SE444565B - 6,6'-OXIBIS / 4-HALO-2H-PYRANE-3 (6H) -ON / COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF - Google Patents

6,6'-OXIBIS / 4-HALO-2H-PYRANE-3 (6H) -ON / COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF

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Publication number
SE444565B
SE444565B SE8200522A SE8200522A SE444565B SE 444565 B SE444565 B SE 444565B SE 8200522 A SE8200522 A SE 8200522A SE 8200522 A SE8200522 A SE 8200522A SE 444565 B SE444565 B SE 444565B
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Sweden
Prior art keywords
preparation
halo
formula
gamma
oxibis
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SE8200522A
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Swedish (sv)
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SE8200522L (en
Inventor
T M Brennan
D P Brannegan
P D Weeks
D E Kuhla
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Pfizer
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Priority claimed from US05/721,885 external-priority patent/US4082717A/en
Application filed by Pfizer filed Critical Pfizer
Publication of SE8200522L publication Critical patent/SE8200522L/en
Publication of SE444565B publication Critical patent/SE444565B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Pyrane Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cosmetics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Furan Compounds (AREA)
  • Saccharide Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Picture Signal Circuits (AREA)
  • Transforming Electric Information Into Light Information (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Processing Of Color Television Signals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Seasonings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Control Of El Displays (AREA)

Description

8200522-4 Chem., 49 (5), 827-832 (1976). Denna föreing syntetiserades tidigare enligt det förfarande som beskrives i den amerikanska §_ patentskriften 3.468.915. 8200522-4 Chem., 49 (5), 827-832 (1976). This compound was previously synthesized according to the procedure described in U.S. Pat. No. 3,468,915.

Synteser av gamma-pyroner såsom pyromekonsyra, maltol, etyl- maltol och andra 2-substituerad 3-hydroxi-gamma-pyroner be- skrives i de amerikanska patentskrifterna 3.130.204; 3.133.089; 3.140.239; 3.159.652; 3.365.469; 3.376.317; 3.468.915; 3.440.183 och 3.446.629.Syntheses of gamma-pyrones such as pyromeconic acid, maltol, ethyl-maltol and other 2-substituted 3-hydroxy-gamma-pyrones are described in U.S. Pat. Nos. 3,130,204; 3,133,089; 3,140,239; 3,159,652; 3,365,469; 3,376,317; 3,468,915; 3,440,183 and 3,446,629.

Maltol och etylmaltol förstärker aromen och smaken hos en mång- bald olikartade livsmedelsprodukter. Dessutom användes dessa föreningar såsom komponenter i parfymer och essenser. 2-alkenyl- pyromekonsyrorna rapporteras i den amerikanska patentskriften 3.644.635 och 2-arylmetylpyromekonsyrorna beskrives i den ameri- kanska patentskriften 3.365.469,-vilka inhlberar tillväxt av bakterier och svampar och är användbara såsom arom- och smak- förstärkande medel i livsmedel och drycker och såsom lukt-2 förstärkande medel i parfymer.Maltol and ethyl maltol enhance the aroma and taste of a wide variety of food products. In addition, these compounds were used as components in perfumes and essences. The 2-alkenyl pyromeconic acids are reported in U.S. Pat. No. 3,644,635 and the 2-arylmethylpyromeconic acids are described in U.S. Pat. No. 3,365,469, which involve the growth of bacteria and fungi and are useful as flavoring and flavoring agents in foods and beverages and as odor-2 enhancers in perfumes.

Svenska patentet 433 079 anger ett förfarande för framställ- ning av en gamma-pyron, som har formeln: J? o' ¥ ,- ..Swedish patent 433 079 discloses a process for the preparation of a gamma-pyrone, which has the formula: J? o '¥, - ..

