NL7906529A - Gamma-amino butyric acid derivs - CNS inhibitors, inters. for pharmaceuticals and veterinary materials - Google Patents
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Abstract
Description
_ 1 __ 1 _
793253/Ar/GS793253 / Ar / GS
Aanvraagster: Roussel ïïclaf S.A., te Parijs, FrankrijkApplicant: Rousselïclaf S.A., Paris, France
Korte aanduiding: Werkwijze voor de bereiding van esters van cyclo- propaancarbonzuurderivatenShort designation: Process for the preparation of esters of cyclopropanecarboxylic acid derivatives
De uitvinding heeft betrekking op een werkwijze voor de bereiding van nieuwe esters van cyclopropaancarbonzuurderivaten.The invention relates to a process for the preparation of new esters of cyclopropanecarboxylic acid derivatives.
Be nieuwe esters zijn de 5-benzyl-3-furyl-methylesters van d, 1 of dl-trans-3,3-&iniethyl~2-cyclopentylideenmethyl-cyclöpropagsn-l-5 carbonzuur met formule 1 van het formuleblad, en worden bereid door reaktie van een 3»3-dimethyl-2-cyclopentylideenmethyl-cyclopropaan- 1-carbonzuur met formule 2 van het formuleblad, met geschikte ste-rische configuratie, of een funktioneel derivaat daarvan zoals het chloride, anhydride, gemengd anhydride, ester of metaalzout, met 10 5-bensyl-3-furylmethylaloohol of een derivaat daarvan zoals een halo-genide of alkalimetaalzout.The new esters are the 5-benzyl-3-furyl-methyl esters of d, 1 or dl-trans-3,3- & inethyl-2-cyclopentylidene-methyl-cyclopropagn-1-5 carboxylic acid of formula 1 of the formula sheet, and are prepared by reaction of a 3'-3-dimethyl-2-cyclopentylidenemethyl-cyclopropan-1-carboxylic acid of formula 2 of the formula sheet, with suitable steric configuration, or a functional derivative thereof such as the chloride, anhydride, mixed anhydride, ester or metal salt, with 10-bensyl-3-furylmethyl alcohol or a derivative thereof such as a halide or alkali metal salt.
Be nieuwe esters met formule 1 en in het bijzonder de esters van-de zuren met dl-trans en d-trans-configuratie bezitten een sterke inseoticide-werking en een geringe giftigheid ten opzichte van de 15 mens en warmbloedige dieren. Zij bezitten bovendien een anthelmin-tische werking.The new esters of the formula I, and in particular the esters of the acids with dl-trans and d-trans configuration, have a strong inseoticid activity and a low toxicity to humans and warm-blooded animals. They also have an anthelmintic effect.
Be bereiding van de als uit gangsverb indingen toegepaste zuren met formule 2 van het formuleblad alsmede bepaalde esters daarvan is beschreven in de Nederlandse octrooiaanvrage 67 11770, waaruit 20 de onderhavige aanvrage is afgesplitst.The preparation of the acids of formula II of the formula sheet used as starting compounds as well as certain esters thereof is described in Dutch patent application 67 11770, from which the present application has been split off.
Be bereiding van de esters met formule 1 kan uitgevoerd worden door 5-be&syl-3-fu2'ylmethylalcohol direkt te laten reageren met het zuur in aanwezigheid van een sterk zuur als katalysator, terwijl het gevormde water bij voorkeur azeotropiseh verwijderd wordt.The preparation of the esters of formula 1 can be carried out by reacting 5-benzyl-3-sulfylmethyl alcohol directly with the acid in the presence of a strong acid as a catalyst, preferably removing the water formed azeotropically.
