GB2094792A - Preparation of 3,7,11-trimethyl-2,4,dodecadienoates - Google Patents

Preparation of 3,7,11-trimethyl-2,4,dodecadienoates Download PDF

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GB2094792A
GB2094792A GB8205484A GB8205484A GB2094792A GB 2094792 A GB2094792 A GB 2094792A GB 8205484 A GB8205484 A GB 8205484A GB 8205484 A GB8205484 A GB 8205484A GB 2094792 A GB2094792 A GB 2094792A
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Egyt Gyogyszervegyeszeti Gyar
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids

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Abstract

3,7,11-trimethyl-2,4-dodecadienoates of the general formula /I/ <IMAGE> wherein R<1> represents hydrogen or an alkoxy group, Z<1> represents hydrogen, or R<1> and Z<1> together form a double bond, Z<2> and Z<3> each represent hydrogen or together form an ethylene group, R<2> and R<3> each denote an alkyl group, provided that when Z<2> and Z<3> form an ethylene group, R<1> is hydrogen, R<2> is methyl and R<3> is ethyl, are prepared by reacting a compound of the general formula /II/ <IMAGE> wherein R<1>, Z<1>, Z<2>, Z<3> and R<3> have the above specified meanings, and Q represents a group of the general formula /IIIB/ -COR /IIIB/ wherein R stands for an alkyl, phenyl or phenyl-/lower alkyl/ group, and with a compound of the general formula /VI/ Li-Cu/R<2>/2 /VI/ wherein R<2> has the above defined meaning. The advantage of the process is that it consists of less reaction steps than the known methods and can be used also on an industrial scale. The compounds of formula /I/ are insect growth regulators and can be used to advantage in plant protection. The intermediates of formula /II/ are new.

