compounds of the formula IXa which have a CH3 group in the 2- or 4-position can be obtained by reducing the corresponding thiophene carboxylates using complex hydrides such as Na-bis (methoxyethoxy) aluminum hydride. If desired, the compounds of formula IXa can also be obtained by hydrolysis of the corresponding carbamate esters, e.g. of the corresponding benzyl carbamate can be obtained. The carbamate esters required as starting compounds can e.g. from the corresponding acids via which azides are obtained, followed by a Curtius rearrangement.

If the preparation of the starting compounds is not described, these are known or can be prepared and purified analogously to known methods or those described here.

The compounds according to the invention have herbicidal activity, herbicidal here being understood in a general sense as a compound which permits growth inhibition or growth influencing of plants. With plants are meant germinating seeds, seedlings and established vegetation including underground parts.

The valuable herbicidal activity of the compounds according to the invention goes e.g. from the damage caused by test quantities of 1.4 to 5.6 kg / ha after pre- or post-em application (pre- or post-emergence) in mono- and dicotyledonous plants such as Lepidium sativum, Avena sativa, Agrostis alba 55 and Lolium perenne can be observed. Because of this herbicidal action, the compounds according to the invention are suitable for combating dicotyledonous or monocotyledonous weeds, as is confirmed by additional provisions with representative compounds 60 with test amounts corresponding to an application amount of 0.2 to 5.0 kg (for example 0.2, 1.0 and 5.0 kg) per ha of a compound according to the invention on dicotyledon weeds such as Amaranthus retroflexus, Capsella bursa-pastoris, Chenopodium alba, Stellaria media, Senecio vulgaris, Galium aparine, 65 and on grasses such as Agropyron repens, Agrostis alba , Alope-curus myosuroides, Apera spica-Venti, Avena fatua, Echi-nochloa crus-galli, Bromus tectorum, Sorghum halepense, Digitaria spp and Setaria spp. Show additional experiments

655 312 6

Favorable soil resistance of the compounds according to the invention. The compounds according to the invention can also fertilize. Form of microcapsules can be used.

The compounds according to the invention are less toxic. Additives which can be accentuated for herbicides can likewise be used against crop plants than against weeds. The selective herbicidal preparations used are e.g. for herbicidal activity e.g. in corn, soybeans, cotton, sugar and 5 to improve the effect and to avoid foaming, gluing and cork beet, potatoes, alfalfa, sunflowers, rapeseed, rosion.

Peanuts and flax observed, depending on the term used. The term surfactants as used herein

Substance and application amount. The det according to the invention means any material which is acceptable for herbicides, and the compounds are therefore also suitable for use as selective emulsifiability, wettability and dispersibility herbicides in useful plants. 10 gives or the improvement of other surface properties

The present invention accordingly also relates to a combination such as e.g. Spread and liability on plant animal drives to control unwanted plants (Unlen causes.

herbs), especially in crops, preferred examples of such surfactants are sodium, in one of the crops mentioned above, lignin sulfonate and lauryl sulfate.

by treating the site in question with a herbicide. The term thinner as used herein means an effective amount (with a selectively herbicidally liquid or solid herbicidally acceptable material, the amount if the site to be treated is a crop area). is used to dilute the active ingredient to a usable or a particularly preferred and advantageous method desired form. For dusts or according to the invention, the pre-em application (pre-em Un-granules, e.g. talc, kaolin or diatomaceous earth, for herbs and useful plants) of a compound of formula I in 20 liquid concentrated forms e.g. a hydrocarbon such as the selective control of weeds in crop xylene or an alcohol such as isopropanol, and for liquid Ap crops. application forms e.g. Water or diesel oil.

For the generally herbicidal and also for the selectively herbicidal. The preparations according to the invention can also contain the anidic application of the compounds according to the invention, the substances which have biological activity, how the amount to be applied will vary depending on the culture, e.g. Compounds with a similar or complementary herbicide (if selective application is intended) and andicidal activity or compounds with antagonistic, other variables such as the compound used, type of agicidal or insecticidal activity.

application, treatment conditions, etc. The following are specific examples of herbicides

Experts can describe the suitable application amount by means of preparations. (Parts are parts by weight). Routine tests determine e.g. by comparison in the 30th

Greenhouse of the activity of the compound according to the invention Example A

with a standard for which the application quantity is known. 25 parts of a compound according to the invention, e.g. the

In general, however, satisfactory results are obtained. Compound No. 25.25 parts of fine, synthetic silicate, 2 targets with an amount of approximately 0.1 to 5.0 kg / ha, in particular 35 parts of sodium lauryl sulfate, 3 parts of sodium lignin sulfonate and especially from 0.2 to 4.0 kg / ha, preferably from 0.5 to 45 parts of finely divided kaolinite are mixed and so long

3.0 kg / ha, the application being repeated if necessary, ground until the average particle size is approximately 5 microns. When used in crops, the spray powder obtained is generally not more than 3 kg / ha before use with water. thins into a spray liquor with the desired concentration.

The compounds according to the invention can and are advantageously in the form of herbicidal preparations together, Example B

with thinners acceptable for herbicides. Appropriate emulsion concentrate formulations contain 0.01 to 99% by weight of 20 parts of a compound according to the invention, e.g. the

Active ingredient, 0 to 20% of surface-active compound acceptable for herbicides. No. 25.40 parts of xylene, 30 parts of dimethylformative substances and 1 to 99.99% of a solid or liquid veramid and 10 parts of an emulsifier (for example ATLOX 4851 B, thinner, higher ratios of surface-active substances: a mixture of Ca-alkylarylsulfonate and polyethoxylated

Active ingredients are sometimes desired and are fulfilled by the triglyceride from Atlas Chemie GmbH) are strongly incorporated into the preparation or in the tank mix. Mix in until a homogeneous liquid is obtained. The emulsion concentrate thus contained in the form of the preparations in general contains 0.01 to 25% by weight of active ingredient with water before use. so diluted.

Smaller amounts of active ingredient can of course be present, depending on the intended application and example C physical properties of the active ingredient. Concentrated granules

Formulations which are diluted before use, 5 kg of a compound according to the invention e.g. the Ver contain 2 to 90% by weight, preferably 10 to 80, compound no. 25, are dissolved in 251CH2C12. The solution weight% of active ingredient. then becomes 95 kg of attapulgite with a grain size of 24/48 mesh / inch

Suitable formulations of the inventive and mixed. The solvent is removed from compounds including dusts, granules, pellets, reduced pressure.

Pension concentrates, wettable powders, emulsions. The invention is illustrated by the following examples, er sionszentrate etc. They are refined by known methods, 60; Temperatures are given in ° C. Pressure details e.g. by mixing the compounds according to the invention in torr and Rf values on silica gel, unless otherwise obtained with thinners. Liquid preparations are given.

e.g. by mixing the constituents, fine-grained solid preparations by mixing and grinding, suspension concentration end compounds would occur by wet grinding and granules and pellets by Im- 65 Example 1

impregnate or coat submitted carriers with N- (2,4-dimethyl-thien-3-yl) -N- (1,3-dioxolan-2-ylmethyl) active ingredient or by agglomeration techniques (fluidized bed -chloroacetamide (process a))

e.g.) received. To a well-stirred mixture of 1.7 g (0.0063 mol)

N- (2,4-dimethylthien-3-yl) -N- (1,3-dioxolan-2-yl-methyl) -hydroxyacetamide, 58 mg benzyltriethylammonium chloride,

7 ml of toluene and 7 ml of 30% NaOH are added dropwise, without cooling, 1.31 g (0.0069 mol) of p-toluenesulfonyl chloride in 3.5 ml of toluene. After the exothermic reaction has ended, stirring is continued for 20 hours at room temperature.

The toluene phase is then separated, washed with water and dried over Na2S04. The solvent is removed by red evaporation and recrystallization of the crude residue in diethyl ether gives the N- (2,4-dimethylthien-3-yl) -N- (1,3-dioxolan-2-ylmethyl) tosyloxyacetamide ("tosylate" ) from m.p. 101-103 °.

A stirred mixture of 2.16 g (0.0051 mol) of the tosylate, 1.84 g (0.0066 mol) of tetrabutylammonium chloride,

8 ml of water and 16 ml of toluene are heated to 90 ° for 6 hours. The toluene phase is separated off, dried (Na2S04) and concentrated in vacuo. The residue is chromatographed on a silica gel column. Elution with hexane-ethyl acetate 2: 1 gives the title compound in the form of analytically pure crystals of mp 76-78.