25 Set kan echter voordelig zijn om vooraf het zuur om te zetten in een derivaat zoals het chloride, anhydride, gemengd anhydride, ester of metaalzout. Bij toepassing van een zuuranhydride of zuur-chloride voert men de reaktie met 5-benzy 1-3-furylmethylalcohol bij voorkeur uit in aanwezigheid van een tertiaire base zoals pyridine 50 of triethylamine, en in een geschikt oplosmiddel, bijvoorbeeld ben--eeen of tolueen.However, set can be advantageous to previously convert the acid to a derivative such as the chloride, anhydride, mixed anhydride, ester or metal salt. When using an acid anhydride or acid chloride, the reaction with 5-benzy 1-3-furylmethyl alcohol is preferably carried out in the presence of a tertiary base such as pyridine 50 or triethylamine, and in a suitable solvent, for example benzene or toluene .
7906529 * - 2 -7906529 * - 2 -
, „ V, "V
De condensatie van een halogeenverbinding van 5-benzyl-3-furyl-methylalcohol, in het bijzonder het bromide van deze alcohol, met een metaalzout van een zuur met formule 2 wordt in het algemeen uitgevoerd in een organisch oplosmiddel zoals dimethylformamide.The condensation of a halogen compound of 5-benzyl-3-furyl-methyl alcohol, especially the bromide of this alcohol, with a metal salt of an acid of formula 2 is generally carried out in an organic solvent such as dimethylformamide.
5 De omestering van lagere alkylesters van de zuren met formule 2 met 5-benzyl-3-furylmethylalcohol wordt uitgevoerd door verwarming van de uitgangsverbindingen in aanwezigheid van een alkalimetaal onder continue verwijdering van de vrijkomende lagere alcohol.The transesterification of lower alkyl esters of the acids of formula II with 5-benzyl-3-furylmethyl alcohol is carried out by heating the starting compounds in the presence of an alkali metal while continuously removing the lower alcohol that is released.
Voor de bereiding van de optisch aktieve zuren met formule 2 10 kan men tevens het overeenkomstige dl-trans-zuur splitsen met behulp van een optisch actieve organische base.For the preparation of the optically active acids of the formula II, it is also possible to cleave the corresponding dl-trans-acid using an optically active organic base.
De uitvinding zal nader toegelicht worden door de hierna volgende voorbeelden.The invention will be further illustrated by the following examples.
Voorbeeld I .Example I.
15 5-benzyl-3-furylmethylester van dl-trans cyc1op enty1i de enmethyl-1-cyc1o-propaancarbonzuur5-Benzyl-3-furylmethyl ester of dl-trans cyclopentyl the enmethyl-1-cyclopropanecarboxylic acid
Trap A: dl-trans 3,5-dimethyl-2-cyclopentylideenmethyl-1-cyclopropaan-carbonzuurchloride 20 1e) Bereiding yan^het natriumzout^van het zuur:Step A: dl-trans 3,5-dimethyl-2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid chloride 1) Preparation of the sodium salt of the acid:
In 10 cm^ methanol met 10% water, lost men 1,08 g dl-trans 3,3-dimethyl-2-cyclopentylideenmethyl-1-cyclopropaancarbonzuur op, voegt natriummethylaat toe tot geringe rose verkleuring met fenolfta-leine, verwijdert de methanol door destillatie onder vacuum, voegt 25 benzeen toe en destilleert opnieuw om het water uit het medium volledig te verwijderen. Men verkrijgt op deze wijze het natriumzout van dl-trans 3>3-<ümethyl-2-cyclopentylideenmethyl-1-cyclopropaancarbon-zuur.Dissolve 1.08 g of dl-trans 3,3-dimethyl-2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid in 10 cm @ 3 of methanol with 10% water, add sodium methylate to slight pink coloration with phenolphthalene, remove the methanol by distillation under vacuum, add benzene and distill again to completely remove the water from the medium. The sodium salt of dl-trans 3> 3- <umethyl-2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid is thus obtained.