Description

1 GB2094792A 1
SPECIFICATION
A process for the preparation of 3,7,11 1-trimethyl-2,4-dodecadienoates and intermediates therefor The invention relates to a new process for the preparation of 3,7,11 - trimethyi-2,4-dodecadienoates of the general formula /1/ R 2 10 ill 3 3 Z_ /I/ wherein RI represents hydrogen or lower alkoxy group, Z' stands for hydrogen, or RI and Z' together form a double bond, Z2 and Z3 each represent hydrogen or together form an ethylene group, R 2 and R3 each denote a lower alkyl group, with the proviso that if Z2 and Z3 together form an ethylene group, RI may only stand for hydrogen, R 2 for methyl and R 3 for ethyl.
Certain representatives of the compounds of the general formula /I/ (e.g. isopropyl-(l 1 methoxy-3,7,1 1-trimethyl-2/E/,4/E/-dodecadienoate), hereinafter: methoprene, and ethyl- 25 /3,7,1 1-trimethyl-2/E/,4/E/-dodecadienoate/, hereinafter: hydroprene] are commercial prod ucts and can be used in plant-protection and animal-breeding on a large scale as insect growth regulators.
Methoprene is highly effective in controlling mosquito species [e.g. yellow fever mosquito /Aedes aegypti/: W.L. Jakob, Mosq. Neus 32, 592 /1972/, W.L.Jakob, J. Econ. Entomol. 30 66, 819 /1973/; C.A. Henrick et al., J. Agric. Food Chem. 24, 207 /1976/]; flies [e.g.
house fly /Musca domestica/: W.L. Jacob, J. Econ. Entomol. 66, 819 /1973/, W.F. Plapp and S.R. Vinson, Pestic. Bochem. Physiol. 3, 131 /1973/; C.A. Henrick et al,,.J. Agric. Food Chem. 23, 396 /1975/; P.B. Morgan et aL, Can. Entomol. 107, 413 /1975/; C. A. Henrick et al., J. Agric. Food Chem. 24, 207 /1976/]; aphids [e.g. yellow mealworm /Tenebrio molitor/, C.A. Henrick et al., J.Agric. Food Chem., 24, 207 /1976/, pea louse /Acyrthosi phon pisum/, C.A. Henrick et al., J. Agric. Food Chem., 24, 207 /1976/], and cockroaches /e.g. Nauphoeta cinerea; W. Radwan and F. Sehnal, Experienta 30, 615 /1974//.
Hydroprene is highly active on potato aphids [J. Benskin and Perron, Can. Entomol. 105, 619 /1973/1, mealybugs [R.A. Hamlen, J.Econ. Entomol. 68, 223 /1975/; C.A. Henrick et 40 al., Bioorganic Chemistry 7, 235 /1978/] and other pests which attack stored grain /R.G.
Strong and Diekman, J. Econ. Entomol. 66., 1167/1973//.
The 3,7,1 1-trimethyl-2,4-dodecadienoates containing a cyclopentane ring /1. R1 = Z' = H, Z2 + Z3 =ethylene group, R 2 = CH3, R 3 = C2H5/ exhibit a strong growth inhibiting activity on yellow fever mosquitos /Aedes aegypti/ and on budworms /Heliothis virescens/ /C.A. Henrick 45 et al., Bioorganic Chem. 7, 235 /1978//.
To prepare compounds of ethyl-/3,7,1 1-trimethyl-2/E/, 4/E/dodecadienoate/type, C.A.
Henrick et al. have elaborated several methods [J. Org. Chem. 40, 8 /1975/]. According to one of these syntheses 6,7-dihydro-citronelial is reacted with the anion of diethyl-2-oxopropyl phosphonate, the 2-oxo-6,1 0-dimethyl-3-undecene thus-obtained is treated with the lithium salt 50 of acetic acid. The 3-hydroxy-3,7,1 1-trimethyl-4-undecenic acid thusobtained is converted into the corresponding acid chloride with phosphoryl chloride and N-ethyl- diisopropyl amine. The reaction of the acid chloride thus-obtained with ethanol gives the 2/Z/ stereoisomer of hydroprene and, due to the double bond migration, the corresponding 3,5- dodecadienoic acid derivative /10%/. The main disadvantage of this method lies in the rather low yield of the 55 esterification and in the considerable by-product formation.
According to an improved method of this process C.A. Henrick et al. started from 3,3 dimethyl-acrylic acid. When reacting this compound with the lithium compound of diisopropyl amine the corresponding dianion was obtained, which was reacted with 6,7- dihydro-citronelial.
The 3-hydroxy-2-isopropenyl-5,9-dimethyl-dodecanoic acid thus-qrbtained was thermally rear- 60 ranged into 5-hydroxy-3,7,1 1-trimethyl-2/Z/-dodecenoic acid, which was converted, in acidic medium, into a 6-membered lactone. This lactone was reacted with sodium methylate to obtain the 2/Z/ stereoisomer of hydroprene which, by reacting with thiophenol, was converted into a 6.5:3.5 mixture of hydroprene and the 2/Z/ stereoisomers thereof. The reaction is unfavoura ble because of the expensive starting material and the low yield of the reaction steps.
GB2094792A 2 In a further method of C.A. Henrick et al. (J. Org. Chem. 40, 8 /1975/; J. Agric. Food Chem. 23, 396 /1975/] 6,7-dihydro-citronelial was reacted with the lithium compound of 1propyne. The 4-hydroxy-6,1 0-dimethyl-2- undecine thus-obtained was treated with orthoacetic ethylester, the ethyl- /3,7,1 1-trimethyl-3,4-dodecadienoate/ thus-obtained was converted with a 5 base into a 6.5:3.5 mixture of hydroprene and the 2/Z/ stereoisomer thereof. The method is less economic because of the rather low yield of certain reaction steps /e.g. the yield of the first step /addition/ is 29%/.
