DK155882B - METHOD OF PREPARING ALFA-CYANOBENZYL CARBOXYL TESTERS - Google Patents
METHOD OF PREPARING ALFA-CYANOBENZYL CARBOXYL TESTERS Download PDFInfo
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- C07C255/00—Carboxylic acid nitriles
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- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
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Description
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Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af visse insecticidt aktive estere af den såkaldte "syntetiske pyrethroidtype".The present invention relates to a process for the preparation of certain insecticide-active esters of the so-called "synthetic pyrethroid type".
Det er i henhold til tysk fremlæggelsesskrift nr. 2.231.312 kendt, at visse syntetiske pyrethroider kan fremstilles ved omsætning af et substitueret cyclopropancarbonylhalogenid med en 3-substitueret benzaldehyd i nærværelse af vandigt natrium- eller kaliumcyanid.It is known in German Patent Specification No. 2,231,312 that certain synthetic pyrethroids can be prepared by reacting a substituted cyclopropanecarbonyl halide with a 3-substituted benzaldehyde in the presence of aqueous sodium or potassium cyanide.
Ved denne fremgangsmåde fås pyrethroider af følgende type: ΛΟΝ _/ cool -/j> ' 2This method gives pyrethroids of the following type: ΛΟΝ _ / cool - / j> '2
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Det har nu vist sig, at udbyttet af esteren af den ved formel I viste type samt andre estere, der hører til området "syntetiske pyrethroider", kan fremstilles mere effektivt og med højere udbytter ved anvendelse af en bestemt katalysator.It has now been found that the yield of the ester of the type of formula I as well as other esters belonging to the field of "synthetic pyrethroids" can be more efficiently produced and with higher yields using a particular catalyst.
Opfindelsen angår således en fremgangsmåde til fremstilling afThe invention thus relates to a process for the preparation of
a-cyanobensyl-carboxylatestere med den almene formel IIα-cyanobenzyl-carboxylate esters of the general formula II
AA
€N __/ r-co-o-ch-t x\ ii€ N __ / r-co-o-ch-t x \ ii
hvor R er en alkylgruppe, som eventuelt er substitueret med en halogensubstitueret phenylgruppe, eller er en cycloalkylgruppe, som eventuelt er substitueret med én eller flere alkyl-, alkenyl-eller halogenalkenylgrupper, som hver indeholder op til 8 carbon-atomer, og A er phenoxy, phenylthio eller benzyl, hvor et benzal-dehyd med den almene formel IIIwherein R is an alkyl group optionally substituted by a halogen substituted phenyl group, or is a cycloalkyl group optionally substituted by one or more alkyl, alkenyl or haloalkenyl groups each containing up to 8 carbon atoms and A is phenoxy , phenylthio or benzyl, wherein a benzaldehyde of the general formula III
OCH-^ ^ IIIAND- ^ III
omsættes med et acylhalogenid med den almene formel R-CO-Hal, hvor Hal betegner bromid eller chlorid, i nærværelse af vand, et vandopløseligt cyanid og et i det væsentlige med vand ublandbart aprot opløsningsmiddel, hvilken fremgangsmåde er ejendommelig ved, at omsætningen udføres i nærværelse af en faseoverføringskatalysator.react with an acyl halide of the general formula R-CO-Hal, wherein Hal represents bromide or chloride, in the presence of water, a water-soluble cyanide and a substantially water-immiscible aprotic solvent, the process being characterized in that the reaction is carried out in the presence of a phase transfer catalyst.
Faseoverføringskatalysatoren kan være et hvilket som helst reagens, som er i stand til at accelerere interfasereaktioner i vandig/orga-niske tofasesysterner.The phase transfer catalyst may be any reagent capable of accelerating interphase reactions in aqueous / organic two-phase systems.
Faseoverføringskatalysatoren kan være en oniumforbindelse, især en kvatemær oniumforbindelse med den almene formel R1 + ,1 4 r -x-R y tThe phase transfer catalyst may be an onium compound, especially a quaternary onium compound of the general formula R1 +, 1 4 r -x-R y t
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1 2 hvor X betegner et nitrogen-, phosphor- eller arsenatom, R , R , 3 4 R og R hver betegner en alkyl-, aralkyl-, alkaryl- eller aryl-gruppe, og Y betegner en monovalent ion, f.eks. et halogenid såsom chlorid, bromid eller iodid, eller et alkylsulfat såsom methylsul-fat eller ethylsulfat eller en sulfoniumforbindelse med den almene formel R6 + 5 I 71 2 wherein X represents a nitrogen, phosphorus or arsenic atom, R, R, 3 4 R and R each represent an alkyl, aralkyl, alkaryl or aryl group, and Y represents a monovalent ion, e.g. a halide such as chloride, bromide or iodide, or an alkyl sulfate such as methyl sulfate or ethyl sulfate or a sulfonium compound of the general formula R6 + 5 I 7
R -S-R' J YR -S-R 'J Y
5 6 7 hvor R , R og R hver betegner en alkylgruppe, og Y betegner en monovalent ion, f.eks. et halogenid såsom chlorid, bromid eller iodid, eller et alkylsulfat såsom methylsulfat eller ethylsulfat. Det foretrækkes, at alkylgrupperne indeholder 1-18 carbonatomer, og at aralkyl- og alkarylgrupperne indeholder op til 10 carbonatomer; arylgruppen er fortrinsvis phenyl.Wherein R, R and R each represent an alkyl group and Y represents a monovalent ion, e.g. a halide such as chloride, bromide or iodide, or an alkyl sulfate such as methyl sulfate or ethyl sulfate. It is preferred that the alkyl groups contain 1-18 carbon atoms and that the aralkyl and alkaryl groups contain up to 10 carbon atoms; the aryl group is preferably phenyl.
Eksempler på egnede oniumforbindelser er tetra-n-butylammoniumbro-mid, tetra-n-butylammoniumchlorid, methyltri-2-methylphenyl-ammoni-umchlorid, tetramethylphosphoniumiodid, tetra-n-butylphosphonium-bromid, methyltriphenylarsoniumiodid, ethyl-2-methylpentadecyl-2--methylundecylsulfoniumethylsulfat, methyldinonylsulfoniummethyl-sulfat og n-hexadecyldimethylsulfoniumiodid. Der er opnået særdeles gode resultater med kvaternære ammoniumforbindelser.Examples of suitable onium compounds are tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, methyltri-2-methylphenylammonium chloride, tetramethylphosphonium iodide, tetra-n-butylphosphonium bromide, methyltriphenylarsonium iodide, ethyl triphenylarsonium iodide, ethyl triphenylarsonium iodide methylundecylsulfonium ethylsulfate, methyldinonylsulfonium methylsulfate and n-hexadecyldimethylsulfonium iodide. Very good results have been obtained with quaternary ammonium compounds.