2e) Bereiding van het zuurchloride: 30 Het hierboven verkregen natriumzout wordt gesuspendeerd in 30 cm 3 benzeen, en men koelt het reaktiemengsel af, voegt 2 cnr pyridine toe, en vervolgens 4>7 crtr oxalylchloride. Men roert, verwijdert het gevormde neerslag door affiltreren, wast het met benzeen, voegt de ben- 7906529 * c - 3 - zeenwasvloeistoffen toe aan het hoofdfiltraat en verkrijgt een benzeenoplossing van het dl-trans 3»3-dimethyl-2-cyclopentylideenme-thyl-1-cyclopropaancarbonzuurchloride, dat als zodanig voor de volgende trap gebruikt wordt.2e) Preparation of the acid chloride: The sodium salt obtained above is suspended in 30 cm 3 of benzene, and the reaction mixture is cooled, 2CN of pyridine is added, and then 4> 7% oxalyl chloride. The mixture is stirred, the precipitate formed is removed by filtration, it is washed with benzene, the benzene washing liquids are added to the main filtrate and a benzene solution of the dl-trans 3, 3-dimethyl-2-cyclopentylidenemethyl is obtained. -1-cyclopropanecarboxylic acid chloride, which is used as such for the next step.
5 Trap B: 5-benzyl-3-furyl-methyle ster van dl-trans 3,3-dimethyl-2-oyolopentylideenmethyl-1-cyclopropaancarbonzuur5 Step B: 5-Benzyl-3-furyl-methyl star of dl-trans 3,3-dimethyl-2-oyolopentylidenemethyl-1-cyclopropanecarboxylic acid
Aan de hierboven verkregen benzeenoplossing van het zuurchloridi i voegt men 1,5 cnr pyridine en 1,05 S 5-benzyl-3-furylmethylalcohol opgelost in 10 cm^ benzeen toe. Ken roert het reaktiemengsel gedurende 10 16 uur bij kamertemperatuur, voegt water toe, scheidt de organische fase af door decanteren, extraheert de waterige fase met ether, wast de verenigde organische fasen achtereenvolgens met een koude waterigs zoutzuuroplossing, met water, met een waterige natriumbicarbonaatop-lossing, vervolgens met water, droogt, concentreert tot droog, lost 15 het verkregen produkt op in benzeen, leidt de benzeenoplossing door een aluminiumoxydekolom, concentreert het eluaat tot droog en verkrijgt 1,234 S van de 5-benzyl-3-furylmethylester van dl-trans 3,3-dimethyl-cyclopentylideenmethyl-1-cyclopropaancarbonzuur die vast is bij kamertemperatuur, en een smeltpunt bezit van 40°C.To the benzene solution of the acid chloridine obtained above, 1.5 cm 3 of pyridine and 1.05 S of 5-benzyl-3-furylmethyl alcohol dissolved in 10 cm @ 2 of benzene are added. The reaction mixture is stirred for 10-16 hours at room temperature, added water, separated the organic phase by decantation, extracted the aqueous phase with ether, washed the combined organic phases successively with a cold aqueous hydrochloric acid solution, with water, with an aqueous sodium bicarbonate solution. release, then with water, dries, concentrates to dryness, dissolves the product obtained in benzene, passes the benzene solution through an alumina column, concentrates the eluate to dryness and obtains 1,234 S of the 5-benzyl-3-furylmethyl ester of dl-trans 3,3-dimethyl-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid which is solid at room temperature and has a melting point of 40 ° C.