Recently G. Cardillo and al. have published a process for the preparation of the methyl ester analogue of hydroprene /1, RI =Z1 =Z2=Z3 = H, R 2 = R 3 = CH3/ /J, C, S. Perkin 1. 1979, 1729/. On starting from 3-methyl-3-buten-l-ol a dianion was formed with 2 moles of butyl 10 lithium, which was then reacted with 6,7-dihydro-citronellal to obtain 1, 5-dihydroxy-3-methy lene-7,1 1-dimethyl-dodecane. This compound was acylated, the di-acyl compound thus-obtained was partially hydrolyzed. The 5-acetoxy-3-methylene-7,1 1-dimethyl- dodecan-l-ol thus-obtained was oxidized with Jones reagent to form the corresponding carboxylic acid, which was esterified with diazomethane, then the ester was converted into a mixture of 2/E/, 4/E/ and 2/Z/, 4/E/ 15 stereoisomers with sodium hydride in the presence of crown ethers. The process is uneconomic because of the expensive starting material and reactants.
According to a method for the preparation of methoprene C. A. Henrick and al. [J. Org.
Chem. 40, 1 /1975/] started from 7-methoxy-6,7-dihydro-citroneliaI and acetoacetate.
The latter compound was dimerized in acidic medium, the dimer was treated with sodium 20 alcoxide to obtain 3-methyl-glutaconate, which was condensed with 7- methoxy-6,7-dihydro citronellal in the presence of alcoholic potassium hydroxide. The 1 1- methoxy-4-carboxy-3,7,1 1 trimethyl-2/Z/,4/E/-dodecadienoic acid thus-obtained was decarboxylated by heating in the presence of 2,4-dimethylpyridine. As main product, 1 1-methoxy-3,7,1 1- trimethyl-2/Z/,4/E/ dodecadienoic acid was obtained from the reaction mixture, and also the unreacted starting 25 material, a lactonization product and the 10-methoxy-2,6,10-trimethyl-1, 3/Z/-undecadiene formed in consequence of the twofold decarboxylation could be isolated. The dodecadienoic acid was isomerized with thiophenol into a mixture of the 2/E/,4/E/ and 2/Z/, 4/E/ stereoisomers, then the corresponding ammonium salt was formed, and the salt of the 2/E/, 4/E/ stereoi- somer was separated by crystallization. The acid recovered from the ammonium salt was treated 30 with a mixture of thionyl chloride and dimethy1formamide and the corresponding acid chloride thus-obtained was reacted with isopropanol to produce methoprene.
This method is less effective and economic because of the facts that even theoretically at least two moles of aceto-acetate are necessary to produce one mole of methoprene; after the decarboxylation the separation of the side-products is rather complicated; a part of the methoxy 35 group is eliminated when forming the acid chloride, and the end-product is contaminated with isopropyl-/3,7,1 1 -trimethyI-2/E/,4/E/1 0-dodecatrienoate/ and isopropyl- /3,7,1 1 -trimethyl 1 1-chloro-2/E/,4/E/-dodecadienoate/.
According to a further method of C.A. Henrick and al. /Bioorganic Chemistry 7, 235 /1978// ethyi[3-/3,7-dimethyl-l-octylidene/-2-methyl-2-cyclopentene- carboxylate] is synthe- 40 sized from 1-ethoxycarbonyl-cyclopropyl-triphenyi-phosphonium fluoroborate and diethyl-/2 oxopropyl-phosphonate/. The reaction of these compounds gave ethyl-/ 3- diethyl-phosphoryl-2 methyl-l-cyclopentene-carboxylate/, which was reacted with 6,7-dihydro- citronelial to obtain the cyclopentane analogue of hydroprene. The preparation of phosphonium fluoroborate used as starting material is very expensive and the yield of certain reaction steps is rather low /20% and 45 10%/.
The aim of the present invention was to provide a more economic process for the preparation of the compounds of the general formula /I/ possessing valuable biological effects, which comprises less reaction steps and which can be more readily carried out also in industrial scale.
According to the invention there is provided a process for the preparation of 3,7,1 1-trimethyl2,4-dodecadienoic acid derivatives of the general formula /1/, wherein the substituents have the same meanings as above, which comprises reacting a compound of the general formula /Il/ Q 1 0 COOR3 41 2 3 Z Z /111, wherein W, Z1, Z2, Z3 and R 3 have the above specified meanings, and Q represents a group of the general formula /IIIB/, -COR /IIIB/ 1 3 GB2094792A 3 R stands for a lower alkyl, phenyl or phenyl-/lower alkyl/ group and with a compound of the general formula /V1/ Li-Cu/R 2 /2 /V1 / wherein R 2 has the above defined meaning.
The term "lower alkyl- refers to straight or branched saturated aliphatic hydrocarbon groups containing 1-4 carbon atoms /e.g. methyl, ethyl, n-propyl, isopropyl, n- butyl and isobutyl/. 10 The term "lower alkoxyrelates to straight or branched alkylether groups containing 1 -4 carbon atoms, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy. The "phenyl-/Iower alkyl/ group" may stand for benzyl or phenylethyl. The term "halogen atom" may be all the four halogen atoms, such as fluorine, chlorine, bromine or iodine, and represents preferably chlorine.