Oniumforbindelsen kan være et hydroxid eller et salt og kan anvendes som den funktionelle del af en stærkt basisk anionbytterharpiks med en strukturel del (polymermatrix) og en funktionel del (ionaktiv gruppe). Af særlig vigtighed er polystyrenharpikser, f.eks. copoly-mere af aromatiske monovinylforbindelser og aromatiske polyvinyl-forbindelser, især styren/divinylbenzen-copolymere. Den funktionelle del er en kvaternær ammonium-, phosphonium- eller arsoniumgruppe. Eksempler på anvendelige stærkt basiske anionbytterharpikser er sådanne afledt af trimethylamin (f.eks. de produkter, der kendes under handelsnavnene "Amberlite IRA-400", "Amberlite IRA-401", "Amberlite IRA-402", "Amberlite IRA-900", "Duolite A-101-D", "Duolite ES-111", "Dowex 1", "Dowex 11", "Dowex 21K" og "Ionac A-450") og sådanne afledt af dimethylethanolamin (f.eks. de produkter, der 4The onium compound can be a hydroxide or salt and can be used as the functional part of a highly basic anion exchange resin with a structural part (polymer matrix) and a functional part (ion active group). Of particular importance are polystyrene resins, e.g. copolymers of aromatic monovinyl compounds and aromatic polyvinyl compounds, especially styrene / divinylbenzene copolymers. The functional moiety is a quaternary ammonium, phosphonium or arsonium group. Examples of useful highly basic anion exchange resins are those derived from trimethylamine (for example, the products known under the trade names "Amberlite IRA-400", "Amberlite IRA-401", "Amberlite IRA-402", "Amberlite IRA-900" , "Duolite A-101-D", "Duolite ES-111", "Dowex 1", "Dowex 11", "Dowex 21K" and "Ionac A-450") and such derived from dimethylethanolamine (e.g. products containing 4
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kendes under handelsnavnene "Amberlite IRA-410", "Amberlite IRA-911", "Dowex 2", "Duolite A-102-D", "Ionac A-542" og "Ionac A-5501') .are known under the trade names "Amberlite IRA-410", "Amberlite IRA-911", "Dowex 2", "Duolite A-102-D", "Ionac A-542" and "Ionac A-5501").
Der er opnået særdeles gode resultater med de af trimethylamin afledte produkter.Very good results have been obtained with the trimethylamine derived products.
Andre egnede faseoverføringskatalysatorer er makrocycliske poly-ethere, der kendes under betegnelsen "crown-ethere". Disse forbindelser samt deres fremstilling er beskrevet i litteraturen, f.eks. i Tetrahedron Letters No. 18 (1972), side 1793 - 1796, og betegnes sædvanligvis ved angivelse af det samlede antal atomer, som udgør den makrocycliske ring, sammen med antallet af- oxygenatomer i denne ring. Den makrocycliske polyether, hvis formelle kemiske navn er 1,4,7,10,13,16-hexaoxacyclooctadecan, betegnes således "18-crown-6". Andre eksempler på egnede makrocycliske polyethere er 3,4-benzo--1,6,9,12,15,18,21-heptaoxacyclotricos-3-en og 3,4-benzo-l,6,9,12--tetraoxacyclotetradec-3-en. 18-Crown-6 er særlig velegnet.Other suitable phase transfer catalysts are macrocyclic polyethers known as "crown ethers". These compounds as well as their preparation are described in the literature, e.g. in Tetrahedron Letters No. 18 (1972), pages 1793 - 1796, and is usually denoted by the total number of atoms constituting the macrocyclic ring together with the number of oxygen atoms in that ring. Thus, the macrocyclic polyether, whose formal chemical name is 1,4,7,10,13,16-hexaoxacyclooctadecane, is referred to as "18-crown-6". Other examples of suitable macrocyclic polyethers are 3,4-benzo-1,6,9,12,15,18,21-heptaoxacyclotricos-3-ene and 3,4-benzo-1,6,9,12-tetraoxacyclotetradec -3-one. 18-Crown-6 is particularly suitable.
Andre egnede faseoverføringskatalysatorer er overfladeaktive midler. Et "overfladeaktivt middel" er defineret som i Kirk-Othmer, "Encyclopedia of Chemical Technology", 2. udgave, bind 19 (1969), side 508: "En organisk forbindelse, som i samme molekyle indeholder to forskellige strukturelle grupper, hvoraf én er vandopløselig, og én er vanduopløselig."Other suitable phase transfer catalysts are surfactants. A "surfactant" is defined as in Kirk-Othmer, "Encyclopedia of Chemical Technology", 2nd Edition, Volume 19 (1969), page 508: "An organic compound containing in the same molecule two different structural groups, one of which is water-soluble and one is water-insoluble. "
Det overfladeaktive middel er fortrinsvis ikke-ionisk, f.eks. et poly(alkylenoxy)derivat dannet ved omsætning af en højere alkohol, alkylphenol eller fedtsyre med ethylenoxid eller propylenoxid.The surfactant is preferably nonionic, e.g. a poly (alkyleneoxy) derivative formed by reacting a higher alcohol, alkylphenol or fatty acid with ethylene oxide or propylene oxide.
Egnede alkoholer, alkylphenoler eller fedtsyrer indeholder en al-kylgruppe med 8-20 carbonatomer, og antallet af alkylenoxyenheder er i området 1 - 50. Et særlig velegnet ikke-ionisk overfladeaktivt middel (som i eksemplerne er betegnet "Dobanol 91-6") er fremstillet af en Cg-C-^-n-alkanolblanding og indeholder gennemsnitlig 6 ethy-lenoxyenheder. Det ikke-ioniske overfladeaktive middel kan være en alkylbenzen indeholdende en lige alkylgruppe. Egnede alkylbenze-ner indeholder alkylgrupper med 8-20 carbonatomer.Suitable alcohols, alkylphenols or fatty acids contain an alkyl group of 8-20 carbon atoms and the number of alkylene oxy units is in the range of 1 to 50. A particularly suitable nonionic surfactant (referred to in the examples as "Dobanol 91-6") is prepared from a Cg-C - ^ n-alkanol mixture and contains an average of 6 ethyleneoxy units. The nonionic surfactant may be an alkylbenzene containing a straight alkyl group. Suitable alkylbenzenes contain alkyl groups of 8-20 carbon atoms.
Det molære forhold mellem mængden af faseoverføringskatalysator og mængden af benzaldehyd med den almene formel III kan variere inden for vide grænser, men er hensigtsmæssigt fra 1:5 til 1:500.The molar ratio of the amount of phase transfer catalyst to the amount of benzaldehyde of the general formula III may vary widely, but is conveniently from 1: 5 to 1: 500.
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Anvendelsen af lave molære forhold vil kræve længere tid til reaktionens tilendebringelse, medens anvendelsen af højere molære forhold naturligvis forøger de omkostninger, der medgår til at producere en given mængde ester. Valget af reaktionstiden og molært forhold mellem katalysator og benzaldehyd er gensidigt afhængigt af hinanden, og dette valg vil i det enkelte tilfælde afhænge af lokale økonomiske faktorer. Der opnås sædvanligvis særdeles gode resultater med molære forhold fra 1:10 til 1:100.The use of low molar ratios will require longer time for the completion of the reaction, while the use of higher molar ratios naturally increases the costs involved in producing a given amount of ester. The choice of reaction time and molar ratio of catalyst to benzaldehyde are mutually dependent, and this choice will in each case depend on local economic factors. Usually very good results are obtained with molar ratios of 1:10 to 1: 100.