20 Analyse: C24H28°3 = 3^4,46Analysis: C24H28 ° 3 = 3 ^ 4.46
Berekend: <# 79,09 H# 7,74 Gevonden: 79,4 8,0 TJ.V. Spectrum (ethanol): max. 207 - 208m/1 = 24.000 25 Voorbeeld II: 5-b enzyl-3-furylmethylester van d-trans 3,3-dimethyl- 2-cyclopentylideenmethyl-l-cyclopropaancarbonzuurCalculated: <# 79.09 H # 7.74 Found: 79.4 8.0 TJ.V. Spectrum (ethanol): max. 207 - 208m / 1 = 24,000 Example II: 5-b enzyl-3-furylmethyl ester of d-trans 3,3-dimethyl-2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid
Trap A: d-trans 3,5-dimethyl-2-cyclopentylideernethyl-1-cyclc - propaancarbonzuurStep A: d-trans 3,5-dimethyl-2-cyclopentylideneethyl-1-cyclc - propanecarboxylic acid
Men laat in ethylacetaat 1-efedrine reageren met dl-trans 3,3-50 dimethyl-2-cyelopentylideenmethyl-1-cyclopropaancarbonzuurv Men iso1-Ephedrine is reacted in ethyl acetate with dl-trans 3,3-50 dimethyl-2-cyelopentylidenemethyl-1-cyclopropanecarboxylic acid.
leert door af zuigen een neerslag, dat na zuivering het 1-efedrine zout van het d-trans-3,3-dimethyl-2-cyclopentylideenmethyl-1-cyelo-_propaancarbonzuur (zout A) levert. Smp. = 162°Clearns by suction a precipitate which, after purification, yields the 1-ephedrine salt of the d-trans-3,3-dimethyl-2-cyclopentylidenemethyl-1-cyelo-propane carboxylic acid (salt A). Mp. 162 ° C
79065297906529
VV
• «r (ο = 1,1$·, chloroform).• (r = 1.1 $, chloroform).
ïïit het filtraat (oplossing in ethylacetaat) wint men een pro-dukt dat na zuivering het 1-efedrinezout van 1-trans 3»3-dimethyl- 2-cyclopentylideenmethyl-1-cyclopropaancarbonzuur (zout B) levert.The product is recovered from the filtrate (solution in ethyl acetate) which, after purification, yields the 1-ephedrine salt of 1-trans 3'-3-dimethyl-2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid (salt B).
5 Smp. = 112°C, Γ-Jf--13° (o. 1,1# chloroform).5 Mp. 112 ° C, Γ-Jf - 13 ° (o. 1.1 # chloroform).
Boor aanzuren van het zout A verkrijgt men het d-trans 3»3-di-Boric acidification of the salt A gives the d-trans 3 »3-di-
methyl-2-cyclopentylideenmethyl-1-cyclopropaancarbonzuur, smp. = 60°Cmethyl 2-cyclopentylidene methyl-1-cyclopropanecarboxylic acid, m.p. = 60 ° C
(weinig duidelijk) (a — 1,1$> chloroform) I(little clear) (a - 1.1 $> chloroform) I.
(zuur A„).(acid A „).
10 Boor aanzuren van het zout B, verkrijgt men het 1-trans 3,3-di- methyl-2-cyclopentylideenmethyl-1-cyclopropaancarhonzuur, smp. = éO°C (weinig duidelijk), / J 0°C (c = 1%)t chloroform) (zuur B1).By acidifying the salt B, the 1-trans 3,3-dimethyl-2-cyclopentylidenemethyl-1-cyclopropanecaronic acid is obtained, m.p. = 0 ° C (little clear), / 0 ° C (c = 1% t chloroform) (acid B1).
Hoewel het draaiïngsvermogen van de verkregen zuren in de buurt 15 van nul ligt, heeft de splitsing wel plaats gevonden. Boor ozonisatie van het d-trans chrysanthemumzuur evenals door ozonisatie van het zuur A.j afkomstig van het efedrinezout, smp. = 162°C, komt men tot hetzelfde 1-trans carbonzuur, smp. = 212°0, CJ D 35 (c_ = 1,8, methanol) /"zie, H. STATJBIHGER en L. EÏÏZICKA, Helv.Chem.Although the rotational capacity of the acids obtained is close to zero, the cleavage has taken place. Boron ozonation of the d-trans chrysanthemum acid as well as ozonation of the acid A.j from the ephedrine salt, m.p. = 162 ° C, the same 1-trans carboxylic acid is obtained, m.p. = 212 ° C, CJ D 35 (c = 1.8, methanol) / see, H. STATJBIHGER and L. ISOLICKA, Helv. Chem.