Example 2

N- (2,4-Dimethylthien-3-yl) -N-methoxyethylchloroacetamide (process a)

0.93 g (0.008 mol) of mesyl chloride in 20 ml of dry CH2C12 are cooled without cooling a stirred mixture of 2.0 g (0.008 mol) of N-2,4- (dimethylthien-3-yl) -N-methoxy-ethyl -hydroxyacetamide and 0.92 g (0.008 mol) of 4-dimethylaminopyridine (DMPA) in 80 ml of dry CH2C12.

The mixture thus obtained, which contains DMPA hydrochloride and the methanesulfonate of the starting compound, is heated, evaporated for 25 hours and then under vacuum.

The remaining oil solidifies after chromatography on silica gel (eluted with diethyl ether) and cooling at - 20 °; Mp 54-55 °.

Example 3

Ethyl N-chloroacetyl-N- (2-carbomethoxy-4-methyl-thien-3-yl) -aline (process b)

9.9 g (0.04 mol) of N- (2-carbomethoxy-4-methylthien-3-yl) chloroacetamide are added in portions to a well-stirred suspension of 1.5 g (0.05 mol) of NaH (80 % dispersion in mineral oil) in 250 dry dimethoxyethane (DME).

After the addition has ended, the remaining solution of the Na salt is stirred for a further hour at 50 °, then left to cool to room temperature and then with a solution of 7.25 g (0.04 mol) of ethyl 2-bromopropionate in Treated 50 ml dry DME.

After a reaction period of 4 hours at 50 °, the mixture is filtered and evaporated in vacuo (50 ° / 0.01 Torr). After chromatography on silica gel (eluted with diethyl ether-hexane 2: 1), the remaining brown oil is subjected to bulb tube distillation, the analytically pure title compound, b.p. 135 ° / 0.005 torr, being obtained.

Example 4

N- (1H-pyrazol-l-ylmethyl) -N- (2,4-dimethylthien-3-yl) chloroacetamide (method b)

To a well-stirred mixture of 19.35 g (0.095 mol) of N- (2,4-dimethylthien-3-yl) chloroacetamide, 4.15 g (0.01 mol) of benzyldimethylhexadecylammonium chloride, 40 g (1 mol ) NaOH, 200 ml of CH2C12 and 40 ml of H20 are added to 17 g (0.11 mol) of solid 1-chloromethyl-pyrazole hydrochloride in such a way that the temperature does not exceed 25 °.

When the addition is complete, the reaction mixture is

7 655 312

rend 2> / 2 hours at room temperature. Then 100 ml H20 are added. The organic phase is separated off, washed with 3,200 ml portions of water, dried over Na2SO4 and evaporated to dryness. The residue 5 is chromatographed on silica gel. Elution with hexane-diethyl ether 1: 1 gives the analytically pure title compound in the form of a syrup which crystallizes after cooling overnight at -20 °, mp. 88-89 ° (crystallization in diethyl ether).

Example 5

Ethyl N- (chloroacetyl) -N- (3,5-dimethyl-isoxazol-4-yl) alanine (process b)

9.4 g (0.05 mol) of N- (3,5-dimethylisoxazol-4-yl) chloroacetamide in 150 ml of dry CH3CN are added dropwise to an (80% is dispersion in mineral oil) in 25 ml of dry CH3CN. After the exothermic reaction (34 °) has ended, the solution of the Na salt is left to cool to room temperature and then treated with 9.05 g (0.05 mol) of ethyl 2-bromopropionate in 25 ml of dry CH3CN. 20 After the addition has ended, the reaction mixture is heated to 50 ° for 3 hours and then evaporated to dryness. The residue is taken up in 100 ml of diethyl ether and the solution is filtered. After the filtrate has been evaporated, an oil remains which is chromatographed on silica gel 25. Elution with diethyl ether-hexane 1: 1 gives the title compound of mp 49-50 °.

Example 6

N- [l- (lH-pyrazol-l-yl) ethyl] -N- (2,4-dimethylthien-3-yl) 30 chloroacetamide (method)

8.5 are added to a stirred solution of 12.7 g (0.1 mol) of 2,4-dimethyl-3-aminothiophene in 100 ml of dry benzene containing 16 g of molecular sieves (3 Â) and 2 drops of H2S04 conc ml (0.15 mol) of acetaldehyde added so that the reaction temperature does not exceed 25 °.

After the addition of the aldehyde is complete, the reaction mixture is stirred for a further 24 hours at room temperature and then filtered. Removal of the solvent gives the ship see base as a light brown liquid.

40 9.7 g (0.086 mol) of chloroacetyl chloride are added dropwise to the stirred solution of 13 g (0.085 mol) of this material in 75 ml of dry toluene at −30 °.

When the addition is complete, the reaction solution is stirred for a further 30 minutes at -30 ° and 12 g (0.085 mol) of 1-trimethylsilylpyrazole are added at the same temperature. After the addition, the solid CO 2 / acetone bath is removed, the mixture is left to stand until it has reached room temperature and stirring is continued for 20 hours.

The reaction mixture is then filtered and evaporated in vacuo. The remaining syrup is chromatographed on silica gel with hexane / diethyl ether 3: 2 as the eluent, and then gives the title compound which, after recrystallization in diethyl ether, has an mp of 76-78 °.

55

Example 7

N- (4-methoxy-2-methylthien-3-yl) -N- (2-ethoxyethyl) chloroacetamide (method d)

To a well-stirred mixture of 6.05 g (0.03 mol) of 6oN- (2-ethoxyethyl) -4-methoxy-2-methylthiophene-3-amine, 4.15 g (0.03 mol) of K2CO3.10 ml H20 and 100 ml of CH2C12 are added dropwise to 3.4 g (0.03 mol) of chloroacetyl chloride in 10 ml of CH2C12 without cooling the solution. After the exothermic reaction (27 °) has ended, stirring is continued for 1 hour at room temperature.

The CH2C12 phase is separated off, washed twice with 100 ml of H20, dried (Na2S04) and evaporated in vacuo. The remaining crude title compound is analytical

655 312

purely; Rf = 0.23 (hexane / diethyl ether 1: 2). A small portion of this material is subjected to Kugelrohr distillation: bp 168-170 ° / 0.05 Torr.

8th

The following compounds of the formula I are obtained by one or more of the processes according to Examples 1 to 7: (Me is CH3; Et is C2H5).

Table A

Verb.Aryl no.

1 4-methien-3-yl

2 do.

3 2-methien-3-yl

4 2,4-diMe-thien-3-yl

5 do.

6 do.

7 th.

8 do.

9 th.

10 do.

11 2-MeS02-4-methien-3-yl

12 2,4-diMe-thien-3-yl

13 do.

14 do.

15 2-MeCO-4,5-dimethien-3-yl

16 2,4-diMe-thien-3-yl

17 do.

18 do.

19 do.

20 do.

21 do.

22 do.

23 do.

24 th.

25 do.

26 do.

27 th.

28 2,4-diMe-thien-3-yl

29

30th

31

32

33

34

do.

do.

do.

do.

do.

do.

CH2OC, H5

ch2ch2och3

ch2ch2och3

ch3 c2h5

ìc3h7

ch2-ch = ch2

CH2C (CH3) = CH2

ch2-ceeCH

C (CH3), - C = CH

CH2OEt

CH2CF3

CH2-C (C1) = CH, CH2-C (Br) = CH2 pyrazolyl-1-CH-> CH2COOMe

CH2COOEt

CH2COOC3H7i CH2-COOC (CH3) 2C s CH

CH (CH3) COOCH3

CH (CH3) COOC3H7i

CH, CON (CH3), CH-> CONHC3H7i CH2CONHN = C (CH3) 2 CH2- (l-pyrazolyl) CH (CH3) (1 -pyrazolyl) CH2- (3,5-diMe-pyrazolyl-1)

CH (CH3) -Q

ch-0

CH (CH3) - | Q

cli * ~ U

CH (Me)

£

Me

CHZ-N

0

-ih

a

characterization

M.p. 25-26;

Rf = 0.45 (cyclohexane / ethyl acetate 1: 1)

Rf = 0.3 (cyclohexane / ethyl acetate 6: 4)

Mp 45-46 °

Mp 50-51 °

Mp 85-86 ° mp 95-96 °

Mp 60-61 °

Mp 45-46 "

M.p. 48-49 20

n q = 1.5345

Sdp. 118-21: /0.005 Torr mp 77-79

n p = 1.5342 20

n p = 1.5192

M.p. 82 84 m.p. 135-137 °

Mp 141 mp 88-89 ° mp 76-78 ° mp 143-144 °

Mp 132-133 °

CH (Me) - K

>

1

J- «Me

No.