En anden fordel ved fremgangsmåden ifølge opfindelsen er, at det molære forhold mellem mængden af acylhalogenid (R-CO-Hal) og mængden af benzaldehyd er 1:1 eller et lille overskud i forhold dertil. Dette molære forhold er fortrinsvis i området fra 1,1:1,0 til 1,0:1,0.Another advantage of the process of the invention is that the molar ratio of the amount of acyl halide (R-CO-Hal) to the amount of benzaldehyde is 1: 1 or a small excess relative thereto. This molar ratio is preferably in the range of 1.1: 1.0 to 1.0: 1.0.
Det molære forhold mellem mængden af vandoplø'seligt cyanid og mængden af aromatisk aldehyd er hensigtsmæssigt fra 1,5:1 til 1,0:1,0 og fortrinsvis fra 1,3:1 til 1,02:1,00. Med "vandopløseligt cyanid" menes et vandopløseligt salt af hydrogencyanid. Blandt de vandopløselige cyanider foretrækkes alkalimetalcyanider og jordalkali-metalcyanider. Natriumcyanid foretrækkes især, da det giver esterne med den almene formel II på den korteste reaktionstid.The molar ratio of the amount of water-soluble cyanide to the amount of aromatic aldehyde is suitably from 1.5: 1 to 1.0: 1.0 and preferably from 1.3: 1 to 1.02: 1.00. By "water-soluble cyanide" is meant a water-soluble salt of hydrogen cyanide. Among the water-soluble cyanides, alkali metal cyanides and alkaline earth metal cyanides are preferred. Sodium cyanide is particularly preferred as it gives the esters of general formula II in the shortest reaction time.
Den temperatur, ved hvilken fremgangsmåden udføres, er hensigtsmæssigt over 0°C og er fortrinsvis i området 10°C - 50°C. Der er opnået særdeles gode resultater med temperaturer i området 15 - 40°C. Fremgangsmåden har den fordel, at omgivelsestemperaturer er meget velegnede.The temperature at which the process is carried out is conveniently above 0 ° C and is preferably in the range of 10 ° C - 50 ° C. Very good results have been obtained with temperatures in the range of 15 - 40 ° C. The method has the advantage that ambient temperatures are very suitable.
Eksempler på egnede, i det væsentlige vand-ublandbare aprote opløsningsmidler er alkaner eller cycloalkaner eller en blanding deraf; specielle eksempler er n-hexan, n-heptan, n-octan, n-nonan, n-decan og deres isomere (f.eks. 2-methylpentan, 3-methylpentan, 2-methylhexan, 3-methylhexan og 2,4,4-trimethylpentan) og cyclohexan og methylcyclohexan. Benziner, som er rige på alkaner, er også særdeles velegnede, f.eks. med et kogeinterval ved atmosfæretryk mellem 40 og 65°C, 60 og 80°C og 80 og 110°C. Der er opnået særdeles gode resultater med n-heptan og cyclohexan.Examples of suitable, substantially water-immiscible aprotic solvents are alkanes or cycloalkanes or a mixture thereof; particular examples are n-hexane, n-heptane, n-octane, n-nonane, n-decane and their isomers (e.g. 2-methylpentane, 3-methylpentane, 2-methylhexane, 3-methylhexane and 2.4, 4-trimethylpentane) and cyclohexane and methylcyclohexane. Gasoline which is rich in alkanes is also very suitable, e.g. with a boiling range at atmospheric pressure between 40 and 65 ° C, 60 and 80 ° C and 80 and 110 ° C. Very good results have been obtained with n-heptane and cyclohexane.
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Andre særdeles velegnede, i det væsentlige med vand ublandbare aprote opløsningsmidler er aromatiske carbonhydrider og chlorerede carbonhydrider, f.eks. benzen, toluen, o-, m- og p-xylen, trimethyl-benzener, dichlormethan, 1,2-dichlormethan, chloroform, monochlor-benzen og 1,2- og 1,3-dichlorbenzen. Der er opnået særdeles gode resultater med toluen og xylen.Other particularly suitable, essentially water-immiscible aprotic solvents are aromatic hydrocarbons and chlorinated hydrocarbons, e.g. benzene, toluene, o-, m- and p-xylene, trimethylbenzenes, dichloromethane, 1,2-dichloromethane, chloroform, monochlorobenzene and 1,2- and 1,3-dichlorobenzene. Very good results have been obtained with toluene and xylene.
Ved fremgangsmåden ifølge opfindelsen kan man gå ud fra umættede eller mættede vandige opløsninger af vandopløseligt cyanid, og i sidstnævnte tilfælde i nærværelse eller fravær af fast vandopløseligt cyanid. Med nogle opløsningsmidler har det vist sig, at tilstedeværelsen af fast vandopløseligt cyanid forbedrer udbyttet og reaktionstiden.The process according to the invention may be based on unsaturated or saturated aqueous solutions of water-soluble cyanide, and in the latter case in the presence or absence of solid water-soluble cyanide. With some solvents it has been found that the presence of solid water-soluble cyanide improves yield and reaction time.
Ved anvendelse af alkaner eller cycloalkaner i kombination med vandige opløsninger af cyanid i fravær af fast vandopløseligt cyanid er det muligt at holde reaktionstiderne på et minimum. Ved anvendelse af aromatiske carbonhydrider eller chlorerede carbonhydrider i kombination med vandige opløsninger af cyanid i fravær af fast vandopløseligt cyanid fås lidt længere reaktionstider, men det foretrækkes ikke desto mindre undertiden at gå frem på denne måde, da den resulterende reaktionsblanding kan anvendes direkte til pesticidpræparater uden yderligere fraskillelse af esteren fra opløsningsmidlet. Ved anvendelse af aromatiske carbonhydrider og chlorerede carbonhydrider i kombination med fast vandopløseligt cyanid fås korte reaktionstider. Fast vandopløseligt cyanid kan imidlertid også anvendes i nærværelse af (cyclo)alkaner.When using alkanes or cycloalkanes in combination with aqueous solutions of cyanide in the absence of solid water-soluble cyanide, it is possible to keep reaction times to a minimum. By using aromatic hydrocarbons or chlorinated hydrocarbons in combination with aqueous solutions of cyanide in the absence of solid water-soluble cyanide, slightly longer reaction times are obtained, but it is nevertheless sometimes preferred to proceed in this way, as the resulting reaction mixture can be used directly for pesticide preparations without further separation of the ester from the solvent. By using aromatic hydrocarbons and chlorinated hydrocarbons in combination with solid water-soluble cyanide, short reaction times are obtained. However, solid water-soluble cyanide can also be used in the presence of (cyclo) alkanes.
Der kan opnås gode reaktionstider, når de molære forhold mellem mængden af vand og den samlede mængde vandopløseligt cyanid er højere end 0,05.Good reaction times can be obtained when the molar ratio of the amount of water to the total amount of water-soluble cyanide is higher than 0.05.
Andre eksempler på i det væsentlige med vand ublandbare aprote opløsningsmidler er dialkylethere og i det væsentlige med vand ublandbare alkanonert f.eks. diethylether, diisopropylether og diis obutylke ton. Der kan anvendes blandinger af opløsningsmidler, f.eks. af alkaner og aromatiske carbonhydrider, f.eks. af n-heptan indeholdende op til 10 vægtprocent benzen og/eller toluen.Other examples of substantially water-immiscible aprotic solvents are dialkyl ethers and substantially water-immiscible alkananates, e.g. diethyl ether, diisopropyl ether and diis obutylke ton. Solvents may be used, e.g. of alkanes and aromatic hydrocarbons, e.g. of n-heptane containing up to 10% by weight of benzene and / or toluene.