20 Acta 7, 201 (1924)/7.20 Acta 7, 201 (1924) / 7.
Trap B: d-trans_3,3-dimethyl-2-cyclopentylidesnmethyl-1-cyclopropaan-carbonzuurohloride 1e) Bereiding van het natriumzout van het zuur:Step B: d-trans-3,3-dimethyl-2-cyclopentylmethyl-1-cyclopropane-carboxylic acid chloride 1st) Preparation of the sodium salt of the acid:
In 2 cm methanol lost men 1,14 g d-trans 3 * 3-&imethyl-2-cyclo-25 pentylideenmethyl-1-cyclopropaancarbonzuur op, voegt de hoeveelheid 2,06 N natriumhydroxyde-oplossing in methanol toe die noodzakelijk is ter verkrijging van een lichtrose verkleuring in aanwezigheid yan fenolftaleine, verwijdert de methanol onder verminderde druk, voegt benzeen toe en concentreert opnieuw tot droog onder verminderde 50 druk om het water volledig uit het medium te verwijderen. Men verkrijgt op deze wijze het natriumzout van d-trans 3»3-<liEiethyl-2-oy-clopentylideenmethyl-1-cyclopropaancarbonzuur.1.14 g of d-trans 3 * 3- & imethyl-2-cyclo-pentylidenemethyl-1-cyclopropanecarboxylic acid are dissolved in 2 cm of methanol, the amount of 2.06 N sodium hydroxide solution in methanol necessary to obtain a light pink discoloration in the presence of phenolphthalein, removes the methanol under reduced pressure, adds benzene and concentrates again to dryness under reduced pressure to completely remove the water from the medium. In this way the sodium salt of d-trans 3, 3-, <RTI ID = 0.0> ethyl-2-ol-clopentylidenemethyl-1-cyclopropanecarboxylic acid is obtained.
2e) Bereiding van het zuurchloride _ Het hierboven verkregen natriumzout wordt gesuspendeerd in 30 ce 7906528 5 -5 - benzeen, men koelt het reaktiemengsel af, voegt onder stikstofatmos-feer 2 cm pyridine en vervolgens 4,7 cm oxalychloride toe, roert, concentreert tot droog, onder verminderde druk, voegt benzeen toe en concentreert opnieuw tot droog voor het volledig verwijderen van de 5 'benzeen en het oxalychloride. Men verwijdert het gevormde neerslag door filtreren, wast het met benzeen, voegt de benzeenwasvloeistoffen aan het hoofdfiltraat toe en verkrijgt een benzeenoplossing van d-trans 3 , 5-dimethyl-2-eyclopentylideenmethyl-1-cyclopropaancarbon-zuurchloride dat als zodanig voor de volgende trap gebruikt wordt» 10 Trap C: 5-benzyl 5-fugylmethylester van d-trans 3>3-cLi^eifoy]l“2-cy- clopentylideenmethyl-1-cyclopropaancarbonzuur2e) Preparation of the acid chloride The sodium salt obtained above is suspended in ce 7906528 5 -5-benzene, the reaction mixture is cooled, 2 cm of pyridine is added under nitrogen atmosphere and then 4.7 cm of oxaly chloride is stirred, concentrated to dry, under reduced pressure, adds benzene and concentrates again to dryness to completely remove the 5 'benzene and the oxaly chloride. The precipitate formed is removed by filtration, washed with benzene, the benzene washings are added to the main filtrate and a benzene solution of d-trans 3,5-dimethyl-2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid chloride is obtained as such for the next step. 10 stage C: 5-benzyl 5-fugylmethyl ester of d-trans 3> 3-cyclic phenyl] 2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid is used
