IL31196A - 10,11-epoxy-3,7,11-trimethyl-dodec-2-enoic acid,corresponding esters,amides,alcohols and nitriles and their preparation - Google Patents

10,11-epoxy-3,7,11-trimethyl-dodec-2-enoic acid,corresponding esters,amides,alcohols and nitriles and their preparation

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IL31196A
IL31196A IL31196A IL3119668A IL31196A IL 31196 A IL31196 A IL 31196A IL 31196 A IL31196 A IL 31196A IL 3119668 A IL3119668 A IL 3119668A IL 31196 A IL31196 A IL 31196A
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reacted
epoxide
converted
trans
trimethyl
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Sparamedica Ag
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
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    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
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    • C07—ORGANIC CHEMISTRY
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/46—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by amide or nitrile radicals
    • C—CHEMISTRY; METALLURGY
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    • C07B2200/09—Geometrical isomers

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  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description

SPARAMBDICA A.O.
Qt29415 represent an alkyl group having at least 2 carbon atoms, phpnyl or di(lower alkyl ) aminoalkyil.
An alkoxycarbonyl group X chiefly signifies a lower alkoxycarbonyl group having up to 6 carbon atoms, for example, a methoxy-, ethoxy- or isopropoxy-carbonyl. group, especially the methoxycarbonyl group. An aminocarbonyl group X can be mono- or di-substituted by lower alkyl having up to 6 carbon atoms, for example, by methyl, ethyl> isopropyl, especially by methyl. The dialkylaminoalkyl groups and also contain lower alkyl groups having up' to 6 carbon atoms, for example, methyl, ethyl and isopropyl. The substituents R and R, can, d J? together with the attached nitrogen atom, represent a saturated 5- or 6-membered heterocyclic group optionally containing a ttjrtrogonj ■ oxygen or sulphur atom as a further hetero atom.
Examples of such groups include pyrrolidine, piperidino, pyrimidino and morpholino.
Whe X signifies an alkoxymethylene group, the alkoxy residue chiefly signifies a lower alkoxy group having up to 6 carbon atoms, for example, a methoxy, ethoxy or isopropoxy group, especially the methoxy group. A lower alkyl substituent R denotes lower alkyl having up to 6 carbon atoms such as, for example, methyl, ethyl or isopropyl.
Representative examples of the" compounds obtainable by the process of the invention include: acetic acid or benzoic acid,and in the presence of a solvent, such as benzene, toluene, dimethylformamide, 1,2-dimethoxy- ethane or dioxan at a temperature of from room temperature to the boiling point of the solvent.
The phosphine oxide of formula IV can carry aryl, alkoxy or aryloxy residues. The aryl residues denoted by symbols and Rg can, like the residues R^, Rj. and Rg in the phosphoranes of formula III, be mono- or polynuclear, . substituted or unsubstituted, aryl residues. Regarding the alkoxy residues, lower; alkoxy residues with up to 4 carbon atoms (e.g. methoxy, ethoxy and isopropoxy) are preferred.
Regarding the aryloxy residues, phenoxy groups (which oan be singly or multiply substituted by various groups, for example, alkyl, alkoxy, halogen, nitro or dialkylamino) are especially preferred. ■.
The reaction of a starting compound of formula II (which may be epoxldised) with a phosphine oxide of formula IV is normally carried out in the presence of a base, preferably in the presence of an inert organic solvent. Thus, for example, this reaction can be effected in the presence of sodium hydride in benzene, toluene, dimethylformamide, tetra- hydrofuran, dioxan or 1,2-dimethoxyethane, or in the presence of an alkali-metal alcoholate in an alkanol (e.g. sodium methylate in methanol), lat a temperature of from 0° to room · of formula II is reacted with a phosphine oxide of formula IV, in the presence of. about 2 mol of sodium hydride in abs. dioxan, excess sodium hydride being decomposed for example by addition of abs. ethanol.