O! ° R ' ff RI I I vilket innefattar upphettning i sur vattenhaltig lösning, företrädesvis vid en temperatur inom intervallet 70-l60°C tills hydrolysen är väsentligen fullständig, av en 6,6'-oxa- E bis-LÃ-halo-2H-pyran-3(6H)-on] som har formeln (V): (I) e. 8200522-4 vari R betecknar väte eller alkyl med l-4 kolatomer, R"' betecknar väte eller alkyl med l-4 kolatomer och X betecknar klor eller brom.O! Which comprises heating in acidic aqueous solution, preferably at a temperature in the range of 70-160 ° C until the hydrolysis is substantially complete, of a 6,6'-oxa-E bis-L1-halo-2H-pyran -3 (6H) -one] having the formula (V): (I) e. 8200522-4 wherein R represents hydrogen or alkyl having 1-4 carbon atoms, R "'represents hydrogen or alkyl having 1-4 carbon atoms and X represents chlorine or bromine.

Den syra som erfordras för hydrolysen kan sättas till reaktions- blandningen, t.ex. genom upplösning av den intermediära före- ningen med formeln (V) i»en vattenhaltig oorganisk eller orga- nisk syra före upphettningen; eller alternativt kan syran bildas in situ under framställningen av lntermediatet såsom beskrives nedan.The acid required for the hydrolysis can be added to the reaction mixture, e.g. by dissolving the intermediate compound of formula (V) in »an aqueous inorganic or organic acid before heating; or alternatively the acid may be formed in situ during the preparation of the intermediate as described below.

Enligt föreliggande uppfinning åstadkommas ett förfarande för framställning av en ny intermediär förening enligt formeln (V) ovan, vilket utmärkas därav, att man dehydratiserar en före- ning, som har formeln X ff/ /,.Û (IJ-ll) HC O R vari R och X har ovan angiven betydelse.According to the present invention there is provided a process for the preparation of a novel intermediate compound of formula (V) above, which is characterized by dehydrating a compound having the formula X ff / /,Û (IJ-II) HC OR wherein R and X have the meanings given above.

Dehydratiaeringen genomföras företrädesvis genom upphettning av föreningen med formeln (II") vid en temperatur av 4000 i 16 timmar.The dehydration is preferably carried out by heating the compound of formula (II ") at a temperature of 4000 for 16 hours.

Såsom beskrives i det svenska patentet 433 079 kan utgångs- föreningen med formeln (II") framställas genom reaktion av en furfurylalkohol i vattenlösning med ett optionellt Samlösningsmeflel vid -lO°C till +lO°C med användning av två ekvivalenter av en halogenhaltig oxidant. Den föredragna halogen- haltiga oxidanten är klor eller bromklorid. Efter omröring vid rumstemperatur i 30 minuter inställes reaktionsblandningens pH på 2 med en stark bas och reaktionsblandningen extraheras med ett lösningsmedel såsom etylacetat. Avlägsning av lösnings- medlet ger 4-halo-6-hydroxi-2H-pyran-3(6H)-onen med formeln (II"), som kan dehydratiseras genom upphettning under vakuum ._ v., ....-_.le._.-r...,..«-.--=~=~«»-~f--=«-f~=~" f* 8200522-4 för erhållande av 6,6'-oxibis[4-halo-2H-pyran-3(6H)-onf.As described in Swedish patent 433 079, the starting compound of formula (II ") can be prepared by reacting a furfuryl alcohol in aqueous solution with an optional co-solvent at -10 ° C to + 10 ° C using two equivalents of a halogen-containing oxidant. The preferred halogen-containing oxidant is chlorine or bromine chloride.After stirring at room temperature for 30 minutes, the pH of the reaction mixture is adjusted to 2 with a strong base and the reaction mixture is extracted with a solvent such as ethyl acetate.Removal of the solvent gives 4-halo-6-hydroxy 2H-pyran-3 (6H) -one of the formula (II "), which can be dehydrated by heating under vacuum ._ v., ....-_. Le ._.- r ..., ..« - .-- = ~ = ~ «» - ~ f - = «- f ~ = ~" f * 8200522-4 to obtain 6,6'-oxibis [4-halo-2H-pyran-3 (6H) onf.