The reaction of the compounds of the general formula /11/ and /Vl/ is preferably carried out in an organic solvent. As reaction medium preferably diethyl ether or tetrahydrofuran can be used. The reaction can be performed in a temperature interval ranging from - 1 OC to - 1 00C, particularly between - 50'C and - 80C. One proceeds preferably under an inert gas, as argon or nitrogen.
The starting materials of the general formula /11/ are new and can be produced as follows:
The starting materials of the general formula /11/, wherein Q represents a group of the general formula /IIIB/, can be prepared by reacting a compound of the general formula /IV/ R1 1 0 Z3 COOR3 /IV/ wherein W, Z1, Z2, Z3 and R 3 have the above defined meanings, with a compound of the general formula /VII/ - CH3-C-O-CO-R NU/ 11 '"2 wherein R represents a lower alky], a phenyl or a phenyl-/lower alkyl/ group. The reaction is preferably carried out in the presence of a catalytic amount of an acid /preferably an organic sulfonic acid, particularly p- toluenesulfonic acid; or a mineral acid, preferably hydrochloric acid/.
As reaction medium, preferably organic solvents /e.g. diethyl ether or tetrahydrofuran/ are used.
The starting materials of the general formula /11/ thus-obtained can be reacted with the compounds of the general formula /V1/ after or without isolation.
The compounds of the general formula /IV/ used for the preparation of the starting compounds of the general formula /11/ are also new and can be prepared by reacting a citronelial derivative of the general formula /Vill/ Ri 1 Z1 G110 /Vill/ wherein R' and Z1 have the above defined meanings, 60 with a dianion prepared from a 3-oxo-ester of the general formula /]X/ Z-COOR 5 /IX/ wherein 65 Z stands for an acetonyl or cyclopentanonyl group and R5 is a lower alkyl group, 4 GB2094792A 4 and by subjecting the product thus-obtained to an elimination reaction.
The dialkyl-cuprous lithium compounds of the general formula /VI/ can be prepared by reacting cuprous iodide with alkyl lithium.
The 3,7,1 1-trimethyl-2,4-dodecadienoic acid can be isomerized into a 7:3 mixture of 2/E/,4/E/ and 2/Z/,4/E/ stereoisomers with thiophenol in a known way /C.A. Henrick et 5 al.: J. Org. Chem. 40, 1 /1975//.
A further advantage of the process according to the present invention is that exclusively the /E/ isomer of the end product is formed, so the complicated procedures for the separation of the isomeric mixture, which result in a considerable loss of the yield, can be eliminated.
The process is illustrated by the following Examples of non-limiting character. Infrared spectra 10 were measured on a Spectromorn 20OG spectrophotometer. 1H-NMR and 13C-NMR spectra were determined on a Jeol FX-1 00 spectrometer. Gas chromatography was carried out With a Pye 105 instrument / 10% SE-54 chromosorb. W 80-100, a gas column of 2 mm X 2 m, carrier: He, 190-260% program 3' /minute/. Mass spectra were determined on JEOL JGC20K and JMS-01SG-2 combined GC-Ms spectrometer /ionization potential 75 eV, 10 kV, 200 A/.
Example 1 Preparation of isopropyl-111-methoxy-3,7,11-trimethyl-21EI,41EIdodecadienoatelMetho- prene, 1: R1 = CH301 Z1 = Z2 = Z3 = H, R 2 =CH3 R 3 = iC3H7/ g /16 millimoles/ of isopropyl-/l 1-methoxy-3-oxo-7,1 1-dimethyl-4/E/- dodecenoate/ are dissolved in 20 g /200 millimoles/ of isopropenyl acetate. Then 0.2 g /1.2 millimoles/ of anhydrous p-toluenesulfonic acid are added, and the reaction mixture is stirred for 6 hours, under stirring. The solution is cooled, 50 ml of ether are added, the ethereous solution is washed first with 50 ml of water then with 50 ml of saturated sodium chloride, dried over magnesium sulfate, filtered and the solvent is distilled off in vacuo. The residue /5.1 g of yellow oil/ is filtered on a short column /50 g of Kieselgel 60, benzene-ethylacetate 3:2/. After distilling off the eluent 3.5 g /62.5%/ of isopropyl-/3-acetoxy-1 1- methoxy-7,1 1-dimethyl2/Z/,4/E/-dodecadienoate/ are obtained.
Rf = 0.65 /hexane-acetone 5:1 / According to a liquid chromatographic analysis the product may contain less than 2% of 2/Z/,4/E/ stereoisomer.
Retention time: 2/E/,4/E/ diastereomer: 5.3 minutes 2/Z/,4/E/ diastereomer: 6.6 minutes 35 IR /NaCI/: 1760, 1710, 1640, 1610, 1450, 1380, 1360, 1245, 1220, 1160, 1130, 1080, 1060, 1000 cm-1.
H-MNR /CC],/: 0.9 /3H, d, J = 6Hz, CH3/, 1 -1.9 /1 9H, m, CH., CH2, CH/, 2.1 /2H, m, CH2/, 2.22 /3H, s, OCCH3/, 3.08 /3H, s, OCH,/, 4.9 /1 H, h, J = 5Hz, CHO/, 5.2-6.3 40 /3H, m, CH = /.
Ms: M+ 345 /2/, m/e 340 /4/, 322 /6/, 280 /15/, 264 /7/, 262 /5/, 237 /8/, 220 /10/, 197 /15/, 136 /20/, 124 /12/, 95 /12/, 81 /16/, 73 /100/, 69 /12/, 43 /55/.