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Gruppen A i den almene formel II er fortrinsvis phenoxy, da denne substituent giver anledning til den mest aktive form af pyrethroid-pesticiderne.The group A of the general formula II is preferably phenoxy since this substituent gives rise to the most active form of the pyrethroid pesticides.
Alkylgrupper som R i den almene formel RC(0)Hal kan være lige eller forgrenet og indeholder fortrinsvis op til 10 carbon-atomer. Alkylgrupperne har fortrinsvis et tertiært eller kvaternært carbonatom bundet til gruppen -C(O)Hal. Eksempler på sådanne alka-noylhalogenider er 2-methylpropanoylchlorid, 2,2-dimethylpropanoyl-chlorid og 2-methylbutanoylbromid. Der er opnået særdeles gode resultater med 2-methylpropanoylchlorid. Som anført kan alkylgruppen som substituenter bære en halogenphenylgruppe. Der er opnået særdeles gode resultater med 1-(4-chlorphenyl)-2-methylpropylgrupper.Alkyl groups such as R in the general formula RC (O) Hal may be straight or branched and preferably contain up to 10 carbon atoms. The alkyl groups preferably have a tertiary or quaternary carbon atom attached to the group -C (O) Hal. Examples of such alkanoyl halides are 2-methylpropanoyl chloride, 2,2-dimethylpropanoyl chloride and 2-methylbutanoyl bromide. Very good results have been obtained with 2-methylpropanoyl chloride. As indicated, the alkyl group as substituents may carry a halophenyl group. Very good results have been obtained with 1- (4-chlorophenyl) -2-methylpropyl groups.
Cycloalkylgrupper som R i den almene formel RC(0)Hal indeholder selv fortrinsvis 3-6 carbonatomer og har, som anført ovenfor, som eventuelle substituenter en gruppe eller grupper valgt blandt alkyl, alkenyl og halogenalkenyl, som hver hensigtsmæssigt indeholder op til 8 carbonatomer. Eksempler på cycloalkylgrupper er cyclopropyl-, cyclobutyl- og cyclohexylgrupper. Der er opnået særdeles gode resultater med eventuelt substituerede cyclopropancarbonylhalogenider, især med 2,2,3,3-tetramethylcyclopropancarbonylhalogenider og 2-(2,2--dichlorvinyl)-3,3-dimethylcyclopropancarbonylhalogenider. De sidstnævnte halogenider kan have cis- eller trans-struktur eller kan være en blanding af sådanne strukturer og kan være en ren optisk isomer eller en blanding af optiske isomere.Cycloalkyl groups such as R in the general formula RC (O) Hal themselves preferably contain from 3 to 6 carbon atoms and, as indicated above, have as optional substituents a group or groups selected from alkyl, alkenyl and haloalkenyl each suitably containing up to 8 carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl and cyclohexyl groups. Very good results have been obtained with optionally substituted cyclopropanecarbonyl halides, especially with 2,2,3,3-tetramethylcyclopropanecarbonyl halides and 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarbonyl halides. The latter halides may have cis or trans structure or may be a mixture of such structures and may be a pure optical isomer or a mixture of optical isomers.
Substituenten Hal i den almene formel RC(0)Hal er fortrinsvis et chlor- eller bromatom og især et chloratom.The substituent Hal of the general formula RC (O) Hal is preferably a chlorine or bromine atom and especially a chlorine atom.
Fremgangsmåden ifølgecpfindelsen kan udføres ved gradvis tilsætning af acylhalogenidet til en blanding, fortrinsvis en omrørt blanding, af de andre udgangsforbindelser (hvilket er særlig fordelagtigt, når R i den almene formel RC(0)Hal er en 2,2,3,3-tetramethyl-cyclopropylgruppe, en 2-(2,2-dichlorvinyl)-3,3-dimethylcyclopropyl-• gruppe eller en 1-(4-chlorphenyl)-2-methylpropylgruppe). Alternativt kan de samlede mængder af udgangsmaterialerne bringes sammen, og reaktionen kan lades forløbe under kraftig omrøring af reaktionsblandingen.The process of the invention can be carried out by gradually adding the acyl halide to a mixture, preferably a stirred mixture, of the other starting compounds (which is particularly advantageous when R in the general formula RC (O) Hal is a 2,2,3,3-tetramethyl -cyclopropyl group, a 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropyl group or a 1- (4-chlorophenyl) -2-methylpropyl group). Alternatively, the total amounts of the starting materials may be brought together and the reaction may be allowed to proceed with vigorous stirring of the reaction mixture.
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Fremgangsmåden er af særlig interesse, når det aromatiske aldehyd er 3-phenoxybenzaldehyd, og acylhalogenidet er 2-(4-chlorphenyl)-3--methylbutanoylchlorid, 2,2,3,3-tetramethylcyclopropancarbonyl-chlorid eller 2-(2,2-dichlorvinyl)-3,3-dimethylcyclopropancarbonyl-chlorid, eftersom de estere, som da dannes, a-cyano-3-phenoxybenzyl--2-(4-chlorphenyl)-3-methyIbutanoat, α-cyano-3-phenoxybenzyl-2,2,3,3-• -tetramethylcyclopropancarhoxylat og a-cyano-3-phenoxybenzyl-2-(2,2--dichlorvinyl)-3,3-dimethylcyclopropancarboxylat, er særlig aktive pesticide forbindelser.The process is of particular interest when the aromatic aldehyde is 3-phenoxybenzaldehyde and the acyl halide is 2- (4-chlorophenyl) -3-methylbutanoyl chloride, 2,2,3,3-tetramethylcyclopropanecarbonyl chloride or 2- (2,2- dichlorovinyl) -3,3-dimethylcyclopropanecarbonyl chloride, since the esters formed are α-cyano-3-phenoxybenzyl-2- (4-chlorophenyl) -3-methylbutanoate, α-cyano-3-phenoxybenzyl-2, 2,3,3- tetramethylcyclopropane carboxylate and α-cyano-3-phenoxybenzyl 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate are particularly active pesticidal compounds.
Fremgangsmåden ifølge opfindelsen belyses nærmere ved følgende eksempler. Alle forsøg er udført ved en temperatur på 23°C. Reaktionsblandingerne er omrørt kraftigt og er analyseret ved gas-væske--chromatografi til bestemmelse af udbyttet af den dannede ester. Reaktionsblandingerne er filtreret til fjernelse af eventuelt udfældet natriumchlorid og fast natriumcyanid, og tørringen af opløsninger er udført over vandfrit natriumsulfåt. Afdestillationen af opløsningsmidlet er udført i filmfordamper ved tryk på 15 mm Hg.The process according to the invention is illustrated in more detail by the following examples. All experiments were performed at a temperature of 23 ° C. The reaction mixtures are stirred vigorously and analyzed by gas-liquid chromatography to determine the yield of the ester formed. The reaction mixtures are filtered to remove any precipitated sodium chloride and solid sodium cyanide, and the drying of solutions is carried out over anhydrous sodium sulfate. The distillation of the solvent is carried out in film evaporator at a pressure of 15 mm Hg.