Aan de verkregen oplossing van d-trans-zuurchloride in benzeen 5 voegt men 2 cm pyridine en 1,12 g 5-benzy1-3-f ury1-methylalcoho1 opgelost in 10 cm ftenzeen toe. Men roert het reaktiemengsel geduren-15 de 16 uur bij kamertemperatuur, verdunt het met water, scheidt de organische fase door decanteren af, extraheert de waterige fase met ether, verenigt de etherextracten met de benzeenoplossing, wast de verkregen organische fase achtereenvolgens met een koude waterige zoutzuuroplossing, met water, met een waterige natriumcarbonaatop-20 lossing en vervolgens met water, droogt, concentreert tot droog, lost het residu· op in benzeen, leidt de verkregen benzeenoplossing door een aluminiumoxydekolom, concentreert het eluaat tot droog en verkrijgt 1,3 g 5-benzyl-3-furylmethylester van d-trans 3»3-dimethyl-2-cyclo-pentylideenmethyl-1-cyclopropaancarbonzuur.To the resulting solution of d-trans-acid chloride in benzene 5 are added 2 cm of pyridine and 1.12 g of 5-benzy1-3-furyl-methyl alcohol 10 dissolved in 10 cm of phtenzene. The reaction mixture is stirred for 15 hours at room temperature, diluted with water, the organic phase is separated by decantation, the aqueous phase is extracted with ether, the ether extracts are combined with the benzene solution, the organic phase obtained is subsequently washed with a cold aqueous solution. hydrochloric acid solution, with water, with an aqueous sodium carbonate solution and then with water, dries, concentrates to dryness, dissolves the residue in benzene, passes the resulting benzene solution through an alumina column, concentrates the eluate to dryness and obtains 1.3 g 5-Benzyl-3-furylmethyl ester of d-trans 3 »3-dimethyl-2-cyclopentylidenemethyl-1-cyclopropanecarboxylic acid.
O λ 25 η£· = 1,5420.O λ 25 η £ = 1.5420.
Analyse : C^HggO^ = 364,46Analysis: C ^ HggO ^ = 364.46
Berekend: C?o 79,09 W/o 7,74 Gevonden: 79,1 7,7 ÏÏ.V. Spectrum (ethanol) 50 max- bij 208 m/1 = 23.500.Calculated: C 79.09 W / o 7.74. Found: 79.1 7.7. Spectrum (ethanol) 50 max- at 208 m / 1 = 23,500.
790652¾-790652¾-
Claims (4)
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR74405A FR1505423A (en) | 1966-08-26 | 1966-08-26 | New derivatives of cyclopropane and method of preparation |
| FR74404A FR1507192A (en) | 1966-08-26 | 1966-08-26 | Novel aryl allylsulfones and method of preparation |
| FR74405 | 1966-08-26 | ||
| FR96425 | 1967-02-24 | ||
| FR96425A FR1527844A (en) | 1966-08-26 | 1967-02-24 | New acids and esters derived from cyclopropane and method of preparation |
| FR110719 | 1967-06-16 | ||
| FR110719A FR93112E (en) | 1966-08-26 | 1967-06-16 | New derivatives of cyclopropane and method of preparation. |
| FR114833A FR94309E (en) | 1966-08-26 | 1967-07-19 | New cyclopropane derivatives and method of preparation. |