A 5% ethereous solution of 0.83 g /38 millimoles/ of methyl lithium is added to a suspension of 3.6 g /20 millimoles/ of cuprous iodide in 100 mi of anhydrous ether under stirring and cooling - WC/, under argon. After stirring for further 5 minutes the reaction mixture is cooled to 70'C and a solution of 1.7 g /5.6 millimoles/ of isopropyi-/3-acetoxy1 1methoxy-7,1 1-dimethyi-2/Z/,4/E/-dodecadienoate/ in 25 mi of anhydrous ether is 50 dropwise added. The mixture is stirred at - 20C for 3 hours, poured onto 100 mi of concentrated ammonium chloride, the ethereous phase is separated, and the aqueous phase is extracted twice with a total amount of 100 mi of ether. The ethereous extracts are combined, washed with saturated sodium chloride, dried over magnesium sulfate, and the solvent is distilled off.
Yield: 1.2 g /82%/ Rf = 0.9 /hexane-acetone 7:3/ B.p.: 140-142'C/6.66 Pa [According to scientific literature: 135-136'C/7.99 Pa, C.A. Henrick et a[.: J. Org. Chem. 40, 1 /1975/J According to a liquid chromatographic analysis the product contains less than 2% of 2/Z/A/E/ stereoisomer.
Retention time: 2/E/,4/E/ diastereomer: 2.33 minutes 2/Z/A/E/ diastereomer: 2.83 minutes IR /NaCI/: 1710, 1640, 1610, 1470, 1440, 1380, 1360, 1230, 1160, 1100, 1080, 1030, 65 G13.2 094 792A 5 970 cm-1. H-NIVIR /CID013/: 0.9 /3H, d, J = 6Hz, CH3/, 1.11-1.8 /19Hf m, CH, CH2, CH3/, 2.1 /2H, rn, CH2/, 2.3 /3H, d, J = 1.5Hz, CH3/, 3.2 /3H, s, OCH3/, 5.1 /1 H, h, J = 6Hz, CHO/, 5.75 /1 H, m, CH = /, 6.15 /2H, m, CH = /.
"C-NMR: 13.8 /q/, 19.6 /t/, 21.3 /q/, 22.0 /q/, 25 /q/, 33.2 /d/, 37.2 /t/, 40.1 /t/, 40.6 /t/, 49.0 /q/, 66.6 /d/, 118.2 M/, 128.3 /d/, 134.9 /d/, 135.7 /d/, 152.0 /d/, 166.6 /s/.
Ms:W 310 /9/, m/e 278 /27/, 236 /9/, 235 /10/, 221 /10/, 193 /13/, 192 /17/, 153 /32/1 111 /33/, 73 /100/, 43 /26/.
Example 2
Preparation R' =Z1 =Z2=Z3 =H, R 2 = CH3, R3 = CM/ To a mixture of 5 g / 18 millimoles/ of ethyl-/ 3-oxo-7,1 1 -dimethyi-4/ E/-dodecenoate/ and 20 g /200 millimoles/ of isopropenyl acetate 0.2 g /1.2 millimoles/ of ptoluene-sulfonic acid 15 are added, and the reaction mixture is stirred for 6 hours under stirring. Then it is cooled, diluted with 50 mi of ether, the ethereous solution is washed first with 25 mi of water then with mi of saturated sodium chloride, dried over magnesium sulfate, and the solvent is distilled off. The residue /5.4 g of a pale yellow oil/ is filtered on a short column /50 9 of Kieselgel 60, benzene-ethylacetate 3:2/. After distilling off the solvent 5 g /87%/ of ethyl-/ 3-acetoxy-7,1 1 - 20 dimethyl-2/Z/,4/E/-dodecadienoate/ are obtained.
Rf = 0.72 /hexane-acetone 5:1 / According to liquid chromatography the product contains less than 2% of 2/Z/,4/E/ stereoisomer.
of ethyl-13,7, 1 1-trimethyl-21E1,41El-dodecadienoate /Hydroprene, 1:
Retention time: 2/E/ 4 /E/ diastereomer: 2.17 minutes 2/Z/A/E/ diastereomer: 2.35 minutes IR /NaCI/: 1760, 1710, 1640, 1600, 1460, 1380, 1360, 1420, 1220, 1150, 1120, 1080, 30 1020cm-1 'H-NIVIR XClJ: 0,9 /9H, dm, CH3/, 1-1.8 /11 H, m, CH, CH2, CH./, 2 /2H, m, CH2/, 2.2 /3H, s, OCCH3/, 4 /2H, q, J = 6Hz, OCH2 /, 5.1-6.3 /3H, m, CH = /. Ms: M+ 310 /3/, m/e 267 /3/, 183 /10/, 173 /9/, 155 /16/, 141 /110/, 126 /8/, 95 /7/, 91 /48/, 83 /12/, 81 /11 /, 69 /27/, 65 /20/, 57 /32/, 56 /25/, 55 /33/, 43 /100/, 41 /55/.
To a suspension of 5 9 /26 millimoles/ of cuprous iodide in 100 mi of anhydrous ether cooled to - WC an ethereous solution of methyl lithium /containing 1.1 g /53 millimoles/ of methyl lithium/ is added under argon. After stirring for 5 minutes the reaction mixture is cooled to - 70C and a solution of 3.5 g /11 millimoles/ of ethyl-/ acetoxy-7, 1 1-dimethyl 2/Z/,4/E/-dodecadienoate/ in 20 mi of anhydrous ether is dropwise added. The reaction 40 mixture is poured onto 100 mi of concentrated ammonium chloride solution, the organic phase is separated, and the aqueous phase is extracted twice with a total amount of 100 mi of ether.
The ethereous solutions are combined, washed with an aqueous saturated sodium chloride solution dried over magnesium sulfate and the solvent is distilled off.
Yield: 2.2 9 /73%/ R,= 0.92 /hexane-acetone 7:3/ B.p.: 132-1 WC/6.66 Pa /According to scientific literature: 1 37-142'C/39 Pa, C.A. Henrick et al. : J. Org. Chem. 40., 8 /1975//. According to liquid chromatographic analysis the product may contain less than 2% of 2/Z/A/E/ stereoisomer.
Retention time: 2/E/,4/E/ diasteriomer: 2.05 minutes 2/Z/A/E/ diastereomer: 2.35 minutes IR /NaCI/: 1710, 1640, 1600, 1460, 1380, 1360, 1220, 1140, 1030, 960 cm-1. 'H-NMR XClJ: 0.9 /9H, rn, CH3/, 1-1.8 /11 H, m, CH, CH2, CH3/, 2 /2H, m, CH2/, 2.15 /3H, d, J = 1.5 Hz, CH./, 4 /2H, q, J = 7Hz, OCH2/, 5.75 /1 H, m, CH = /, 6.15 /2H, m, CH = CH/.
1