Alle udbytter er beregnet på det som udgangsmateriale anvendte aromatiske aldehyd.All yields are calculated on the aromatic aldehyde used as the starting material.
Eksempel 1.Example 1.
Fremstilling af a-cyano-3-phenoxybenzyl-2-(4-chlorphenyl)-3-methyl-butanoat i nærværelse af n-heptan.Preparation of α-cyano-3-phenoxybenzyl-2- (4-chlorophenyl) -3-methyl-butanoate in the presence of n-heptane.
En 50 ml rundbundet kolbe, som er udstyret med magnetomrører, påfyldes 10 millimol 3-phenoxybenzaldehyd, 10 millimol 2-(4-chlor-phenyl)-3-methylbutanoylchlorid, 12 millimol natriumcyanid, vand, eventuelt en katalysator og 20 ml n-heptan, og den resulterende blanding omrøres. Der udføres 7 forsøg på denne måde, jfr. tabel I.A 50 ml round bottom flask equipped with magnetic stirrer is charged with 10 millimoles of 3-phenoxybenzaldehyde, 10 millimoles of 2- (4-chlorophenyl) -3-methylbutanoyl chloride, 12 millimoles of sodium cyanide, water, optionally a catalyst and 20 ml of n-heptane. , and the resulting mixture is stirred. 7 attempts are made in this way, cf. Table I.
9 DK 155882 B9 DK 155882 B
Tabel ITable I
1 2 3 4 5 61 2 3 4 5 6
For- Katalysator Vand Reaktions- Udbytte af ester, søg - tilsat, tid, timer % nr* navn mængde, ml % mol beregnet på aldehydet 11) - - 1,0 ' 3 86 18 mere end 99 2 methyl-tri-2- 5 1,0 2 96 -methyl-heptyl- ammoniumchlo- rid 3 tetra-n-butyl- 2 1,0 5 99 ammoniumchlo- rid 4 tetra-n-butyl- 2 2,0 5 99 ammoniumchlo- rid 5 tetra-n-butyl- 2 1,0 3 99 phosphonium- bromid 6 n-hexadecyldi- 2 1,0 3 97 methylsulfoni- umiodid 7 1,4,7,10,13,- 2 1,0 3 94 16-hexaoxacyc- looctadecan ^ ikke ifølge opfindelsen. (Sammenligningseksempel)Pre-Catalyst Water Reaction Yield of ester, search - added, time, hours% no * name amount, ml% mol based on the aldehyde 11) - - 1.0 '3 86 18 more than 99 2 methyl-tri-2- 5 1.0 2 96 -methyl-heptyl ammonium chloride 3 tetra-n-butyl 2 1.0 5 99 ammonium chloride 4 tetra-n-butyl 2 2.0 5 99 ammonium chloride 5 tetra-n -butyl-2 1.0 3 99 phosphonium bromide 6 n-hexadecyl di-2 1.0 3 97 methylsulfonium iodide 7 1,4,7,10,13, - 2 1,0 3 94 16-hexaoxacyclooctadecane not according to the invention. (Comparative Example)
Kolonne 1 i tabel I angiver forsøgets nummer, kolonne 2 angiver katalysatoren, kolonne 4 angiver den mængde vand, som er sat til udgangsblandingen (bortset fra det vand, som er til stede i natriumcyanidet) , og kolonne 5 angiver reaktionstiden. Udbyttet af den ønskede ester fremgår af kolonne 6. Natriumcyanidet opløses fuldstændigt .Column 1 of Table I indicates the number of the experiment, column 2 indicates the catalyst, column 4 indicates the amount of water added to the starting mixture (other than the water present in the sodium cyanide), and column 5 indicates the reaction time. The yield of the desired ester is shown in column 6. The sodium cyanide dissolves completely.
10 DK 155882BDK DK 155882B
Eksempel 2.Example 2.
Fremstilling af <x-cyano-3-phenoxybenzyl-2-(2,2,-dichlorvinyl)--3,3-dimethylcyclopropancarboxylat i nærværelse af n-heptan.Preparation of <x-cyano-3-phenoxybenzyl-2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropane carboxylate in the presence of n-heptane.
En 50 ml*s rundbundet kolbe, som er udstyret med magnetomrører, påfyldes 10 millimol 3-phenoxybenzaldehyd, en mængde 2-(2,2-di-chlorvinyl)-3,3-dimethylcyclopropancarbonylchlorid, 12 millimol natriumcyanid, vand, eventuelt en katalysator og 20 ml n-heptan. Den resulterende blanding omrøres. Der udføres seks forsøg på denne måde, jfr. tabel II. Kolonne 3, 4 og 5 angiver mængderne af katalysator, vand og tilsat acylchlorid. Udbyttet af den ønskede ester fremgår af kolonne 7.A 50 ml * s round bottom flask equipped with magnetic stirrer is charged with 10 millimoles of 3-phenoxybenzaldehyde, an amount of 2- (2,2-dichlorovinyl) -3,3-dimethylcyclopropanecarbonyl chloride, 12 millimoles of sodium cyanide, water, optionally a catalyst. and 20 ml of n-heptane. The resulting mixture is stirred. Six attempts are made in this way, cf. Table II. Columns 3, 4 and 5 indicate the amounts of catalyst, water and acyl chloride added. The yield of the desired ester is shown in column 7.
Tabel IITable II
1 2 3 4 5 6 71 2 3 4 5 6 7
For- Katalysator Tilsat Acylchlo- Reaktions- Udbytte af søg _ vand, rid, mil- tid, timer ester, % nr. ml limolPre-Catalyst Added Acylchlo Reaction Yield of Search _ Water, Ride, Mild, Hours Ester,% No. ml Limol
Navn Mængde, % mol beregnet på aldehyd 1 2 3 4 5 6 1} - - 1,0 10,2 3 49 21 94 44 99 2 methyl-tri-2- 5 1,0 10,2 1 96 -methylheptyl- ammoniumchlo- rid 3 tetra-n-butyl- 2 1,0 10,5 1 90 ammoniumchlo- . ..Name Amount,% mole calculated on aldehyde 1 2 3 4 5 6 1} - - 1.0 10.2 3 49 21 94 44 99 2 methyl tri-2- 5 1.0 10.2 1 96 -methylheptylammonium chloro - riding 3 tetra-n-butyl 2 1.0 10.5 1 90 ammonium chloro. ..
rid 4 99 4 "Amberlite (1 1,0 10,5 5 95 IRA 400« 2) 9ram) 5 "Dobanol 91-6"3)2 1,0 10,0 2 80 6 1,4,7,10,13,16- 2 1,0 10,0 2 76 -hexaoxacyclo- octadecanrid 4 99 4 "Amberlite (1 1.0 10.5 5 95 IRA 400« 2) 9ram) 5 "Dobanol 91-6" 3) 2 1.0 10.0 2 80 6 1,4,7.10, 13.16-2.0 10.0 2 76 -hexaoxacyclooctadecane
11 DK 155882B11 DK 155882B
1) Ikke ifølge opfindelsen. (Sammenligningseksempel) 2) Varemærke for en stærkt basisk anionbytterharpiks med en styren/-divinylbenzen-copolymer som en polymermatrix og en kvaternær ammo-niumgruppe som ionaktiv gruppe. Der anvendes chloridform.1) Not according to the invention. (Comparative Example) 2) Trademark of a highly basic anion exchange resin with a styrene / divinylbenzene copolymer as a polymer matrix and a quaternary ammonium group as ion active group. Chloride form is used.