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

Aryl

9

Y

655 312

characterization

2,4-diMe-thien-3-yl do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

do.

2,4-diMe-thien-3-yl do.

do.

do.

CH (Me> - | ^ CH2 (2-furyl)

CH2- (2-thienyl)

CH-

lui,

3-Me-isoxazol-5-yl-CH2

N-N

CH, - <Aii — Et

0

CH

• Me

N-N

CH2 ~ ^ "S e

N-N CH2-4Nii-Me

H

N-N nJL SMe

Me ch41>

ch2ch2oh

CH2OEt

CH2OC3H7n

CH2OC4H9n

CH (Me) OMe

CH (Et) OMe

CH2CH2OMe

CH2CH2OEt

CH2CH2OC3H7n

CH (Me) CH2OMe

C (Me) 2CH2OMe

CH (Me) OCH2CH2Cl CH (OMe) CH2OMe CH2OCH2CH2OMe CH (Me) OCH2CH2CN

78-79 ° mp 57-59 ° mp 66-67 ° mp 77-78 ° mp 54-56 ° mp 71-72 ° mp 110-15 °

Mp 119-25 ° mp 120-22 ° mp 68-70 °

M.p. 79-80 °

Bp 115 ° / 0.001 torr n p = 1.5280

Bp 110-11 ° / 0.001 torr

Mp 48-50 °

Mp 55-57 °

Mp 54-55 °

Bp 110 ° / 0.01 torr

Rf = 0.36 (diethyl ether / hexane

1: 1)

Bp 148-150 ° / 0.03 torr

M.p. 76-78 °

Mp 62-64 °

Rf = 0.3 (diethyl ether / hexane 1: 1) bp 117-18 ° / 0.005 torr mp 59-64 °

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

91'c

98

99

100

101

102

103

104

105

106

107

108

109

110

10th

Aryl

characterization

2,4-diMe-thien-3-yl

/ N = |

CH2OCH2-N _ [

do. CH (Me) OCH2

M

<-Q

do.

do.

do.

do.

do.

do.

do.

do.

do.

2-Me-4-Et-thien-3-yl do.

do.

2-Et-4-methien-3-yl do.

2,4-diet-thien-3-yl)

do.

do.

2-iC3H7-4-methien-3-yl

4-OH-2-methien-3-yl

2-Me-4-MeO-thien-3-yl

2-Me-4-EtO-thien-3-yl

2-Me-4-i-C3H7-thien-3-yl

2-Me-4-nC4H90-thien-3-yl

2-Me-4-OCH2-CH = CH2-thien-3-yl

2-Me-4-OCH2-C = CH-thien-3-yl

2-MeOCH2-4-MeO-thien-3-yl

2-MeS-4-methien-3-yl

2-MeS (0) -4-Me-thien-3-yl 2-MeCO-4-Me-thien-3-yl 2-MeCO-4-Et-thien-3-yl 2-MeC (= NOMe) - 4-methien-3-yl

CH (Me) 0-N = CH-Me CH (Me) 0-N = C (Me) 2 CH2-CH = NOMe CH2-CH = NOEt CH2-C (Me) = NOMe CH2-C (Me) = NOEt CH (Me) CH = NOMe CH (Me) CH = NOEt CH (Me) -N (Me) -COMe CH (Me) CH2OMe CH2OEt pyrazolyl-1-CH2 CH2OC2H5

CH (Me) CH2OMe pyrazolyl-1-CH2 CH2-OEt

CH2CH2OMe pyrazolyl-1-CH2

CH (Me) CH2OMe pyrazolyl-1-CH2

CH2-OEt

CH2CH2-OEt pyrazolyl-1-CH2

do.

CH2OEt pyrazolyl-1-CH2 do.

do.

do.

CH2OEt CH2CH2OMe CH2OEt CH2OEt pyrazolyl-1-CH2 CH2OEt

2-MeC (= NOMe) -4-methien-3-yl pyrazolyl-1 -CH2

2-MeC (OEt) 2-4-methien-3-yl

2-Me-4-0-C0Me-thien-3-yl

2-COOMe-4-methien-3-yl do.

do.

2-iC3H7-4-COOMe-thien-3-yl 2-Et-4,5-diMe-thien-3-yl do.

do.

2,4-diMe-5-Cl-thien-3-yl do.

CH2OEt CH (Me) CH2OMe CH2C = CH CH2OEt CH (Me) COOEt pyrazolyl-1-CH2

CH2OEt CH2COOC3H7i pyrazolyl-1-CH2 CH2OEt

CH2OCH2CH2OCH3

Rf = 0.31 (hexane / ethyl acetate 3: 2) Rf = 0.23 (hexane / ethyl acetate 4: 1) mp 76-78 °

M.p. 57-59 °

Mp 68-70 °

Rf = 04 (hexane / ethyl acetate 4: 1)

Bp 142-44 ° / 0.2 torr mp 49-50 °

Mp 53-54 °

Rf = 0.47 (diethyl ether / hexane 7: 3)

Rf = 0.47 (diethyl ether / hexane 7: 3)

Mp 63-65 °

20,

n j-j = 1.5242

23

n p = 1.5328

Mp 90-92 °

Mp 24 °

Bp 168-170 ° / 0.05 torr

Mp 44-46 °

Sp 180 / 70.001 Torr Sp 135 ° / 0.001 Torr Sp 148-150 ° / 0.001 Torr Mp 100 °

Mp 37-38 °

syn: mp 89-91 °

anti: mp 75-76 ° syn: mp 123 ° mp 46-47 °

M.p. 119-21 ° m.p. 20-22 ° bp. 13570.005 torr n p = 1.5273

20, îin n j-j = 1.5112 n p = 1.5509 n q = 1.5412 n p1 = 1.5321

11

655 312

Verb.No.

Aryl

characterization

110a 2,4-diMe-5-Cl-thien-3-yl

110b do.

111 do.

112 2,5-diBr-4-methien-3-yl

113 2-Me-4-MeO-5-Br-thien-3-yl

114 2,4-diMe-5-COOMe-thien-3-yl

115 2,4-diMe-furan-3-yl

116 2,4-diMe-furan-3-yl

117 do

118 do.

119 do.

120 1,2,4-triMe-pyrrol-3-yl

121 do.

122 do.

123 do.

tetrahydrofuryl-2-CH-) iC3H1

pyrazolyl-1-CH2 CH2OEt pyrazolyl- 1-CH- »CH2OEt CH2OEt CH2CH2OMe CH2-CH = NOMe CH2-C (Me) = NOMe pyrazolyl-1-CH2 CH2-OEt CH2CH2OMe pyrazolyl-1-CH2 CH2-C (Me) = CH2

124 2-COOEt-N, 3,5-tri-mepyrrol-4-yl pyrazolyl-1-CH2

125 3,5-diMe-isoxazol-4-yl

126 do.

127 do.

128 do.

129 3,5-diet-isoxazol-4-yl

130 do.

131 do.

132 3,5-diMe-isothiazol-4-yl

133 do.

134 do.

135 do.

136 3-Me-5-EtO-pyrazol-4-yl

137 l, 3,5-triMe-pyrazol-4-yl

138 l, 3,5-triMe-pyrazol-4-yl

139 do.

140 do.

141 do.

142 do.

143 l-Me-3,5-diet-pyrazol-4-yl

144 do.