Claims (13)

1. A process for the preparation of 3,7,1 1-trimethyi-2,4-dodecadienoates of the general formula /1/ 6 GB2094792A 6 2 0OR3 5 j2 Z_ 73 wherein 10 R' represents hydrogen or a lower alkoxy group, ZI stands for hydrogen, or /I/ R' and ZI together form a double bond, Z2 and Z3 each represent hydrogen or together form an ethylene group, R 2 and R 3 each denote a lower alkyl group, with the proviso that if Z2 and Z3 together form an ethylene group, R' may only stand for 15 hydrogen, R2 for methyl and R 3 for ethyl, characterized by reacting a compound of the general formula /11/ Q 1 0 COOR3 Z2 Z3 wherein W, Z1, Z2, Z3 and R3 have the above specified meanings, and Q represents a group of the general formula /IIIB/ -COR /IIIB/ wherein R stands for a lower alky], phenyl or phenyl-/lower alkyl/ group and with a compound of the general formula /V]/ Li-Cu/R 2 /2 /V1/ wherein R 2 has the above defined meaning.
2. A process as claimed in claim 1, wherein the reaction is carried out under inert gas. 40
3. A process as claimed in claim 1, wherein the reaction is carried out under argon.
4. A process as claimed in any of claims 1 to 3 which comprises carrying out the reaction at a temperature between - 1 OOT to - 1 0T.
5. A process as claimed in any of claims 1 to 4 which comprises carrying out the reaction at a temperature between - 50T and - 80T.
6. A process as claimed in any of claims 1-5, which comprises carrying out the reaction in an aprotic solvent.
7. A process as claimed in claim 6 wherein the aprotic solvent is diethyl ether or tetrahydrofuran.
8. A process as claimed in any of claims 1 to 7 wherein the compound of the general 50 formula /11/, wherein Q represents a group of the general formula /11113/ and R', R3, Z1 Z2 and Z3 are as defined in claim 1 is obtained by the reaction of a compound of the general formula /[V/ 0 31 Z3 C 0 OR 11VI/ wherein W, Z1, Z2, Z3 and R3 have the same meanings as above, and a compound of the general formula /VII/ 1 7 GB2094792A 7 CH3-C-O-CO-R /VII/ 11 CH2 wherein R is as defined in claim 1 and is used after or without isolation.
9. A process as claimed in claim 8 wherein the compound of the general formula /IV/ is reacted with a compound of the general formula /VII/ in the presence of a catalytic amount of 10 an aromatic sulfonic acid.
10. A process as claimed in claim 9 wherein the aromatic sulphonic acid is p-toluenesulfonic acid.
11. A process as claimed in claim 1 substantially as hereinbefore described.
12. A process as claimed in claim 1 substantially as hereinbefore described with reference to 15 the Examples.
13. Compounds of the general formula /11/, as defined in claim I Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Ltd.-1 982. Published at The Patent Office, 25 Southampton Buildings, London, WC2A 1AY, from which copies may be obtained.
GB8205484A 1980-04-01 1981-03-31 Preparation of 3,7,11-trimethyl-2,4-dodecadienoates Expired GB2094792B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU76680A HU179373B (en) 1980-04-01 1980-04-01 Process for producing 3-alkyl-7,11-dimethyl-e-bracket-e-bracket closed,4-bracket-e-bracket closed-dodecadienic and 2-bracket-e-bracket closed,4-bracket-e-bracket closed,10-dodecatrienic acid inhibiting growth of insects
HU299780A HU181239B (en) 1980-12-16 1980-12-16 Process for the stereospecific preparation of 3,7,11-trimethyl-2,4-dodecadienic acid derivatives with inhibiting activity against growth of insects