Compounds of formula I in which X represents a tertiary amido group are accessible by condensation of a compound of formula II with a [tert. amido-methyl] -phosphorane of formula III. Compounds of formula I in which X represents ·■;·■¾,·■.' a tertiary amido group or a primary or secondary amido group ' can be manufactured in such a way that a compound of formula II ;."- · ;: ·, is either reacted directly with an amide of formula IV and epoxidised, or first epoxidised and thereafter reacted with an amide of formula IV, or that an ester obtained by reaction of a compound of formula II with an ester of the compounds III or IV is saponified in a known manner (e.g. by treatment with aqueous alcoholic caustic soda), the free acid obtained is transformed by the action of a halogenating agent, for example, thionyl chloride,: into the acid halide and this is reacted with ammonia or with a mono- or di-substituted amine to give the desired amide and epoxidised.
Compounds of formula I in which X represents an alkoxymethylene group can.be obtained by reacting a compound of formula II with acetylene in a manner known per se (e.g. in the presence of sodium amide in liquid ammonia), partially hydrogenating the unsaturated triple compound obtained with the help of a partially deactivated catalyst (e.g. with the The compounds disclosed in e.g. German Patent Specification Ho, 1,204,453, Ο.Λ. Vol. 9294e, G.A.
Vol. 66, 85654b, CA. 6 , 12871k and Life Sciences £, 2323 (1965) are in the Tenebrio molitor test in the average one order of magnitude less active than the compounds of the present invention.
In an analogous manner, when employing - 9»10-epoxy-6,10-dime-thyl-aocLec-5-en-2-one . '· or ' 5»6; 9,10-diepoxy-6, 10-dimethyl-dodec-2-one ' . by reaction with. [cyano-methyl]-diethoxy- phosphine oxide' there is obtained , ll~epoxy~3 , 75 ll-trimethyl-trideca-2 , 6-diene-, - r-nitrile · or 6,7; 10,ll-diepoxy-3,7»H-trimethyl-tridec- -2-ene-i-nitrile · Example 4- 19.6 g of 6, 10-dimethyl-undec-9-en-2-one Ccitronellylacetone] together with 35 S -of fethoxycarbonyl--nethyl]-triphenyl-phosphorane and 3 g. of benzoic acid are dissolved in 100 ml of abs; benzene* - The reaction mixture is heated under reflux conditions for 22 hours under nitrogen gassing, then evaporated, taken up in 5 0 ml of. 80% methanol and exhaustively extracted with hexane. The combined extracts are washed with an ice-cold .saturated aqueous sodium hydrogen carbonate solution and with water, then dried over sodium sulphate and evaporated. The residual 3 , » ll-trimethyl-dodeca-g-cis/trans , 10)-dien^i^oic acid ethyl ester is purified by distillation.
Bop.: 89-90°C/0o 02 Torr.
S °ί" 5.7 ill-trimethyl-dodeca-^-cis/trans- .. -lO dieri^i^oic acid ethyl ester are introduced into 500 ml of 0o -N 50% aqueous, ethanolic caustic soda and stirred at. room, temperature for 5 days. The of water, extracted twice with ether, the aqueous alkaline solution is acidified with 3-N hydrochloric acid and exhaustively extracted with ether. The combined extracts are washed neutral with a saturated aqueous sodium chloride solution, dried over sodium sulphate and evaporated. The residual 3 , 71 ll-trimethyl-dodeca-(2-cis/trans ? acid is purified by distillation, B.p. : 128°C/0, 1 Torr. 14,8 g of 3 < 7¾ll-trimethyl-dodeca-(2~cis/trans 10)-dien^i«oic acid are mixed with 4, 92 g. of pyridine and 50 ml of abs. ether and treated dropwise with ice-cooling with 9 » 5 g of thionyl chloride. In so doing, the internal temperature should not exceed 6°Ce The reaction mixture is . subsequently stirred at 35°C for 30 minutes. The solids which separate out are filtered off and washed with ether. The ether phase is evaporated. The residue is taken up in ca 100 ml of ether and treated dropwise with ice-cooling with 21 , 9 g of diethylamine in 40 ml of ether. After 30 minutes, the mixture is poured onto ice and exhaustively extracted with ether.