145 1,3-diMe-5-EtO-pyrazol-4-yl

CH (Me) COOEt CH2CH2OMe CH2OEt pyrazolyl-1-CH2 CH2-C (Me) = CH2

ch2-c = ch

CH2-OEt

CH2OEt CH2CH2OMe pyrazolyl-1-CH2

ch2c = ch

CH2CH2OMe

CH2OEt

CH2CH> OMe

CH2-OC3H7n

Et

CH2-CsCH pyrazolyl-1-CH2

CH2-OC3H7n

CH2CH2OMe CH2OEt

Rf = 0.35 (cyclohexane / ethyl acetate 7: 3)

Rf = 0.38 (cyclohexane / ethyl acetate 6: 4)

Mp 68-73 °

Mp 75-77 °

Mp 98-99 °

Bp 140 ° / 0.005 torr

Rf = 0.5 (diethyl ether)

n p = 1.5422 mp 49-50 ° mp 45-46 °

Bp 118 ° / 0.001 Torr b.p. 107-108 ° / 0.001 Torr 20

n p = 1.4908

Mp 43-45 °

Mp 109-14 ° mp 109-12 ° mp 111-113 ° bp 130 ° / 0.001 torr mp 66-67 ° bp 135 ° / 0.001 torr mp 80-82 ° mp 115-117 ° M.p. 96-97 °

20th

D

= 1,5008

Bp 130 ° / 0.001 torr mp 54-56 °

Intermediates

Example 8

3,5-Dimethyl-4-aminothiophene-2-carboxylic acid methyl ester

A solution of 45.2 g (0.21 mol) of 3,5-dimethyl-4-nitro-thiophene-2-carboxylic acid methyl ester in 1000 ml of CH3OH is stirred for 2 hours at 10 bar in the presence of 4.5 g of palladium (10% on coal).

When the hydrogenation has ended, the mixture is filtered, the catalyst is washed with CH3OH and the filtrate is evaporated to dryness.

The crystalline residue is treated with diethyl ether and gives the analytically pure title compound of mp. 88-89 °.

Example 9 2,4-Dimethyl-3-aminothiophene

To a mixture of 890 ml (3 mol) sodium bis (2-methoxyethoxy) aluminum hydride (70% solution in toluene)

and 600 ml of dry toluene, with vigorous stirring, a solution of 100 g (0.58 mol) of 3-amino-4-methylthio-phen-2-carboxylic acid methyl ester in 700 ml of dry toluene is added dropwise such that the reaction temperature is 55 ° not 55 exceeds.

After the addition has ended, the mixture is stirred for a further 30 minutes and the reaction mixture is then carefully added in small portions at 0 ° to 1200 ml of a 20% KOH solution.

The toluene phase is then separated off, dried over 60 MgS04 and concentrated in vacuo. The remaining brown liquid is distilled under reduced pressure and thus gives the analytically pure title compound of bp 49-52o / 0.01 Torr.

65 Example 10

4-methoxy-2-methyl-3-aminothiophene

A well-stirred mixture of 55.4 g (0.2 mol) of benzyl-N- (4-methoxy-2-methylthien-3-yl) carbamate, 40 g (0.7 mol)

655 312

KOH, 600 ml of ethanol and 120 ml of water are heated under reflux for 2 hours. The resulting solution is then concentrated in vacuo and the residue diluted with 500 ml of water. A slightly yellow oily phase separates, which is taken up in 400 ml of diethyl ether. The aqueous phase is also extracted with 400 ml of ether.

The combined ether solutions are dried (Na2S04) and filtered. Dry HCl gas is then passed through the filtrate for 30 minutes, care being taken by cooling in an ice bath to ensure that the temperature does not exceed 10 °.

The precipitated hydrochloride of the title compound has an mp of 230 ° (the free base melts at 61-63 °).

Example 11 2-Methylthio-4-methyl-3-aminothiophene

6 g (0.22 gram atoms) of freshly prepared aluminum amalgam are added over a period of 2 minutes to 18.9 g (0.1 mol) of 2-methylthio-4-methyl-3-nitrothiophene dissolved in 200 ml of moist diethyl ether. The violent reaction that sets in after 5-10 minutes is kept under control by ice cooling.

After 45 minutes after the exothermic reaction has proceeded and all the aluminum has reacted, a further 6 g of aluminum amalgam are added.

The reaction mixture is kept under reflux for 2 hours; during this period the formation of thiophenamine is completed.

The organic phase is decanted and the residue is washed with two 50 ml portions of diethyl ether. The combined ethereal solutions are dried (over MgSO4) and concentrated in vacuo. The remaining crude title compound is distilled under reduced pressure and has a b.p. 79-81 ° / 0.5 Torr.

Example 12

The following list lists compounds of the formula IX which are obtained by one or more of the processes according to Examples 8 to 11.

Ex. 12.1 l, 3-di-CH3-5-OC2H5-4-NH2pyrazole

(Rf = 0.28 tetra-hydrofuran: hexane 9: 1)

Ex. 12.2 3,5-di-CH3-4-NH2-isothiazole (mp. 82-84 °)

Example 12.3 4-C2H5-2-CH3-3-amino-Rf = 0.25 (diethyl-thiophene, ether: hexane 2: 1)

Ex. 12.4 4-n-Butoxy-2-methyl-3-ami mp 25 °; no-thiophene (Rf = 0.25 (diethyl ether / hexane 2: 1)

Ex. 12.5 5-C2H50-3-CH3-4-NH2-py- mp 81-83 °

razole

Ex. 12.6 3,5-di-C2H5-l-CH3-4-NH2-bp 68-70 ° / 0.001 pyrazole torr

Example 12.7 3,5-di-C2H5-4-NH2-isoxazole Rf = 0.39 (diethyl ether)

Ex. 12.8 (3-NHr4-Methien-2-yl) mp 80-81 ° ethanone

Ex. 12.9 (3-NH2-4-Et-thien-2-yl) mp 68 °

ethanon

Ex. 12.10 (3-NH2-4,5-diMe-thien-2 m.p. 120-23 ° yl) ethanone,

Ex. 12.11 2-Et-4-Me-3-NHthiophene, bp. 74-7670.01

Torr

Ex. 12.12 2,4-diEt-3-NH2-thiophene, Rf = 0.24 (CH2Cl2)

20th

12

Example 13

N- (2,4-dimethylthien-3-yl) acetoxyacetamide

To 12.7 g (0.1 mol) of 2,4-dimethyl-3-aminothiophene, 13.8 g (0.1 mol) of K2C03.20 ml of water and 150 ml of CH2C12 s, 15 g (0.11 Mol) acetoxyacetyl chloride added dropwise.

After the exothermic reaction has ended, the mixture is stirred for a further 1 hour. The organic phase is evaporated, washed with water, dried (MgS04) and concentrated in vacuo 10. The solid residue is treated with hexane and provides the analytically pure title compound of mp. 110-112 °.

Example 14

is N- (2,4-dimethylthien-3-yl) hydroxyacetamide

NH3 gas is passed through a stirred solution of 15.9 g (0.07 mol) of N- (2,4-dimethylthien-3-yl) acetoxyacetamide in 300 ml of CH3OH for 30 minutes.

After the exothermic (40 °) reaction (steamed 20 by cooling with ice water), the mixture is stirred for a further 30 minutes and the reaction solution is then evaporated to dryness. The remaining residue is recrystallized from ethyl acetate, the analytically pure title compound being obtained in the form of colorless crystals of mp. 85-87 °.

25th

Example 15

N- (2-ethoxyethyl) -4-methoxy-2-methylthiophene-3-amiti To 70 ml (0.245 mol) sodium bis- (2-methoxyethoxy) aluminum hydride (70% solution in toluene) and 30 ml dry A solution of 9.4 g (0.041 mol) of N- (4-methoxy-2-methylthien-3-yl) ethoxyacet-amide in 125 ml of dry toluene is added dropwise with stirring in 30 ml of toluene. After the exothermic reaction has ended, stirring is continued for 90 minutes and the reaction solution is then carefully added in small 35 portions at −10 ° to 100 ml of a 20% KOH solution.

The toluene phase is separated off and the aqueous phase is extracted twice with 100 ml of toluene. The combined toluene solutions are dried (over Na2SO4) and concentrated in vacuo. The remaining light brown liquid is analytically pure, Rf = 0.32 (hexane / diethyl ether 1: 2).

Ex. 12.13 2-Et-4,5-diMe-3-NH2-thiophene,

n p = 1.5511 n p = 1.5581

45 Example 16

N - [(methoxymethyl) ethyl-2,4-dimethyl-thiophene-3-amine The solution of 6.4 (0.05 mol) of 2,4-dimethyl-3-aminothiophene and 5.3 g (0, 06 mol) of methoxyacetone in 100 ml of dry toluene is heated to boiling under reflux until the theoretical amount of water has been separated off on a water cutter (272 hours). The toluene phase is allowed to stand until it has reached room temperature and then concentrated in vacuo. The remaining ship base is clean enough for the next stage.

55 9.2 g (0.048 mol) of this residue are dissolved in 100 ml of dry toluene and without cooling to a well-stirred solution of 28 ml (0.098 mol) of sodium bis (2-methoxyethoxy) aluminum hydride (70% solution in toluene) Given 15 ml of dry toluene.