Följande exempel belyser framställningen av de nya intermediära föreningarna enligt förfarandet enligt uppfinningen.The following examples illustrate the preparation of the novel intermediate compounds according to the process of the invention.

I de spektraldata som anges i exempel l(a) anges NMR-kemiska data i enlighet med inom litteraturen konventionella symboler och alla skiftningar uttryckes såsom X-enheter från tetrametyl- silan: _ _ _ ¿ d = dublett I q = kvartett m = multiplett Exempel l (a) Framställning av 4-bromo-6-hydroxi-2-metyl-EH-pyran-3(6d)- on (utgångsförening) _ ' Till en lösning av 25 g l-(2-furyl)-l-etanol i l25 ml tetra- hydrofuran och l25 ml vatten vid O-SOC sattes droppvis 2,2 ckvivalenter brom. Under hela tillsatsen hölls temperaturen vid 5-lO°C. Efter bromtillsatsen omrördes lösningen vid rums- tempertur i 30 minuter och pH inställdes på 2,1 med 2N Naom- lösning. Reaktionsblandningen extraherades med etylacetat (3 x 100 ml). Etylacetatextrakten kombinerades, torkades över MgS04, flltrerades och indunstades till torrhet. Återstoden É- kromatograferades på kiselgel och eluerades med kloroform/etyl- acetat (95:5). Produkten var en orangefärgad olja som på - ~ nytt kromatograferades pà kiselgel och eluerades med kloroform/ i etylacetat (95:5).In the spectral data given in Example 1 (a), NMR chemical data are given according to symbols conventional in the literature and all shifts are expressed as X units of tetramethylsilane: _ _ _ ¿d = doublet I q = quartet m = multiplet Example 1 (a) Preparation of 4-bromo-6-hydroxy-2-methyl-EH-pyran-3 (6d) -one (starting compound) To a solution of 25 g of 1- (2-furyl) -1- ethanol in 125 ml of tetrahydrofuran and 125 ml of water at 0-SOC was added dropwise 2.2 equivalents of bromine. Throughout the addition, the temperature was maintained at 5-10 ° C. After the bromine addition, the solution was stirred at room temperature for 30 minutes and the pH was adjusted to 2.1 with 2N Naom solution. The reaction mixture was extracted with ethyl acetate (3 x 100 mL). The ethyl acetate extracts were combined, dried over MgSO 4, filtered and evaporated to dryness. The residue was chromatographed on silica gel eluting with chloroform / ethyl acetate (95: 5). The product was an orange oil which was again chromatographed on silica gel eluting with chloroform / in ethyl acetate (95: 5).

NMR (CDCI3, 5) 7,3 (lH, d); 5,6 (lH, d); 4,7-5,0 (lH, q); 1,1-1,5 (BH, m). v¿ (b) Framställning av slutprodukt 4-bromo-6-hydroxi-2-metyl-2H-pyran-3(6H)-on upphettades under vakuum i l6 timmar vid 40°C. Den resulterande oljeartade fasta substansen kristalliserades ur isopropylalkohol för erhållning av 6,6'-oxibis[Ä-bromo-2-metyl-2H-pyran-3(GH)-onj, smältpunkt 12500. -ww-»n-W-A. _." ., _ . . ywwlwwwwv-É-fl “www fy fl 8200522-4 Exemgel 2 Försöket i exempel l upprepades med utgång från en förening, som har formeln >: /0“ / / , Ho “ o R för erhållande av en förening, som har formeln X f O¿2~ \\~ //1 íç n o\o\o 'R vari R är väte, etyl, propyl eller butyl och X är brom eller klor. 3 § smältgunkt (OC) CH3 Cl 177-179 CH CH Cl 132-135 2 3NMR (CDCl 3, δ) 7.3 (1H, d); 5.6 (1H, d); 4.7-5.0 (1H, q); 1.1-1.5 (BH, m). (b) Preparation of final product 4-bromo-6-hydroxy-2-methyl-2H-pyran-3 (6H) -one was heated under vacuum for 16 hours at 40 ° C. The resulting oily solid was crystallized from isopropyl alcohol to give 6,6'-oxibis [α-bromo-2-methyl-2H-pyran-3 (GH) -one, m.p. 12500. -ww- »n-W-A. _. "., _.. ywwlwwwwv-É- www“ www fy fl 8200522-4 Example 2 The experiment in Example 1 was repeated starting from a compound having the formula>: / 0 “/ /, Ho“ o R for obtaining of a compound having the formula X f O¿2 ~ \\ ~ // 1 íç no \ o \ o 'R wherein R is hydrogen, ethyl, propyl or butyl and X is bromine or chlorine. CH3 Cl 177-179 CH CH Cl 132-135 2 3