| FR114833 | 1967-07-19 | ||
| FR74404 | 1975-12-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NL7906529A true NL7906529A (en) | 1980-01-31 |
| NL172853B NL172853B (en) | 1983-06-01 |
| NL172853C NL172853C (en) | 1983-11-01 |
Family
ID=38863090
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL6711770A NL162060C (en) | 1966-08-26 | 1967-08-28 | PROCESS FOR PREPARING 2-SUBSTITUTED -3,3-DIMETHYLCYCLOPROPANIC CARBONIC ACIDS AND ESTERS THEREOF. |
| NL7906529A NL172853C (en) | 1966-08-26 | 1979-08-30 | PROCESS FOR PREPARING AN ESTER OF A CYCLOPROPANIC CARBONIC ACID WITH INSECTICIDE ACTION |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL6711770A NL162060C (en) | 1966-08-26 | 1967-08-28 | PROCESS FOR PREPARING 2-SUBSTITUTED -3,3-DIMETHYLCYCLOPROPANIC CARBONIC ACIDS AND ESTERS THEREOF. |
Country Status (14)
| Country | Link |
|---|---|
| AT (2) | AT287671B (en) |
| BE (1) | BE702662A (en) |
| CH (3) | CH491851A (en) |
| CS (3) | CS180599B2 (en) |
| DE (1) | DE1668603B2 (en) |
| DK (3) | DK140720B (en) |
| ES (3) | ES344435A1 (en) |
| FR (5) | FR1505423A (en) |
| GB (2) | GB1207371A (en) |
| IL (2) | IL28541A (en) |
| NL (2) | NL162060C (en) |
| SE (2) | SE369517B (en) |
| SU (1) | SU691076A3 (en) |
| YU (5) | YU33952B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3714153A (en) * | 1970-06-22 | 1973-01-30 | Roussel Uclaf | Novel cyclopropanecarboxylic acids |
| US4045469A (en) | 1971-06-25 | 1977-08-30 | The Procter & Gamble Company | Insecticidal esters of spiro carboxylic acids |
| BE791304A (en) * | 1971-11-12 | 1973-05-14 | Procter & Gamble | 1-ACENAPHTENOL ESTERS |
| DE2326077C2 (en) * | 1972-05-25 | 1985-12-12 | National Research Development Corp., London | Unsaturated cyclopropanecarboxylic acids and their derivatives, their preparation and insecticides containing them |
| HU168432B (en) * | 1973-08-15 | 1976-04-28 | ||
| DE2857020A1 (en) * | 1977-07-04 | 1981-01-08 | Astra Laekemedel Ab | A NOVEL INTERMEDIATE FOR PREPARATION OF THERAPEUTICALLY ACTIVE PYRIDINE COMPOUNDS |
| DE2730515A1 (en) * | 1977-07-06 | 1979-01-18 | Bayer Ag | SUBSTITUTED PHENOXYBENZYLOXYCARBONYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES |
| FR2426673A1 (en) * | 1978-05-25 | 1979-12-21 | Nat Res Dev | PYRETHRINE TYPE PESTICIDES |
| FR2428029A1 (en) * | 1978-06-06 | 1980-01-04 | Roussel Uclaf | ESTERS OF CYCLOPROPANE CARBOXYLIC ACIDS SUBSTITUTED BY A-CYANE ALCOHOL, PROCESS FOR THEIR PREPARATION AND INSECTICIDE OR NEMATICIDE COMPOSITIONS CONTAINING THEM |
| FR2443452A1 (en) * | 1978-12-08 | 1980-07-04 | Roussel Uclaf | NEW PROCESS FOR THE SPLITTING OF DL CIS ACID AND DL CHRYSANTHEMIC TRANS |
| FR2455024A1 (en) * | 1979-04-03 | 1980-11-21 | Roussel Uclaf | NEW PROCESS FOR THE SPLITTING OF ACIDS D, L-CIS 2,2-DIMETHYL 3- (2 ', 2'-DIHALOVINYL) CYCLOPROPANE-1-CARBOXYLIC |
| FR2455018A1 (en) * | 1979-04-26 | 1980-11-21 | Roussel Uclaf | ALLETHROLONE DERIVATIVES AND THEIR PREPARATION PROCESS |