60 After the exothermic reaction (44 °) has ended, the mixture is stirred for a further 90 minutes and the brown reaction solution is then carefully added in small portions at −10 ° to 40 ml of a 20% KOH solution.

The toluene phase is separated off, dried (Na2S04) 65 and concentrated in vacuo. The remaining oil is distilled after column chromatography on silica gel (eluent hexane / diethyl ether 3: 1) under reduced pressure (Kugelrohr) and has a b.p. 94-95 ° at 0.01 Torr.

Example 17

N- (5-ethyl-l, 3,4-oxadiazol-2-ylmethyl) -2,4-dimethylthio-phen-3-amine

The mixture of 12.7 g (0.1 mol) of 2,4-dimethyl-3-ami-no-thiophene, 14.6 g (0.1 mol) of 2-chloromethyl-5-ethyl-l, 3.4 -oxadiazole and 13.8 g (0.1 mol) of K2C03 in 150 ml of dry dimethylformarnide (= DMF) is stirred at 80 ° for 20 hours.

The reaction mixture is cooled to room temperature, poured into 400 ml of water and the water DMF solution is extracted 3 times with 150 ml portions of diethyl ether. The combined ethereal extracts are dried over Na2S04 and concentrated in vacuo. The remaining brown oil is chromatographed on a silica gel column, using hexane / diethyl ether 1: 1 as the eluent, and gives the analytically pure title compound as an orange liquid, Rf = 0.2 (diethyl ether / hexane 1: 1).

Example 18

N- (2,4-dimethylthien-3-yl) glycine hydrazide

82 g (0.412 mol) of N- (2,4-dimethylthien-3-yl) glycine methyl ester and 42 g (1.3 mol) of hydrazine hydrate in 350 ml of alcohol are stirred for 24 hours at room temperature. The mixture is concentrated in vacuo. After adding 150 ml of water, the residue is extracted with 4 x 500 ml portions of ether. The ether phases are combined, dried over Na2S04 and evaporated to dryness. The title compound of mp 68-70 ° remains.

Example 19

N- (2,4-Dimethylthien-3-yl) -N- (4-methyl-5-mercapto-l, 2,4-triazol-3-yl-methyl) amine

A mixture of 15 g (0.075 mol) of N- (2,4-dimethylthien-3-yl) glycine hydrazide and 5.5 g (0.075 mol) of methyl isothiocyanate in 100 ml of ethanol is heated under reflux for 4 hours. The reaction mixture is cooled to 6 ° and the precipitate formed is separated off by filtration; the pure title compound melts at 184-87 °.

Example 20

N- (2,4-Dimethylthien-3-yl) -N- (4-methyl-5-methylmercap-to-l, 2,4-triazol-3-ylmethyl) amine

To a mixture of 9.5 g (0.037 mol) of N- (2,4-dimethylthien-3-yl) -N- (4-methyl-5-mercapto-l, 2,4-triazol-3 -yl) -methyl) amine, 1.1 g of triethylbenzylammonium chloride in 100 ml of toluene and 30 ml of aqueous 50% NaOH solution, 4.7 g (0.037 mol) of dimethyl sulfate are added. The reaction mixture is stirred at room temperature for 5 hours, the organic phase separated, washed and 3 times with 100 ml of water, dried over Na2S04 and

13 655 312

Evaporated to dryness. The residue is recrystallized twice in ether and gives the title compound of mp 92-96 °.

Example 21

N-f2,4-dimethylthien-3-yl) -N- (5-methyl-l, 3,4-thiadiazol-2-ylmethyl) amine

5.5 g (0.05 mol) of acetic anhydride are added dropwise to 10 g (0.05 mol) of N- (2,4-dimethylthien-3-yl) glycine hydrazide in 175 ml of CH2C12. The mixture is stirred at 20 ° for 1 hour and evaporated to dryness. The oily residue is dissolved in 150 ml of pyridine and 11.1 g (0.05 mol) of phosphorus pentasulfide are added to the solution in small portions. The reaction temperature rises to 48 °. The mixture is then heated under reflux for 2 hours and then stirred for a further 16 hours at room temperature. After evaporation to dryness, the residue is dissolved in CH2C12 and the solution is treated in succession with ice water, with cold dilute NaOH solution and with water, dried over Na2SO4 and evaporated to dryness. Chromatography of the residue on a silica gel column gives the title compound as an oil, Rf = 0.23 (eluent: ethyl acetate / hexane 6: 4).

25th

Example 22

N- (2,4-Dimethylthien-3-yl) -N- (5-methyl-l, 2,4-triazol-3-yl-methyl) amine

5 g (0.05 mol) of acetamine hydrochloride are added to a stirred solution of 2.2 g (0.055 mol) of NaOH 30 in 125 ml of CH3OH. 15 minutes later, 10 g (0.05 mol) of N- (2,4-dimethylthien-3-yl) glycine hydrazide are added and the mixture is then heated under reflux for 18 hours. The residue is evaporated to dryness, treated with 35 CH2C12 and freed from insoluble by-products by filtration. After evaporating the CH2C12, the title compound of mp. 85-87 ° remains.

Example 23

40 N- (2,4-dimethyl-thien-3-yl) glycine-isopropylidene hydrazide 7 g (0.035 mol) of N- (2,4-dimethyl-thien-3-yl) glycine hydrazide in 50 ml acetone are kept Stirred for hours at room temperature. The title compound which crystallizes out is filtered off, mp. 126-28 °.

45

Example 24

The following compounds of the formula VII are obtained analogously to one or more of the above Examples 13 to 23: 50:

Verb Ar no.

characterization

24.1

2,4-di-CH3-thien-3-yl

CH2CH2-OCH3

Rf = 0.32 (diethyl ether-hexane 3: 1)

24.2

do.

c2h5

Rf = 0.23 (diethyl ether-hexane 1: 1)

24.3

do.

ch2-1 "P

Rf = 0.38 (diethyl ether-hexane 1: 1)

24.4

do.

ch2-C ^ 3

Rf = 0.39 (diethyl ether-hexane 2: 1)

24.5

2-CH3S-4-CH3-thien-3-yl ch2ch2-och3

Bp 86o / 0.01 torr

24.6

1,3,5-tri-CH3-pyrazol-4-yl do.

Bp 92-9470.01 Torr

24.7

1 -CH3-3,5-di-C2H5-pyrazol-4-yl do.

Rf = 0.38 (acetone-hexane 4: 6)

24.8

1,3,5-tri-CH3-pyrazol-4-yl c2h5

Rf = 0.2 (ethyl acetate-CH3OH 2: 1)

24.9

3-CH3-5-OC2H5-pyrazol-4-yl ch2ch2och3

Rf = 0.25 (ethyl acetate-CH3OH 9: 1)

655 312

14

Verb Ar no.

24.10 2,4-di-CH3-thien-3-yl

24.11 do.

24th December

24.13 2,4-di-C2H5-thien-3-yl

24.14 2-CH3-4-C2H5-thien-3-yl

24.15 2-C2H5-4-CH3-thien-3-yl

24.16 2,4-di-CH3-thien-3-yl

24.17 do.

24.18 do

24.19 do

CH2CH2OC2H5 CH2CH2OC3H7-n

CH2CF3

CH2CH2OCH3

/ CH3

CH - CH2OCH3 / CH3

CH - CH2OCH3 / CH3

ch2-c ch2

CH-

n iP

ch2T-N ^ ch.

ch

&

characterization

Rf = 0.48 (diethyl ether) Rf = 0.57 (diethyl ether)

n p = 1.4786

n p = 1.5238

Bp 98-100 ° / 0.09 torr

Rf = 0.52 (ether-hexane 7: 3)

Rf = 0.55 (diethyl ether-hexane 1: 1)

Rf = 0.15 (CH2C12)

24.20 do.

24:21 do.

ch2con (ch3) 2

ch2cooch3

20th

n q = 1.5579 bp. 82-8770.005 torr

Example 25

N- (2-Carbomethoxy-3,5-dimethylthien-4-yl) chloroacetamide To 12.25 g (0.066 mol) of 3,5-dimethyl-4-aminothiophene-2-methyl carboxylate, 9.1 g (0.066 Mol) K2C03.25 ml of water and 150 ml of methylene chloride are added, without cooling, 7.5 g (0.066 mol) of chloroacetyl chloride.