The combined extracts are washed with a saturated sodium hydrogen carbonate solution, dried over sodium sulphate and evaporated. The residual N,N~diethyl-3.7«ll-trimethyl~dodeca-(2-cis/trans , 10)- acid amide is purified by distillation. B.p. 130°C/0.05 Torr.
Example 5 9.6 g of sodium hydride (50$ in mineral oil) are washed twice with 50 ml hexane and after the addition of 70 ml abs. dioxan are treated at 10-12°C with 19.5 g diethylphosphono- acetamide in 0 ml dioxan and subsequently stirred for 1 l/2 hours at room temperature. Thereafter, the reaction mixture is cooled to 10-12°C and at this temperature treated drop- wise with 19· g of 6,10-dimethyl-undeca-(5-trans^9}-dien- 2-one (trans-geranylacetone). After stirring for 20 hours at room temperature, the mixture is treated carefully with 6 ml ¾ i:..?of glacial acetic acid in order to destroy excess sodium hydride, then poured into 500 ml of sodium chloride solution, extracted with ether and worked up. The 2,7, 11-trimethyl- dodeca^2-cis/trans,6-trans, lO trien^i^oic acid amide (20.-6 g), obtained by chromatography With hexane-ethylacetate (1:1) on silicagel followed by a high vacuum distillation, boiled after the distillation at 127-129°C/0.001 Torr. The compound may be transformed by epoxydation into the 10, ll-epoxy-3,7> 11-trl- methyl-dodeca-£-cis/trans,6-trans)-dieri^iioic acid amide.
In an analogous, manner by the use o sodium hydride ( 50 in mineral oil),, diethylphosphono- N-isobutyl-acetamide · and 6, lO-dimethyi-undeca-5-trans 9-dien-2-one. (trans-geranylacetone1), . there can be obtained N-isobutyl-3,7, ll-trimethyl-dodeca-<(2-cis/ 137-139°/0. OO Torr utyl-3, , ll-trirr acid amide; '■···■■ . and by the use of sodium hydride ( 0 in mineral oil), diethylphosphono-- Ν,Ν-diethylacetamide and 6, 10-dimeth l-undeca^5-trans 2-one are obtained; bp. 104-107°C/0.001 Torr (decomp. ) n^ = 1. 5000.
A solution of 4.03 g of sodium in 87. 5 ml of abs. methanol is added dropwise within a period of 45 minutes and at a temperature of 0-3°C to a solution of 50.9 g of trans- 9-bromo-10-hydroxy-6, 10-dimethyl-5-undecen-2-one in .87.5 ml of abs. methanol. The reaction mixture is stirred for 30 minutes and then poured into 1000 ml of saturated sodium chloride solution, extracted with hexane and worked up. The pure trans-9, 10-epoxy-6, 10-dimethyl-5-undecen-2-one (29.4 g) obtained by distillation boiled at 79-80°C/0.08 Torr.; n^° = I.4638. .47 g of- sodium hydride (50$ in mineral oil) are washed twice with 0 ml of abs. hexane and after the addition of 30 ml of abs. dioxan are treated dropwise at 10-12°C with 11.2 g of diethylphosphonoacetamide in 0 ml of abs. dioxan (hot dissolved). The reaction mixture is stirred for i 1/2 hours at room temperature and subsequentl treated dropwise at - 12°C with 12 g of trans-9> 10-epoxy-6, 10-dimethyl-5-undecen-2-one. The mixture is stirred at room temperature for 20 hours, treated under ice cooling with 5 ml abs. ethanol in order to destroy excess sodium hydride, poured into a saturated sodium chloride solution, extracted with ether and worked up. trans)-dodeca- omatography and thereafter Torr.