3) Varemærke for et ikke-ionisk overfladeaktivt middel fremstillet ud fra Cg-C^-alkoholblanding og indeholdende gennemsnitlig seks ethylenoxyenheder; alkoholblandingen består af 85% n-alkanoler og 15% 2-alkylalkanoler.3) Trademark for a non-ionic surfactant prepared from Cg-C4 alcohol mixture and containing an average of six ethylene oxy units; the alcohol mixture consists of 85% n-alkanols and 15% 2-alkylalkanols.
Eksempel 3.Example 3
Fremstilling af a-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclo-propancarboxylat i nærværelse af n-heptan.Preparation of α-cyano-3-phenoxybenzyl-2,2,3,3-tetramethylcyclopropane carboxylate in the presence of n-heptane.
De nedenfor angivne metoder A og B anvendes til fremstilling af denne ester. Dette eksempel viser, at der ved gradvis tilsætning af syrechloridet til reaktionsblandingen i løbet af et tidsrum på 0,5-2 timer fås betydelige forøgelser af udbyttet ved slutningen af dette tidsrum.Methods A and B listed below are used to prepare this ester. This example shows that by gradually adding the acid chloride to the reaction mixture over a period of 0.5-2 hours, significant increases in the yield are obtained at the end of this time.
Metode A.Method A.
En 50 ml rundbundet kolbe, som er udstyret med magnetomrører, påfyldes 10 millimol 3-phenoxybenzaldehyd, 10 millimol 2,2,3,3-tetra-methylcyclopropancarbonylchlorid, 12 millimol natriumcyanid, 1,00 ml vand, eventuelt en katalysator og 20 ml n-heptan. Det molære forhold mellem vand og NaCN er 4,64, og der er ikke fast NaCN til stede. Katalysatoren tilsættes i en mængde på 0,20 millimol. Den resulterende blanding omrøres i 1,5 timer og analyseres.A 50 ml round bottom flask equipped with magnetic stirrer is charged with 10 millimoles of 3-phenoxybenzaldehyde, 10 millimoles of 2,2,3,3-tetramethylcyclopropanecarbonyl chloride, 12 millimoles of sodium cyanide, 1.00 ml of water, optionally a catalyst and 20 ml of n heptane. The molar ratio of water to NaCN is 4.64 and no solid NaCN is present. The catalyst is added in an amount of 0.20 millimoles. The resulting mixture is stirred for 1.5 hours and analyzed.
Metode B. (Gradvis tilsætning af syrechloridet).Method B. (Gradual addition of the acid chloride).
Den kolbe, som anvendes til metode A, påfyldes 10 millimol 3-phen-oxybenzaldehyd, 12 millimol natriumcyanid, 10 ml n-heptan, 1,00 ml vand og eventuelt 0,20 millimol af en katalysator, idet det molære forhold mellem vand og NaCN er 4,64. En mængde på 10 millimol 2,2,3,3-tetramethylcyclopropancarbonylchlorid opløst i 10 ml n-heptan indføres i kolben i løbet af 70 - 75 minutter. Udbyttet af esteren bestemmes ved slutningen af dette tidsrum.The flask used for Method A is charged with 10 millimoles of 3-phenoxybenzaldehyde, 12 millimoles of sodium cyanide, 10 ml of n-heptane, 1.00 ml of water and optionally 0.20 millimoles of a catalyst, the molar ratio of water to NaCN is 4.64. An amount of 10 millimoles of 2,2,3,3-tetramethylcyclopropanecarbonyl chloride dissolved in 10 ml of n-heptane is introduced into the flask over 70 - 75 minutes. The yield of the ester is determined at the end of this time.
12 DK 155882 B12 DK 155882 B
Der udføres fem forsøg på denne måde. Tabel III angiver de eventuelt anvendte katalysatorer. Tabellen angiver også udbyttet af den ønskede ester.Five experiments are performed in this way. Table III lists the catalysts, if any, used. The table also indicates the yield of the desired ester.
Tabel IIITable III
Forsøg Katalysator Udbytte af ester, %Test Catalyst Yield of ester,%
nr. Metode A Metode BNo. Method A Method B
1*} ingen 17 40 2 1,4,7,10,13f16-hexaoxa- 18 97 cyclooctadecan 3 tetra-n-butylammonium- 20 98 chlorid 4 methyl-tri-2-methyl- 18 96 hepty1ammoniumchlorid 5 "Dobanol 91-6" 44 98 ** Ikke ifølge opfindelsen. (Sammenligningseksempel)1 *} none 17 40 2 1,4,7,10,13f16-hexaoxa-18 97 cyclooctadecane 3 tetra-n-butylammonium-98 chloride 4 methyl-tri-2-methyl-18 96-heptylammonium chloride 5 "Dobanol 91-6 44 98 ** Not according to the invention. (Comparative Example)
Jfr. forklaringen i sammenhæng med tabel II.Cf.. the explanation in the context of Table II.
De anvendte katalysatormængder er 2 molprocent i forsøg 2 - 4 og 10 molprocent i forsøg 5, beregnet på 3-phenoxybenzaldehyd.The catalyst amounts used are 2 mole percent in Experiments 2 - 4 and 10 mole percent in Experiment 5, calculated on 3-phenoxybenzaldehyde.
Den i forsøg 4, metode B, vundne reaktionsblanding filtreres, og filtratet vaskes to gange med 20 ml af en 1M vandig opløsning af natriumbicarbonat og én gang med 20 ml vand. Det vaskede filtrat tørres, og n-heptanet fjernes fra det tørrede filtrat, hvorved esteren fås som en bleggul olie. Denne olie opløses i 2,5 ml methanol ved 23°C, og den resulterende opløsning afkøles til en temperatur på -20°C, hvorved fås et bundfald af esteren. Esteren filtreres og har en renhed på over 98%.The reaction mixture obtained in Experiment 4, Method B is filtered and the filtrate is washed twice with 20 ml of a 1M aqueous solution of sodium bicarbonate and once with 20 ml of water. The washed filtrate is dried and the n-heptane is removed from the dried filtrate to give the ester as a pale yellow oil. This oil is dissolved in 2.5 ml of methanol at 23 ° C, and the resulting solution is cooled to a temperature of -20 ° C to give a precipitate of the ester. The ester is filtered and has a purity of over 98%.
Eksempel 4.Example 4
Fremstilling af <x-cyano-3-phenoxybenzyl-2- (4-chlorphenyl) -3-methyl-butanoat i stor målestok.Preparation of <x-cyano-3-phenoxybenzyl-2- (4-chlorophenyl) -3-methyl-butanoate on a large scale.
13 DK 155882 B13 DK 155882 B
Metoderne A (ikke ifølge opfindelsen), B og C sammenlignes til fremstilling af den ønskede ester.Methods A (not according to the invention), B and C are compared to produce the desired ester.