After the exothermic reaction (36 °), stirring is continued for 1 hour, the organic phase is separated off, washed with water and dried over Na2S04. After removal of the solvent, the title compound remains as colorless crystals of mp. 157-58 °.

Example 26

N- (2-chloro-3,5-dimethylthien-4-yl) chloroacetamide

3.3 g (0.0245 mol) are added at 0 ° to a stirred solution of 5.0 g (0.0245 mol) of N- (2,4-dimethylthien-3-yl) chloroacetamide in 50 ml of dry CH2C12. Drops of sulfuryl chloride.

After the addition has ended, the reaction mixture is left to stand until it has reached room temperature and then stirred for a further 20 hours. The solvent is removed in vacuo and the crystalline residue is digested with hexane, the analytically pure title compound of mp. 166 ° (dec.) Being obtained.

Example 27

N- [2- (1, l-diethoxy) ethyl-4-methyl-thieti-3-yl] chloroacetamide

15 g (0.065 mol) of N- (2-acetyl-4-methylthien-3-yl) chlorine

40 acetamides are dissolved in a warm (50 °) mixture of 60 g dry ethanol, 60 g triethyl orthoformate and 7 drops concentrated HCl.

The reaction mixture is left to stand at room temperature for 30 hours, evaporated in vacuo (50 ° / 0.01 Torr) and the remaining brown syrup is chromatographed on a silica gel column. Elution with hexane / diethyl ether 2: 1 gives the title compound of mp 57-58 ° (colorless crystals).

see example 28

N- [2- (1-methoxyimino) ethyl-4-methylthien-3-yl] chloroacetamide

The solution of 1.5 g (0.0065 mol) of N- (2-acetyl-4-methyl-thien-3-yl) chloroacetamide and 6.6 g (0.14 mol) of meth-55 oxyamine in 50 ml of dry toluene, which contains 5 g of molecular sieves (3 Â), is heated under reflux for 7 hours.

The yellow reaction solution is then filtered and evaporated in vacuo. The remaining crude syn / anti isomer mixture is separated by chromatography using hexane / 60 diethyl ether as the mobile phase.

First, 0.6 g of pure isomer (syn) with an mp of 101-102 ° (Rf = 0.33, hexane / diethyl ether 1: 1) is eluted. The elution continues on the silica gel column and the analytically pure anti-form (0.4 g) of mp 87-89 ° (Rf = 0.21) is obtained.

65

Example 29

The following compounds of formula III are obtained analogously to one or more of Examples 25 to 28.

15

655 312

E.g.

Ar

Character

sation

29.1

2-COOCH3-4-CH3-thien-3-yl

M.p. 118-119 '

29.2

2-CH3S-4-CH3-thien-3-yl

M.p. 105-106 '

29.3

2,4-di-CH3-thien-3-yl

M.p. 128-129 '

29.4

3,5-di-CH3-isoxazol-4-yl

Mp 96-98 °

29.5

3,5-diC2H5-isoxazol-4-yl

Mp 67-69 °

29.6

4-CH3-thien-3-yl

Mp 93-96 °

29.7

2-CH3-4-C2H5-thien-3-yl

Mp 114 °

29.8

2-CH3-4-OCH3-thien-3-yl

Mp 144-45 °

29.9

2,4-di-CH3-furan-3-yl

Mp 95-97 °

10/29

3,5-di-CH3-isothiazol-4-yl

Mp 104-06 °

11/29

3-CH3-5-OC2H5-pyrazol-4-yl

M.p. 125-27 °

29/12

2-COOC2H5-N, 3,5-tri-CH3-pyr-

rol-4-yl

Mp 163-65 °

29.13

2-C2H5-4-CH3-thien-3-yl

Mp 105 °

29.14

2,4-di-C2H5-thien-3-yl

Mp 145 °

29.15

2-COCH3-4-CH3-thien-3-yl

Mp 110 °

29.16

2-CH3-4-OC4H9n-thien-3-yl

Mp 129-30 °

29.17

2-C2H5-4,5-diCH3-thien-3-yl

M.p. 147-48 °

Example 32

N- (4-methoxy-2-methylthien-3-yl) ethoxyacetamide

The solution of 8.4 is added to 9.8 g (0.068 mol) of 4-methoxy-2-methyl-3-aminothiophene, 9.45 g (0.068 mol) of K2C03.35 ml of water and 100 ml of 5 CH2C12 without cooling g (0.069 mol) of ethoxyacetyl chloride in 20 ml of CH2C12.

After the exothermic reaction (32 °) has ended, the mixture is stirred for a further hour. The organic phase is separated off, washed twice with 150 ml of water, dried 10 over Na2SO4 and evaporated by means of red evaporation. The residue is chromatographed on a silica gel column using hexane / diethyl ether 1: 1 as the eluent. The title compound thus obtained has an mp. Of 40-41 °.

i5 Example 33

The following compounds of the formula ArNHCOY3 are obtained analogously to Example 32.

E.g.

31.1

31.2

31.3

E.g. Ar

20th

characterization

Example 30

N- (2,4-dimethylthien-3-yl) -N-methoxyethyl-hydroxy-acetamide

18.4 g (0.1 mol) of N- (2,4-dimethylthien-3-yl) hydroxyacetamide in 50 ml of dry dimethylformamide (DMF) become a well-stirred suspension of 3.0 g (0.05 1 mol) of NaOH (80% dispersion in mineral oil) dropped in 50 ml of dry DMF.

After the exothermic reaction (50 °), the solution of the Na salt is allowed to cool to room temperature and then treated with a solution of 10.4 g (0.11 mol) of 2-chloroethyl methyl ether in 20 ml of dry DMF. After the addition has ended, the reaction mixture is heated to 100 ° for 4 hours and then evaporated to dryness (40 ° / 0.1 Torr).

The residue is taken up in 200 ml of diethyl ether, washed with 250 ml of water, dried over MgS04 and filtered. The oily residue that remains after evaporating the filtrate is chromatographed on a silica gel column. It is eluted with diethyl ether and the desired compound is obtained as a viscous liquid (Rf = 0.25 / diethyl ether).

Example 31

The following compounds of the formula II, in which Ar represents 2,4-dimethylthien-3-yl, are obtained analogously to the process according to Example 30:

33.1 2,4-di-CH3-thien-3-yl -CH2-OCH3 mp 62-63 °

33.2 do.

-CH3

-CH2OCH3 do.

-CH2OCH3

Mp 168-69 ° mp 140-42 °

164-65 ° mp 85-87 °

Bp 120 ° / 0.001 torr mp 128-30 °

35

-CH2OC2H5 mp 37-38 ° -CH2OC3H7-n mp 43-45 ° CF3 mp 94-97 °

-CH2OCH3 m.p. 48-49 °

ch2ch = noch3 ch2ch = noc2h5

ch2c = still 3

I.

ch,

Characterization Rf = 0.21 (hexane-ethyl acetate 3: 2) Rf = 0.25 (hexane-ethyl acetate 3: 2) mp 69-710

25 33.3 do.

33.4 do.

33.5 l, 3,5-tri-CH3-pyrazol-30 4-yl

33.6 l-CH3-3,5-di-C2H5-pyrazol-4-yl

33.7 3-CH3-5-OC2H5-pyrazol-4-yl

33.8 2,4-di-CH3-thien-3-yl

33.9 do.

33.10 do.

33.11 2,4-di-C2H5-thien-3-yl

40 Example 34

Benzyl (N-4-methoxy-2-methylthien-3-yl) carbamate

63.6 g (0.23 mol) of diphenylphosphoryl azide and 24.4 g (0.23 mol) of triethylamine are combined in one casting to form a suspension of 36.5 g (0.2 mol) of 4-methoxy-2-methylthiophene-3 - carboxylic acid in 300 ml of dry benzene.

The resulting mixture is heated under reflux for 1 hour and then treated with 25 g (0.23 mol) of benzyl alcohol. After a reaction time of 3 ½ hours at 78 °, the reaction mixture is cooled to room temperature, diluted with diethyl ether (350 ml) and successively with 250 ml of 5% HCl, with 250 ml of saturated NaHC03 solution, with 200 ml of saturated NaCl -Washed solution, dried over Na2S04 and evaporated on a red evaporator. The remaining crystalline residue is digested with pentane and delivered

50

55

31.4 CH2-C = NOC2H5 Rf = 0.27 (hexane-ethyl acetate 3: 2)

the pure title compound of mp. 107-108 °.

ch3

31.5 chch = still 3 I

ch3

Example 35

Rf = 0.31 (hexane-ethyl acetate 3: 2). Analogously to Example 34, the following carbamates are obtained using the corresponding acid.