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GB2094792A true GB2094792A (en) 1982-09-22
GB2094792B GB2094792B (en) 1984-03-28

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GB8109962A Expired GB2073754B (en) 1980-04-01 1981-03-31 Preparation of 3,7,11-trimethyl-2,4-dodecadienoates and starting materials therefor
GB8205484A Expired GB2094792B (en) 1980-04-01 1981-03-31 Preparation of 3,7,11-trimethyl-2,4-dodecadienoates

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BG (1) BG35034A3 (en)
CS (1) CS231983B2 (en)
DD (1) DD157906A5 (en)
FR (1) FR2479191A1 (en)
GB (2) GB2073754B (en)
PL (1) PL127841B1 (en)
SU (1) SU1069621A3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320917A2 (en) * 1987-12-17 1989-06-21 Hercules Incorporated Method and composition for storage of plant material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4952710A (en) * 1988-10-07 1990-08-28 G. D. Searle & Co. Cyclopenteneheptenoic acid derivatives and method of preparation thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320917A2 (en) * 1987-12-17 1989-06-21 Hercules Incorporated Method and composition for storage of plant material
EP0320917A3 (en) * 1987-12-17 1990-02-14 Hercules Incorporated Method and composition for storage of plant material

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CS231983B2 (en) 1985-01-16
FR2479191A1 (en) 1981-10-02
CS239181A2 (en) 1984-01-16
BG35034A3 (en) 1984-01-16
GB2073754A (en) 1981-10-21
FR2479191B1 (en) 1984-11-30
GB2073754B (en) 1983-07-13
DD157906A5 (en) 1982-12-15
PL230424A1 (en) 1981-12-23
SU1069621A3 (en) 1984-01-23
GB2094792B (en) 1984-03-28
PL127841B1 (en) 1983-11-30

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