Metode A, i fravær af en faseoverføringskatalysator. (Sammenligningseksempel)Method A, in the absence of a phase transfer catalyst. (Comparative Example)
En 500 ml's rundbundet kolbe, som er udstyret med skovlomrører, påfyl des 100 millimol 3-phenoxybenzaldehyd, 100 millimol 2-(4-chlorphe-nyl)-3-methylbutanoylchlorid, 120 millimol natriumcyanid, 10 ml vand (som opløser al natriumcyanidet) og 200 ml n-heptan. Efter omrøring i 45 timer opvarmes blandingen til en temperatur mellem 40 og 50°C og filtreres. Filtratet vaskes to gange med 50 ml af en 1M vandig natriumbicarbonatopløsning og én gang med 50 ml vand og tørres, og n-heptanet fjernes fra den tørrede opløsning, hvorved fås den ønskede ester i et udbytte på 99% og med en renhed på 96%.A 500 ml round bottom flask equipped with paddle stirrer is charged with 100 millimoles of 3-phenoxybenzaldehyde, 100 millimoles of 2- (4-chlorophenyl) -3-methylbutanoyl chloride, 120 millimoles of sodium cyanide, 10 ml of water (which dissolves all the sodium cyanide) and 200 ml of n-heptane. After stirring for 45 hours, the mixture is heated to a temperature between 40 and 50 ° C and filtered. The filtrate is washed twice with 50 ml of a 1M aqueous sodium bicarbonate solution and once with 50 ml of water and dried, and the n-heptane is removed from the dried solution to give the desired ester in a yield of 99% and with a purity of 96% .
Metode B, i nærværelse af en oniumforbindelse.Method B, in the presence of an onium compound.
Det i afsnit A i nærværende eksempel beskrevne forsøg gentages i nærværelse af 2 molprocent tetra-n-butylammoniumchlorid, beregnet på 3-phenoxybenzaldehyd. Efter 2 timers forløb fås esteren i et udbytte på 99% med en renhed på 94%.The experiment described in section A of this example is repeated in the presence of 2 mole percent tetra-n-butylammonium chloride, calculated on 3-phenoxybenzaldehyde. After 2 hours, the ester is obtained in 99% yield with a purity of 94%.
Metode C, i nærværelse af et ikke-ionisk overfladeaktivt middel.Method C, in the presence of a nonionic surfactant.
Det i afsnit A i nærværende eksempel beskrevne forsøg gentages i nærværelse af 10 molprocent "Dobanol 91-6" (jfr. forklaringen i sammenhæng med tabel II), beregnet på 3-phenoxybenzaldehyd. Efter 3 timers omrøring opvarmes reaktionsblandingen til en temperatur mellem 40 og 50°C og filtreres. Til brydning af den dannede emulsion sættes 50 ml ethanol til filtratet, og filtratet vaskes to gange med 50 ml af en 1M vandig opløsning af natriumbicarbonat og én gang med 50 ml vand, hvorpå det tørres, og n-heptanet fjernes fra den tørrede opløsning, hvorved fås esteren i et udbytte på 98% og med en renhed på 97%.The experiment described in Section A of this example is repeated in the presence of 10 mole percent "Dobanol 91-6" (see the explanation in the context of Table II), calculated on 3-phenoxybenzaldehyde. After stirring for 3 hours, the reaction mixture is heated to a temperature between 40 and 50 ° C and filtered. To break the emulsion formed, 50 ml of ethanol is added to the filtrate and the filtrate is washed twice with 50 ml of a 1M aqueous solution of sodium bicarbonate and once with 50 ml of water, then dried and the n-heptane removed from the dried solution. thereby obtaining the ester in a yield of 98% and with a purity of 97%.
De ovenfor anførte resultater sammenfattes i nedenstående tabel IV.The above results are summarized in Table IV below.
14 DK 155882B14 DK 155882B
Tabel IVTable IV
Forsøg Katalysator Reaktions - Udbytte Esterens nr. -- tid, af es- renhed, %Test Catalyst Reaction - Yield Ester No. - Time, of Purity,%
Navn Mængde, mol- timer ter' % procent beregnet på aldehyd 1 ingen 2) - 45 99 96 2 tetra-n-butyl- 2 2 99 94 ammoniumchlo- rid 3 "Dobanol 91-6"1) 10 3 98 97Name Amount, times per hour calculated on aldehyde 1 none 2) - 45 99 96 2 tetra-n-butyl 2 2 99 94 ammonium chloride 3 "Dobanol 91-6" 1) 10 3 98 97
Jfr. forklaringen i sammenhæng med tabel II.Cf.. the explanation in the context of Table II.
2)2)
Sammenlicnincseksempel Eksempel 5.Comparative Example Example 5.
Fremstilling af a-cyano-3-phenoxybenzyl-2-(4-chlorphenyl)-3-methyl-butanoat i nærværelse af fast cyanid.Preparation of α-cyano-3-phenoxybenzyl 2- (4-chlorophenyl) -3-methyl-butanoate in the presence of solid cyanide.
En 50 ml's rundbundet kolbe, som er udstyret med magnetomrører, påfyldes 10 millimol 3-phenoxybenzaldehyd, 10,5 millimol 2-(4--chlorphenyl)-3-methylbutanoylchlorid, 12 millimol natriumcyanid, 20 ml toluen, en faseoverføringskatalysator og vand. Den på denne måde vundne blanding omrøres i varierende tidsrum, hvorefter den analyseres. Der udføres seks forsøg på denne måde, og resultaterne fremgår af nedenstående tabel VI, som angiver,' hvilke katalysatorer og hvor meget vand, der eventuelt tilsættes. Katalysatorerne anvendes i en mængde på 0,20 millimol.A 50 ml round bottom flask equipped with magnetic stirrer is charged with 10 millimoles of 3-phenoxybenzaldehyde, 10.5 millimoles of 2- (4-chlorophenyl) -3-methylbutanoyl chloride, 12 millimoles of sodium cyanide, 20 ml of toluene, a phase transfer catalyst and water. The mixture thus obtained is stirred for varying periods of time, after which it is analyzed. Six experiments are carried out in this way and the results are shown in Table VI below, which indicates which catalysts and how much water may be added. The catalysts are used in an amount of 0.20 millimoles.
15 DK 155882BDK 155882B
Tabel VITable VI
1 - 2 3 4 5 61 - 2 3 4 5 6
For- Katalysator Vand Molært Reaktions- Udbytte af søg til- forhold tid, timer ester, % nr. sat, mellem ml vand ogPre-Catalyst Water Molar Reaction Yield of search ratio time, hours ester,% no. Set, between ml water and
NaCNNaCN
1 1,4,7,10,13,16-hexaoxa- - 0,012 2 60 cyclooctadecan 20 91 80 97 2 1,4,7,10,13,16-hexaoxa- 0,02 0,105 3 100 cyclooctadecan 3 1,4,7,10,13,16-hexaoxa- 1,00* 4,64 2 95 cyclooctadecan 4 g g 20 100 4 tetra-n-butylammonium- 0,012 2 30 bromid 22 32 5 tetra-n-butylammonium- 0,02 0,105 2 81 bromid g g 6 tetra-n-butylammonium- 1,00* 4,64 2 71 bromid 22 81 alc1 1,4,7,10,13,16-hexaoxa-0.012 2 60 cyclooctadecane 20 91 80 97 2 1,4,7,10,13,16-hexaoxa 0.02 0.105 3 100 cyclooctadecane 3 1.4 7,10,13,16-hexaoxa-1,00 * 4,64 2 95 cyclooctadecane 4 µg 100 100 4 tetra-n-butylammonium 0.012 2 30 bromide 22 32 5 tetra-n-butylammonium 0.02 0.105 2 81 bromide gg 6 tetra-n-butylammonium 1.00 * 4.64 2 71 bromide 22 81 alc
Af sammenligningsgrunde er der ved disse to forsøg intet fast cyanid til stede.For comparative reasons, no solid cyanide is present in these two experiments.