Claims (3)

8200522-4 PATENTKRAV:8200522-4 PATENT REQUIREMENTS: 1. En 6,6'~oxibis[Ä-halo-2H-pyran~3(6H)-on]-förening för användning såsom ett intermediat vid framställning av gamma- pyroner, k ä n n e t e c k n a_d därav, att den har formeln 0% X f fo (V) R \o o \o R » vari R är väte eller alkyl med l-4 kolatomer och X är klor eller brom.A 6,6 '-oxibis [α-halo-2H-pyran-3 (6H) -one] compound for use as an intermediate in the preparation of gamma-pyrones, characterized in that it has the formula O % X f fo (V) R \ oo \ o R »wherein R is hydrogen or alkyl of 1-4 carbon atoms and X is chlorine or bromine. 2. Förfarande för framställning av en 6,6'-oxibis[4~halo-2H- pyran-3(6H)-on]-förening, som har formeln >'~ - >: CN/g / 40 i J (vi ' n \\o, \o vari R är väte eller alkyl med 1-4 kolatomer och X är klor eller brom, k ä n n e t e c k n a t därav, att det innefattar dehydratisering av en förening, som har formeln X \\ n) Ho i R i vari R och X har ovan angiven betydelse. s20os22-4A process for the preparation of a 6,6'-oxybis [4-halo-2H-pyran-3 (6H) -one] compound having the formula> '~ ->: CN / g / 40 in J wherein R is hydrogen or alkyl of 1 to 4 carbon atoms and X is chlorine or bromine, characterized in that it comprises dehydration of a compound having the formula X \\ n) Ho in R wherein R and X are as defined above. s20os22-4 3. Förfarande enligt patentkravet'2Q k ä n n e t e c k n a t därav, att dehydratiseringen genomföras genom upphettning av föreningen med formeln (II") vid en temperatur av 40oC i 16 timmar.3. A process according to claim 2Q characterized in that the dehydration is carried out by heating the compound of formula (II ") at a temperature of 40 ° C for 16 hours.
SE8200522A 1976-08-02 1982-01-29 6,6'-OXIBIS / 4-HALO-2H-PYRANE-3 (6H) -ON / COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF SE444565B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US71090176A 1976-08-02 1976-08-02
US05/721,885 US4082717A (en) 1976-08-02 1976-09-09 Preparation of gamma-pyrones

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SE8200522L SE8200522L (en) 1982-01-29
SE444565B true SE444565B (en) 1986-04-21

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SE7707035A SE433079B (en) 1976-08-02 1977-06-16 PROCEDURE FOR MANUFACTURING V-PYRONS
SE8200520A SE444564B (en) 1976-08-02 1982-01-29 4-HALOGENE DIHYDROPYRANE COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF
SE8200519A SE445042B (en) 1976-08-02 1982-01-29 PROCEDURE FOR MANUFACTURING GAMMA PYRONS
SE8200521A SE452616B (en) 1976-08-02 1982-01-29 PROCEDURE FOR PREPARATION OF 4-HALO-2H-PYRANE-3 (6H) -ON COMPOUNDS
SE8200522A SE444565B (en) 1976-08-02 1982-01-29 6,6'-OXIBIS / 4-HALO-2H-PYRANE-3 (6H) -ON / COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF
SE8200518A SE445041B (en) 1976-08-02 1982-01-29 PROCEDURE FOR MANUFACTURING GAMMA PYRONS