Example 9 19.2 g of sodium hydride (50$ in mineral oil) are washed twice with 100 ml of hexane, cooled to 0-10°C after the addition of 200 ml abs. tetrahydrofuran, and treated drop- wise with 44.8 g (ethoxycarbonylrmethyl)-dlethoxy-phosphine oxide. The mixture is stirred for 1 1/2 hours at room temperature, mixed gradually at 5-15°C with 38.8 g of 6,10-dimeth l undeca-5-trans-9-dien-2-one ( trans-geranylacetone ) , stirred for 20 hours at room temperature and thereafter treated care¬ '"'if" fully under, ice cooling with 30 ml of abs. ethanol in order to destroy excess sodium hydride . The reaction solution is then poured into 2000 ml of saturated sodium chloride solution, extracted with ether, washed, dried and evaporated. The residual 3,7,ll-trimethyl-dodeca-^-cis(30^)/trans(70 ),6-trans, acid ethyl ester after distillation boiled at 115-117°C/0.02 Torr.,. yield 68%. The compound may be transformed by epoxydation into the 10 ll-epoxy-3,7, 11-trimethyl- dodeca-(2-cis(30%)/trans (J0% ) , 6-1rans>dieri¾>ic-acid ethy1 ester In an analogous manner, by the reaction of geranylacetone with various phosphine oxides of the general formula in tetrahydrofuran in the presence, of sodium hydride, there are obtained 3,7,ll-trimethyi-dodeca-{2-cis/trans,6-trans, 10)-trien- J^oic acid ethyl ester or 10, ll-epoxy-3,7, 11-trimethyl-dodeca- (2-cis/trans,6-trans dien'ii oic acid ethyl ester, respectively, • cis. trans Yield of 2-cis/ trans mixture phenyl 40 60 , 75% . 2-chloro-phenyl 4 58 60 2-fluoro-phenyl 44 . 56 65% 2-bromo-phenyl . 44 56 6k 2-methoxy-phenyl 32 68 69% 2, 4-dichloro-phenyl- 45 55 73# 4-nitro-phenyl 46 59% 3-nitro-phenyl 44 36 65% ,·;■'.. 2, 6-dichloro-phenyl 26 7 30% The preferred solvents are tetrahydro uran, dioxah and 1 , 2-dimethoxyethane.
Example 10 . 45 g of 3*7»ll-trimethyl-dodeca- 2-cis/trans, 6-trans, lO^trien^i^oic acid ethyl ester are stirred in 1500 ml of 0. 5-N 0$ aqueous, ethanolic caustic soda at 50°C for 48 hours. The reaction mixture is subsequently diluted with 3000 ml of water, extracted twice with ether, the aqueous alkaline solution is acidified with 2-N- hydrochloric acid with ice-cooling and exhaustively extracted with ether. The combined extracts are washed neutral with a saturated aqueous sodium chloride solution, dried over, sodium sulphate and evaporated. The residual 3>7 * 11÷ trimeth l-dodeca-(2~cis/trans, 6-trans, 10)-trieri^i—oic acid is purified b distillation B. . : 12 -1 0°C 0. 1 Torr. - The l-ethoxy-3,7,ll-trimethyl-dodeca-(2-cis/trans,6- : cis, 10)·triene mixture, can be separated up by fractional distillation into :l-ethoxy-3,7> ll-trlmethyl-dodeca-(2-cis,-6-cis, 10)-triene and l-ethoxy-3,7 ll-trimethyl-dodeca-4--trans,6- cis, lOVtriene, and the l-acetoxy-3,7, ll-trimethyl-dodeca-^2- cis/trans,6-cis, 10)-triene can be separated up into l-acetoxy-3,7ill-triiiiethyl-dodeca-i( -cis,6-cis, 10)-triene and 1-acetoxy-3,7 H-trimethyl-dodeca-C2-trans,6-cis, 10)-triene, and converted into the corresponding (2-cis>6-cis)- or (2-trans,6-cis)-10, 11-epoxy-farnesyl ethyl ether (2-cls,6-ci6)- or (2-trans,6-ci¾)-10, 11-epoxy-farnesyl acetate .and (2-cis, 6-cis)- or (2-trans,6-cis)-10,ll-epoxy-farnesol compound. .4 g of l-ethoxy-3,7* ll-trimethyl-dodeca-£-trans, 6.-cis lOVtriene in 100 ml of methylene chloride are cooled to 0°C, treated portionwise with ¾. g of m-chloroperbenzoic acid, stirred at 0°C for 1 1/2 hours, then successively washed with 1-N caustic soda and water, dried over sodium sulphate and evaporated. The residual 10, ll-epoxy-l-ethoxy-3, 1, 11-trimethyl dodeca^2-trans,6-cis^diene; is split into the corresponding 6,7-epoxy compound by fractional distillation of portions, b.p. 93-94°c/0.05 Torr.