Det anvendte natriumcyanid består af partikler med en største dimension på 0,5 mm og indeholder 0,44 vægtprocent vand. Molforholdet mellem vand og natriumcyanid er beregnet under hensyn til det i natr: umcyanidet tilstedeværende vand og det eventuelt tilsatte vand. Til sammenligning kan det anføres, at molforholdet mellem vand og natriumcyanid i en mættet vandig opløsning af natriumcyanid med en temperatur på 23°C er 4,1.The sodium cyanide used consists of particles with a maximum dimension of 0.5 mm and contains 0.44% by weight water. The molar ratio of water to sodium cyanide is calculated taking into account the water present in the sodium cyanide and any water added. By comparison, it can be stated that the molar ratio of water to sodium cyanide in a saturated aqueous solution of sodium cyanide at a temperature of 23 ° C is 4.1.
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| GB804576 | 1976-03-01 | ||
| GB804676 | 1976-03-01 | ||
| GB8044/76A GB1540632A (en) | 1976-03-01 | 1976-03-01 | Preparation of pesticidal benzyl esters |
| GB804676 | 1976-03-01 | ||
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| GB804476 | 1976-03-01 |
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| GR (1) | GR62438B (en) |
| HU (1) | HU181632B (en) |
| IE (1) | IE44059B1 (en) |
| IL (1) | IL51567A (en) |
| IN (1) | IN143789B (en) |
| IT (1) | IT1075420B (en) |
| LU (1) | LU76861A1 (en) |
| MX (1) | MX4513E (en) |
| NL (1) | NL190068C (en) |
| NO (1) | NO145234C (en) |
| NZ (1) | NZ183461A (en) |
| OA (1) | OA05582A (en) |
| PH (1) | PH13719A (en) |
| PT (1) | PT66242B (en) |
| RO (1) | RO71762A (en) |
| SE (1) | SE442633B (en) |
| SU (1) | SU685145A3 (en) |
| YU (1) | YU40667B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153626A (en) | 1977-12-14 | 1979-05-08 | Shell Oil Company | Preparation of α-cyanobenzyl esters |
| JPS54103831A (en) * | 1978-01-27 | 1979-08-15 | Sumitomo Chem Co Ltd | Separation of stereoisomers of higher active cyanoo33 phenoxybenzyl 22*44chlorophenyl**isovalerate |
| FR2416219A1 (en) * | 1978-01-31 | 1979-08-31 | Roussel Uclaf | ESTERS OF OPTICALLY ACTIVE SUBSTITUTE ACETIC ACID AND RACEMIC OR OPTICALLY ACTIVE SUBSTITUTE BENZYL ALCOHOL, HAVING INSECTICIDAL PROPERTIES, THEIR PREPARATION PROCESS AND THE COMPOSITIONS CONTAINING THEM |
| CA1142953A (en) * | 1979-04-03 | 1983-03-15 | Dale G. Brown | Process for the preparation of pesticidal esters of certain carboxylic acids using phase transfer catalysts |
| DE2936864A1 (en) * | 1979-09-12 | 1981-04-02 | Bayer Ag, 5090 Leverkusen | (+ -) - TRANS-3- (E, Z-2-CHLOR-2- (4-CHLORPHENYL) -VINYL) -, 2,2-DIMETHYL-CYCLOPROPAN-CARBONIC ACID - (+ -) - (ALPHA) -CYANO -3-PHENOXY-4-FLUOR-BENZYL) -ESTERS, THE INDIVIDUAL E- AND Z-ISOMERS, METHOD FOR THE PRODUCTION OF THESE COMPOUNDS AND THEIR USE AS EECTOPARASITICIDES |
| JPS6245083U (en) * | 1985-09-06 | 1987-03-18 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS515450B1 (en) * | 1971-06-29 | 1976-02-20 |
-
1977
- 1977-02-09 CA CA000271451A patent/CA1122224A/en not_active Expired
- 1977-02-25 PH PH19496A patent/PH13719A/en unknown
- 1977-02-25 NL NLAANVRAGE7702022,A patent/NL190068C/en not_active IP Right Cessation
- 1977-02-26 EG EG119/77A patent/EG13756A/en active
- 1977-02-28 NO NO770673A patent/NO145234C/en unknown
- 1977-02-28 JP JP52020383A patent/JPS6017781B2/en not_active Expired
- 1977-02-28 CS CS771318A patent/CS197286B2/en unknown
- 1977-02-28 PT PT66242A patent/PT66242B/en unknown
- 1977-02-28 SE SE7702168A patent/SE442633B/en not_active IP Right Cessation
- 1977-02-28 HU HU77SE1856A patent/HU181632B/en unknown
- 1977-02-28 AR AR266711A patent/AR227121A1/en active
- 1977-02-28 FI FI770632A patent/FI65989C/en not_active IP Right Cessation
- 1977-02-28 GR GR52866A patent/GR62438B/en unknown
- 1977-02-28 CH CH250677A patent/CH632237A5/en not_active IP Right Cessation
- 1977-02-28 MX MX775480U patent/MX4513E/en unknown
- 1977-02-28 DK DK087977A patent/DK155882C/en active
- 1977-02-28 SU SU772455682A patent/SU685145A3/en active
- 1977-02-28 IE IE426/77A patent/IE44059B1/en not_active IP Right Cessation
- 1977-02-28 IN IN291/CAL/77A patent/IN143789B/en unknown
- 1977-02-28 BR BR7701218A patent/BR7701218A/en unknown
- 1977-02-28 DE DE2708590A patent/DE2708590C2/en not_active Expired
- 1977-02-28 IT IT20781/77A patent/IT1075420B/en active
- 1977-02-28 LU LU76861A patent/LU76861A1/xx unknown
- 1977-02-28 AU AU22769/77A patent/AU507462B2/en not_active Expired
- 1977-02-28 ES ES456367A patent/ES456367A1/en not_active Expired
- 1977-02-28 DD DD7700197602A patent/DD128362A5/en unknown
- 1977-02-28 AT AT132777A patent/AT349454B/en not_active IP Right Cessation
- 1977-02-28 BG BG7735547A patent/BG27893A3/en unknown
- 1977-02-28 RO RO7789558A patent/RO71762A/en unknown
- 1977-02-28 YU YU534/77A patent/YU40667B/en unknown
- 1977-02-28 NZ NZ183461A patent/NZ183461A/en unknown
- 1977-02-28 IL IL51567A patent/IL51567A/en unknown
- 1977-02-28 FR FR7705746A patent/FR2342960A1/en active Granted
- 1977-03-01 OA OA56084A patent/OA05582A/en unknown
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