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SE7707035A SE433079B (en) 1976-08-02 1977-06-16 PROCEDURE FOR MANUFACTURING V-PYRONS
SE8200520A SE444564B (en) 1976-08-02 1982-01-29 4-HALOGENE DIHYDROPYRANE COMPOUNDS FOR USE AS INTERMEDIATE IN THE PREPARATION OF GAMMA PYRONS AND PROCEDURE FOR PREPARING THEREOF
SE8200519A SE445042B (en) 1976-08-02 1982-01-29 PROCEDURE FOR MANUFACTURING GAMMA PYRONS
SE8200521A SE452616B (en) 1976-08-02 1982-01-29 PROCEDURE FOR PREPARATION OF 4-HALO-2H-PYRANE-3 (6H) -ON COMPOUNDS

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SE8200518A SE445041B (en) 1976-08-02 1982-01-29 PROCEDURE FOR MANUFACTURING GAMMA PYRONS

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CA1095921A (en) 1976-08-02 1981-02-17 Thomas M. Brennan Preparation of gamma-pyrones
FR2402654A1 (en) * 1977-09-12 1979-04-06 Shinetsu Chemical Co Tetra:hydro-pyranone derivs. - useful as intermediates for cpds. used as food flavours
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JP2586607B2 (en) * 1987-10-30 1997-03-05 日産化学工業株式会社 Production method of optically active alcohol
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CN102712591B (en) 2009-07-03 2014-06-25 阿普泰克斯科技公司 Fluorinated derivatives of 3-hydroxypyridin-4-ones
WO2017168309A1 (en) * 2016-03-29 2017-10-05 Dr. Reddy’S Laboratories Limited Process for preparation of eribulin and intermediates thereof
CN108609456B (en) * 2016-12-13 2021-03-12 奥的斯电梯公司 Openable expansion panel and elevator suspended ceiling, elevator car and elevator system with same
CN111606879A (en) * 2020-05-25 2020-09-01 安徽金禾实业股份有限公司 Method for preparing 2-hydroxymethyl-3-alkoxy-4H-pyran-4-ketone by one-pot method

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IE42789B1 (en) * 1975-08-28 1980-10-22 Pfizer Preparation of gamma-pyrones
CA1095921A (en) 1976-08-02 1981-02-17 Thomas M. Brennan Preparation of gamma-pyrones