The l-ethoxy-3,7i 11-trimethyl-dodeca-(2-trans,6-cis, 10)- triene can with the aid of N-bromosuccinimide also be converted to the corresponding 10, 11-epoxy compound. 4 Example 12 . 19. 6 g of N-bromosuccinimide are added portionwlse at . ,0-5°C within j50 minutes to a homogeneous solution of ' 26. g of l-acetoxy-3, 7,ll-trimethyl-dodeca- 2-cis/trans, 6-cis, 10j)- triene, 715 ml of tetrahydrofuran and 200 ml of water, The mixture is stirred for hours, then poured into a saturated sodium chloride .solution, extracted with hexane and worked' up. . By chromatography with hexane-15^ ether' on silicagel, 22.5 g v¾-¾*d.f pure 10-bromo-ll-hydroxy-l-acetox (2-°is rans*6-cisydiene are obtained.
A solution of 2.6 g of sodium dissolved in 60 ml of . abs. methanol is added dropwise over a period, of 30 minutes and at 0-2°C to a solution of 20.7 g of 10-bromo-ll-hydroxy-l- acetoxy-3, 7 ll-trimethyl-dodeca-^-cis/trans, 6-cis)-diene in 60 ml of abs. methanol. The mixture is stirred for 30 minutes at 2°G and for 2. 1-/ hours at room temperature, poured into a sodium chloride solution, extracted with hexane, worked up and. distilled. 12.8. g of 10,ll-epoxy-j5, 7,ll-trimethyl-dodeca- (2-cis/trans, 6-cis)-dien-l-ol, b.p. 99-101oc/0. 001 Torr. were ' obtained. ' The same compound can also be prepared starting from l-acetoxy-3, 7> 11-trimethyl-dodeca-^-cis/trans, 6-cis, 10)-triene by epoxidation with a peracid to 10, ll-epoxy-l-acetoxy-3, 7 i H- • - ' Example 13 ■ ·.' ■ ■ "' ' 2. 4 g of sodium hydride. ( 50$ in mineral oil) are washed twice with 20 ml of hexane, cooled to about- 10-.12°C after the addition of 50 ml of abs. dioxan and treated dropwise with 11 . 9 g of 10,ll-epoxy- ,7,ll-trimethyl-dodeca- 2-cis/trans, 6-cig)-dien-l-ol. The mixture is stirred for 2 hours at room temperature, cooled to about 10-15°C, treated dropwise with 8 g of ethyl iodide, stirred at room temperature for 16 hours, then poured into a saturated sodium chloride solution, extracted with hexane and worked up. By chromatography With hexane/l5# · · ethyl acetate on silicagel and subsequent distillation, 10.5 S of pure 10,ll-epoxy-l-ethoxy-3,7,ll-trimethyl-dodeca 2-cis/traiis, 6-ci^-diene are obtained, b, p. 93°c/0.05 Torr.; nD = 1,4710.