31.6 CHCH = NOC2H5 Rf = 0.3 (hexane-ethyl acetate 3: 2)

1

Example 35.1

Benzyl (N-2,4-diCH3-furan-3-yl) carbamate, m.p. 103-5 °.

CH3

31.7 CH2 <^

65

Example 35.2

"_" "" ^ Benzyl (N-4-n-butoxy-2-methylthien-3-yl) carbamate,

Rf = 0.12 (hexane-ethyl acetate 3: 2) mp 83 ° ~

655 312

16

Example 36

4-methoxy-2-methylthiophene-3-carboxylic acid

The title compound is obtained by saponification (K.OH) of the corresponding ethyl ester, mp. 127 °.

Example 37

Analogously to process 36, 4-n-butoxy-2-methylthio-phen-3-carboxylic acid, mp. 66-68 ° is obtained.

Example 38

4-Metkoxy-2-methylthiophene-3-carboxylic acid ethyl ester

20 ml of 50% NaOH solution become a mixture (at room temperature) of 18.6 g (0.1 mol) of 4-hydroxy-2-methyl-thiophene-3-carboxylic acid ethyl ester, 10 ml (0.105 mol) of dimethyl sulfate and 2.3 g (0.01 mol) of benzyltriethylammonium chloride was added dropwise to 100 ml of CH2C12.

After 15 minutes at reflux, the reaction mixture is worked up. The title compound has an Rf value of 0.36 (eluent diethyl ether / hexane 2: 1).

Example 39

3,5-Dimethyl-4-nitrothiophene-2-carboxylic acid methyl ester

Over a period of 40 minutes, a mixture of 30 ml of fuming nitric acid becomes a well-stirred solution of 51.4 g (0.3 mol) of 3,5-dimethylthiophene-2-carboxylic acid ester in 200 ml of glacial acetic acid, cooled to 0 ° (specific weight = 1.5) and 120 ml of acetic anhydride were added dropwise. After the addition has ended, the remaining brown solution is stirred for a further 2 hours at 5 ° and then poured into 3000 ml of ice water.

The aqueous phase is extracted twice with 500 ml of diethyl ether. The ether extracts are washed with water and 3% NaHC03 solution, dried over Na2S04 and evaporated in vacuo.

The residue is subjected to a silica gel column chromatography, using hexane / diethyl ether (10: 1) as the eluent, and gives the title compound of mp 87-88 °.

Example 40

Analogously to the process according to Example 39, using 1,3-dimethyl-5-ethoxypyrazole as starting compound, 1,3-dimethyl-5-ethoxy-4-nitropyrazole with an Rf value of 0.37 on silica gel is obtained with diethyl ether as Eluens.

Test results

Example 41

Herbicidal effects after pre-em application

Pots (7 cm in diameter) are filled with a mixture of peat substrate and sand. The upper surface of the mixture is sprayed with a test liquid which contains a compound according to the invention (for example in the form of the emulsion concentrate according to Example B), and seeds of Lepidium sativum, Agrostis alba, Avena sativa and Lolium perenne are then sown in each pot, after which the seeds of Avena sativa and Lolium perenne are covered with a thin (0.5 cm) layer of gate substrate-sand mixture. The pots are

Table B Treated plant left for 21 days at room temperature with 14 to 17 hours of daylight / day.

The herbicidal activity is determined after the 21-day period. It includes a visual assessment of the degree and type of damage to the different plants.

The compounds of formula I are applied in the above manner in amounts corresponding to 1.4 to 5.6 kg of active ingredient / hectare. It has herbicidal activity, i.e. Significant damage observed in the test plants.

Example 42

Herbicidal effects after post-em application

The procedure is analogous to that of Example 42, 15, the compounds according to the invention being applied at the 2 to 4-leaf stage. (The staggered sowing allows the test plants to reach the 2-4 leaf stage at the same time).

The compounds of the formula I are again applied in amounts corresponding to 1.4 kg / ha to 5.6 kg / ha. The visual determination of the herbicidal activity takes place 21 days after application of the test substance. Herbicidal activity is observed.

25th

Example 43

A selection of the compounds according to the invention is examined in more detail in the following pre-emergence test.

Containers of 30 x 40 cm are filled to a depth of 30 6 cm with a mixture of peat substrate and sand. The upper surface of the mixture is sprayed with a test liquid which contains a compound according to the invention (e.g. in the form of the emulsion concentrate according to Example B) in a certain concentration. The spray volume corresponds to 6001 aqueous test liquid / ha. The process is repeated with different concentrations, the concentrations being selected so that the desired application amounts are achieved. Six types of plants are sown per container. The number of seeds, 40 sown by each plant species, depends on the seed potential of the seeds and the initial growth rate of the individual plants. After sowing the seeds, the treated area is covered with a thin layer (about 0.5 cm) of a peat substrate / sand mixture.

The containers are then left for 28 days at a temperature of 20 to 24 C and 14 to 17 hours a day in daylight (possibly artificial).

45

The herbicidal activity of the tested 50 compounds according to the invention is determined immediately after the end of the 28-day period. The determination includes a visual assessment of the degree and type of damage to the various plants. A particularly advantageous herbicidal activity is, inter alia, observed with Compound Nos. 25,26,47,48, 55, 55,75,84 and 86 of Table A. Some of the results achieved with these compounds with application amounts of 1 kg of active ingredient / ha are summarized in Table B below.

Pre-em treatment 1 kg / ha compound no. /% Damage

25th

26

47

48

55

75

84

86

Amaran. retrofl.

90

90

100

100

100

100

80

90

Capsella b.p.

80

100

100

80

90

70

70

90

Chenop. alb.

80

80

90

50

20th

50

60

60

Galium aparine

80

10th

50

0

10th

10th

50

10th

17th

655312

Table B

Pre-em treatment

1 kg / ha

Treated

plant

Compound No. /% damage

Senecio vulg.

90

80

80

80

80

100

90

100

Stellaria media

90

70

70

80

50

50

70

90

alfalfa

80

60

60

50

80

10th

70

90

Bean

0

0

20th

20th

0

0

10th

10th

Carrot

80

90

90

90

70

100

80

90

Cotton

20th

0

10th

0

0

0

20th

0

Flax

80

30th

60

50

30th

0

20th

10th

Potato

0

10th

10th

0

0

0

0

0

Soya

50

10th

30th

30th

0

10th

30th

30th

Sugar bed

60

10th

10th

0

0

0

20th

30th

Rape

10th

0

20th

0

0

0

20th

10th

Sunflower

0

10th

30th

50

0

0

0

10th

Agropyron repens

90

100

90

60

80

90

90

70

Agrostis alba

100

100

100

100

100

100

100

100

Alopec. myos.

90

90

80

20th

50

80

80

90

Apera sp. venti.

100

100

100

100

100

100

100

100

Avena fatua

80

80

80

40

80

90

50

90

Echinochloa c.g.

90

100

90

90

90

100

90

90

Corn

20th

30th

50

30th

0

50

90

60

Wheat

70

100

90

90

0

100

60

70

Example 44

Post-em treatment

A further test of a selection of compounds according to the invention is carried out in a post-emergence test which is carried out analogously to the pre-emergence test described in Example 43, with the difference that the test liquid is applied only in the 2 to 4 leaf stage. For this purpose, the different types of plants are sown in stages. The greenhouse conditions (temperature

Table C treated temperature, light) are as in Example 43. The herbicidal activity is also determined 28 days after application and is carried out by the method according to Example 41.

30 Particularly advantageous herbicidal properties include observed with Compound Nos. 25,26,47,48, 55,75,84 and 86 of Table A. Some of the results that can be achieved with the application amount of 5 kg of active ingredient / ha are summarized in Table C.

35

Post-em treatment 5 kg / ha

plant

Compound No. /% damage

25th

26

47

48

55 *

75

84

86 *

Amaran. retrofl.

90

80

70

50

80

60

80

90

Capsella b.p.

80

60

20th

20th

80

50

80

60

Chenop. alb.

90

40

40

20th

20th

40

30th

60

Galium aparine

80

60

40

30th

80

20th

70

60

Senecio vulg.