| DE2926671A1 (en) * | 1979-07-02 | 1981-01-15 | Bayer Ag | METHOD FOR THE PRODUCTION OF CYCLOPROPANE-CARBONIC ACID DERIVATIVES AND NEW INTERMEDIATE PRODUCTS THEREFOR AND METHOD FOR THE PRODUCTION THEREOF |
| FR2479192A1 (en) * | 1980-03-28 | 1981-10-02 | Roussel Uclaf | PROCESS FOR THE PREPARATION OF TETRA-SUBSTITUTED CYCLOPROPANIC DERIVATIVES |
| FR2490633A1 (en) | 1980-09-24 | 1982-03-26 | Roussel Uclaf | PROCESS FOR THE PREPARATION OF CYCLOPROPANE CARBOXYLIC ACID DERIVATIVES WITH ALDEHYDE FUNCTION |
| US5504245A (en) * | 1994-09-30 | 1996-04-02 | Eastman Chemical Company | Processes for the preparation of cyclopropanecarboxylic acid and derivatives thereof |
-
1966
- 1966-08-26 FR FR74405A patent/FR1505423A/en not_active Expired
- 1966-08-26 FR FR74404A patent/FR1507192A/en not_active Expired
-
1967
- 1967-02-24 FR FR96425A patent/FR1527844A/en not_active Expired
- 1967-06-16 FR FR110719A patent/FR93112E/en not_active Expired
- 1967-07-19 FR FR114833A patent/FR94309E/en not_active Expired
- 1967-08-14 BE BE702662D patent/BE702662A/xx not_active IP Right Cessation
- 1967-08-15 CH CH601569A patent/CH491851A/en not_active IP Right Cessation
- 1967-08-15 CH CH1843169A patent/CH509961A/en not_active IP Right Cessation
- 1967-08-15 CH CH1143867A patent/CH491071A/en not_active IP Right Cessation
- 1967-08-22 IL IL2854167A patent/IL28541A/en unknown
- 1967-08-22 IL IL3818267A patent/IL38182A/en unknown
- 1967-08-23 CS CS565167A patent/CS180599B2/en unknown
- 1967-08-23 CS CS602967A patent/CS180551B2/en unknown
- 1967-08-23 CS CS565067A patent/CS180598B2/en unknown
- 1967-08-25 SE SE1192167A patent/SE369517B/xx unknown
- 1967-08-25 ES ES344435A patent/ES344435A1/en not_active Expired
- 1967-08-25 DE DE19671668603 patent/DE1668603B2/en active Granted
- 1967-08-25 SE SE13371A patent/SE391330B/en unknown
- 1967-08-25 ES ES344436A patent/ES344436A1/en not_active Expired
- 1967-08-25 DK DK430367A patent/DK140720B/en not_active IP Right Cessation
- 1967-08-26 SU SU671182999A patent/SU691076A3/en active
- 1967-08-26 YU YU168467A patent/YU33952B/en unknown
- 1967-08-26 YU YU168567A patent/YU35568B/en unknown
- 1967-08-28 AT AT789967A patent/AT287671B/en active
- 1967-08-28 NL NL6711770A patent/NL162060C/en not_active IP Right Cessation
- 1967-08-28 AT AT07278/69A patent/AT289754B/en not_active IP Right Cessation
- 1967-08-29 GB GB3954267A patent/GB1207371A/en not_active Expired
- 1967-08-29 GB GB836770A patent/GB1207372A/en not_active Expired
-
1968
- 1968-02-23 ES ES350839A patent/ES350839A1/en not_active Expired
- 1968-02-23 YU YU42168A patent/YU33942B/en unknown
-
1970
- 1970-12-28 DK DK657370A patent/DK131538C/en not_active IP Right Cessation
- 1970-12-28 DK DK657270A patent/DK133579B/en unknown
-
1978
- 1978-02-23 YU YU42178A patent/YU42168A/en unknown
-
1979
- 1979-08-30 NL NL7906529A patent/NL172853C/en not_active IP Right Cessation
- 1979-11-27 YU YU290379A patent/YU290379A/en unknown
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