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AT362790B (en) 1981-06-10
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CS203922B2 (en) 1981-03-31
SE445042B (en) 1986-05-26
IE790587L (en) 1978-02-02
JPS5436266A (en) 1979-03-16
SE8200520L (en) 1982-01-29
PH13557A (en) 1980-06-26
DK153401C (en) 1988-11-28
FI831702A0 (en) 1983-05-16
NO821848L (en) 1978-02-03
NL8105540A (en) 1982-04-01
DK153483B (en) 1988-07-18
HK30781A (en) 1981-07-10
FI831701L (en) 1983-05-16
IE790584L (en) 1978-02-02
YU40166B (en) 1985-08-31
FI72723B (en) 1987-03-31
PH15185A (en) 1982-09-10
FI831704L (en) 1983-05-16
HK30381A (en) 1981-07-10
RO78951A2 (en) 1982-04-12
IE790585L (en) 1978-02-02
CS203923B2 (en) 1981-03-31
SE8200521L (en) 1982-01-29
DE2728499A1 (en) 1978-02-09
NL8105539A (en) 1982-04-01
FI831700L (en) 1983-05-16
JPS5618597B2 (en) 1981-04-30
GB1538371A (en) 1979-01-17
IE45641B1 (en) 1982-10-20
PL215008A1 (en) 1979-12-17
GR68938B (en) 1982-03-29
GB1538373A (en) 1979-01-17
CA1117541A (en) 1982-02-02
NO150042C (en) 1984-08-15
FR2372821A1 (en) 1978-06-30
DE2728499C2 (en) 1986-04-03
DD132494A5 (en) 1978-10-04
MY8100267A (en) 1981-12-31
NO821847L (en) 1978-02-03
LU77600A1 (en) 1978-02-01
NO772193L (en) 1978-02-03
TR19652A (en) 1979-09-17
SE445041B (en) 1986-05-26
FI72723C (en) 1987-07-10
NL182477C (en) 1988-03-16
PL199798A1 (en) 1979-08-27
ATA124480A (en) 1981-01-15
SE8200518L (en) 1982-01-29
BG29136A3 (en) 1980-09-15
NO150043B (en) 1984-04-30
AU2601777A (en) 1978-09-21
BG28988A4 (en) 1980-08-15
HU186026B (en) 1985-05-28
IE45644B1 (en) 1982-10-20
FI831703L (en) 1983-05-16
ES459994A1 (en) 1978-11-16
BE855965A (en) 1977-12-21
SE7707035L (en) 1978-02-03
PH13874A (en) 1980-10-24
FI72722B (en) 1987-03-31
NL8105537A (en) 1982-04-01
JPS5436267A (en) 1979-03-16
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NO150561B (en) 1984-07-30
NL182478C (en) 1988-03-16
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RO78953A (en) 1982-04-12
JPS5436268A (en) 1979-03-16
AT364356B (en) 1981-10-12
DK154079B (en) 1988-10-10
YU146977A (en) 1983-06-30
PT66694A (en) 1977-07-01
YU42613B (en) 1988-10-31
YU274782A (en) 1983-12-31
NL182478B (en) 1987-10-16
DK276177A (en) 1978-02-03
DK326186A (en) 1986-07-09
FI831702L (en) 1983-05-16
MX4597E (en) 1982-06-25
NO150559B (en) 1984-07-30
GB1538372A (en) 1979-01-17
YU43190B (en) 1989-04-30
DE2760220C2 (en) 1987-08-20
AR216080A1 (en) 1979-11-30
NL182805B (en) 1987-12-16
NO150561C (en) 1984-11-07
DK325986D0 (en) 1986-07-09
NL170955C (en) 1983-01-17
FI771934A (en) 1978-02-03
PL115496B1 (en) 1981-04-30
HU185686B (en) 1985-03-28
FI73424B (en) 1987-06-30
JPS5436271A (en) 1979-03-16
NL182805C (en) 1988-05-16
FI72721B (en) 1987-03-31
SU1015826A3 (en) 1983-04-30
YU166383A (en) 1986-02-28
MY8100262A (en) 1981-12-31
CH625235A5 (en) 1981-09-15
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FI72721C (en) 1987-07-10
BR7703970A (en) 1978-07-04
HU180040B (en) 1983-01-28
NO151365C (en) 1985-03-27
PL115497B1 (en) 1981-04-30
JPS5814433B2 (en) 1983-03-18
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IE45642B1 (en) 1982-10-20
JPS5618596B2 (en) 1981-04-30
NO150559C (en) 1984-11-07
FI72720B (en) 1987-03-31
GB1538374A (en) 1979-01-17
JPS5729034B2 (en) 1982-06-19
NL182476B (en) 1987-10-16
DE2760221C2 (en) 1989-10-05
NL8105538A (en) 1982-04-01
RO74367A (en) 1981-11-24
FI831704A0 (en) 1983-05-16
SU955859A3 (en) 1982-08-30
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FR2372821B1 (en) 1980-10-17
HK30681A (en) 1981-07-10
DK153484B (en) 1988-07-18
FI72720C (en) 1987-07-10
ES470743A1 (en) 1979-01-16
ATA440477A (en) 1980-11-15
PH14625A (en) 1981-10-12
NO150042B (en) 1984-04-30
SE452616B (en) 1987-12-07
DK154079C (en) 1989-02-27
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HK30481A (en) 1981-07-10
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