80

50

70

80

90

90

80

90

Stellaria media

90

50

60

10th

30th

40

60

40

alfalfa

80

60

20th

10th

50

20th

70

70

Bean

100

20th

30th

20th

20th

30th

30th

50

Carrot

70

90

30th

100

80

100

100

80

Cotton

70

60

50

40

50

60

70

70

Flax

80

70

90

100

80

90

40

80

Potato

70

30th

20th

10th

10th

10th

40

10th

Soya

90

30th

30th

30th

20th

30th

30th

50

Sugar bed

30th

20th

70

0

10th

10th

0

10th

Rape

40

20th

10th

10th

30th

60

50

40

Sunflower

60

50

30th

80

40

60

90

50

Agropyron repens

70

30th

70

50

50

50

30th

50

Agrostis alba

-

-

-

-

-

-

Alopec. myos.

80

90

80

70

60

90

80

90

Apera sp. venti.

90

100

100

100

100

100

90

90

Avena fatua

90

100

90

80

90

100

100

100

Echinochloa c.g. 1)

80

60

80

80

90

70

80

90

2)

90

80

80

90

100

80

90

100

Corn

80

60

100

90

30th

30th

70

80

Wheat

70

90

80

50

10th

60

60

80

Rice 2)

40

30th

10th

50

30th

30th

30th

40

* 4 kg / ha l) “upland” conditions;

2) «paddy» conditions

655 312

Field trial

Compound No. 25 is further investigated in a pre-em multicultural field screening experiment under the following conditions:

Cultures: Soy ("Steele") - (So)

Cotton («Stoneville 213») (Cot)

Corn (LG 11) (Co)

Wheat (Svenno) (Wh)

Weeds: Alopecurus pratensis - (AI)

Echinochloa crus galli - (Ech)

Galium aparine

Chenopodium album and polyspermum The «Amaranthus retroflexus

18th

(All weeds, with the exception of Alopecurus pratensis, which was sown, were naturally occurring).

- Spray volume: 7501 / ha

- Number of attempts: 3

5 - Evaluation: 28 days after application.

- Standards: Alachlor (= a-chloro-2 ', 6'-diethyl-N-meth-oxymethyl-acetanilide) and metolachlor [= a-chloro-2'-ethyl-6'-methyl-N- (l-methyl -2-methoxyethyl) acetanilide],

The following herbicidal activity (% damage) was observed.

Connection kg / ha

So

Cot

Co

Wh

Al / Ech

Dicots

No. 25th

0.6

0

0

10th

63

92

43

1.25

3rd

3rd

53

80

100

67

2.5

5

7

80

92

100

87

Alachlor

1.25

0

0

0

10th

43

43

2.5

0

3rd

0

53

78

57

Metolachlor

1.25

0

0

0

33

100

30th

2.5

0

0

0

73

100

43

The above results show a herbicidal activity which is superior to that of 30 against dicotyledon weeds. The herbicidal we-commercial standards are the same or superior to selective in soybeans and cotton and the lowest is against monocotyledonous weeds, and the application level of these standards is also in maize.

C.

Claims (7)

655 312 PATENT CLAIMS 1. Compound of Formula I / C0CH2C1 Ar-N <f > * SS I. wherein Ar is a 5-membered heteroaromatic ring which contains 1 or 2 ring heteroatoms selected from O, S and N and is bonded to the N atom of the N (Y) COCH2Cl group by a ring carbon atom, where, if Ar is pyrazolyl, the N (Y) COCH2Cl group is in the 4-position, and Y Allenyl, CH2-CH = C = CH2, a hydrocarbon is selected from the series Q 8 alkyl, C3 .g alkenyl, C3_8 alkynyl, C3_8 cycloalkyl, C5_8 cycloalkenyl, Q ^ cycloalkyl-C ^ alkyl, the hydrocarbon being unsubstituted or selected from the group consisting of halogen Row F, Cl or Br is substituted; or a group CHRj-COY] in which R] represents H or C ^ alkyl, and Y j together with the CO group to which Y j is bound forms an ester or amide function; or a group R2-Az meant the R2 is unsubstituted or substituted by (^ CH2 or CH2-CH2, and Az denotes a heteroaromatic ring selected from a di- or triazole bonded to R2 with a ring nitrogen atom, a 5-membered hetero ring containing 1 to 3 heteroatoms bonded to R2 with a ring carbon atom, selected from O, S and N, and a pyrimidine group; or a 2-oxo-l-pyrrolidinyl group in which a CH2 group can be replaced by O, S or NCH3 and 5-oxo and / or bicyclic benz [c] linked derivatives of such 2-oxo-l-pyrrolidinyl Group, or a group A-OR3, wherein R3 stands for H or a hydrocarbon which is selected from the series consisting of Qsalkyl, C ^ alkynyl, C3.8-cycloalkyl, C5_8cycloalkenyl and C ^ gcycloalkyl-C ^ alkyl, this hydrocarbon being unsubstituted or substituted; or for a group N = C <T, \ R4 ' in which R4 is a hydrocarbon selected from the series consisting of C15 alkyl, C3-5 alkenyl, C3 5 alkynyl, C3.8 cycloalkyl, C3_8 cycloalkenyl and C3 gcycloalkyl-C, ^ - alkyl, the hydrocarbon being unsubstituted or by halogen, selected from F, Cl and Br, is substituted; or allenyl means R4 'H or one of the meanings given for R4, and A represents a hydrocarbon radical which can be linked to R3 to form a hetero ring containing 1 or 2 O-heteroatoms, the N and O atoms connected by A being separated from one another by up to 3 carbon atoms; or a group CHR5-CHR5 ' = NOR4 means what R4 has the above meaning, R5 and R5 'independently of one another are H or CH3 or together are (CH2) 3 or (CH2) 4, or a group CHR6-N (CH3) COCH3 in which Re stands for H or Q_3alkyl. 2. A compound according to claim 1 wherein Ar represents a thiophene, isothiazole or isothiazole ring which is substituted at least in the o, o 'position of the chloroacetamide group by substituents selected from the group consisting of halogen; C] _4alkyl, unsubstituted or substituted by halogen, C ^ alkoxy or C3_fiCycloalkyl; C3_6CycloaIkyl; Formyl or C ^ alkanoyl; C (= NOCMAlkyl) -C ^ 3alkyl; 5 C (OC: _4 alkyl) 2-C, _3 alkyl; CH (OC, ^ alkyl) 2; C, .4 alkyl-S; C ^ alkyl-SO; Q 4 alkyl-S02; C ^ alkoxy-carbonyl; Ci 4 alkoxy, unsubstituted or substituted by halogen or C ^ alkoxy; C ^ alkenyloxy; C2 ^ alkynyloxy; HO and CH2OH and esters thereof, any additional substituents being chosen from the series Q ^ alkyl, halogen and C ^ alkoxycarbonyl. 3. A compound according to claim 2 wherein Ar is 3-thienyl 2,4-disubstituted by substituents selected from Ci_4alkyl and Cj ^ alkoxy. 15 4. Compound according to claim 3 selected from the group wherein Ar and Y for a) 2,4-dimethyl-thien-3-yl and pyrazol-l-ylmethyl respectively. b) 2,4-dimethylthien-3-yl and l (pyrazol-l-yl) ethyl or c) 2,4-dimethylthien-3-yl and CH2OC2H5 or 20 d) 2,4-dimethylthien-3-yl and CH2OC3H7n or e) 2,4-dimethylthien-3-yl and CH (CH3) CH2OCH3 or f) 2-methyl-4-ethylthien-3-yl and CH2OC2H5 or g) 2-methyl-4-methoxy-thien-3-yl and pyrazol-l-ylmethyl or 25 h) 2-Methyl-4-methoxy-thien-3-yl and CH2CH2OC2H5 are available. 5. A compound according to claim 4 wherein Ar is 2,4-dimethyl-thien-3-yl and Y is CH (CH3) CH2OCH3. 6. A process for the preparation of compounds of For-30 mei I according to claim 1, characterized in that a compound of formula VII AR-NH-Y VII 35 wherein Ar and Y are as defined above, with chloroacetyl chloride, or a reactive functional derivative thereof, N-acetylated. 7. A method for controlling weeds, characterized in that a herbicidally effective amount of 40 ner connection according to one of claims 1 to 5 used. 8. Herbicidal preparations containing a compound according to any one of claims 1 to 5 and an acceptable diluent for herbicides. 45 9. Compound of formula VII AR-NH-Y VII 50 55 wherein Ar and Y have the above meaning, as starting material for the process according to claim 6.