If in Example 13 the ethyl iodide is replaced by 9 g of propyl · ' iodide , the 10,ll-epoxy-l-prbpoxy-3,7,ll-trimethyl-dodeca-(2-cis/ · trans, 6-cis-diene is obtained in an analogous manner; n-p. = 1,4703.
In an analogous manner, starting from trans-geranylacetone via trans-nerolidol there is obtained ll.-trimethyl-dodeca 2-cis/trans, 6-trans, 10)·triene which can be converted into 1— ethoxy-3,7,ll-trlmethyl-dodeca-(2-cis/trans, 6-trans ,10)-triene or l-acetoxy-3, 7>H-trimethyl-dodeca- (2-cis/trans, 6-trans,10)-triene by treatment with sodium ethylate or potassium acetate, respectively.
Both these compounds can , if necessary, after separating ·■· ■ ■ Example 15 "■ ' - ..· "' Eggs of the clothes moth [Tiheola biselliellal are sprayed with an aqueous suspension o-f the acitve substance. The hatching rate. of the caterpillars is determined.
Active substance 'Hatchings rate concentration, in. o ·'■ . in o ':. A 0,1 : 0,01 : · - 17 Control 0 ' : 95 Example 23 9.5 g of m-chloro-perbenzoio acid (93$) are added in email portions, under cooling with ice and stirring, to 14.3' g of 4- 5,7fll-trimethyl-dodeca-(2-cie/trans, 6-trans, 10)-trienoy2/-morpholine in 140 ml of methylene chloride. The reaction mixture is stirred under cooling with ice for a further two hours, then diluted with 280 ml of ether, washed with ice-cold 1 W sodium hydroxide solution and with a saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. The residue is chromotographed on silica gel with hexane-aoetone 4il yielding pure 4- 0,li-epoxy-3,7,ll-trlmethyl-dodeca-(2-cls/trans, 6-trans)-dionoy2/-morphollne, b.p. ca. 145°0/0.002 Torr* ^° 1,5094.
The starting material can be prepared as follows. .8 g of thionyl chloride are added dropwise over 15 mlns. and under cooling with ice to a solution of 17 of 3,7»ll-trimethyl-dodeca-(2-cis/trans* 6-trans-10)-trienoic acid. The reaction mixture is stirred at room temperature for a further hour and subsequently filtered in order to separate the precipitated pyrldinium chloride. The filtrate is evaporated and the residue is dissolved in 140 ml of anhydrous benzene and cooled in an ice bath. 14 g of morpholine in 40 ml of anhydrous benzene are added dropwise and the mixture is stirred at room temperature for 30 mlns. The reaction mixture is then poured into ioe-colci. ^ 1 K aqueous hydrochloric acid and extracted exhaustively with ether. The combined ether extracts are washed with saturated aqueous sodium bicarbonate and sodium chloride solutions, dried over sodium sulfate and evaporated. Through chromotography on silica gel with - t t and b u t d til at t r

Claims (2)

1. a saturated 6-membered heteroc clic r Rg represent aryl or dialkylamino . and Ry and Rg represent aryl, alkoxy or aryloxy, if desired, an alkoxycarbony1 group present is. transformed into an aminocarbonyl group and the product obtained is con- verted to an epoxide or in that a compound of general formula II is converted to an epoxide and reacted with a phosphine oxide of general formula IV or in that a compound of formula II is brought into reaction with acetylene, the product obtained is partially hydrogenated and either subjected to an allylic /.rearrangement in the presence of an alkanol and an acid or converted into a primary halide with allylic rearrangement and then either reacted with. an alkali-metal alcoholate and then the product ■ obtained is converted to an epoxide, or reacted with an alkali metal alkanoate and the product obtained converted to an epoxide and hydrolysed (in any order) and thereafter the primary alcohol obtained is reacted with an alkyl halide, and in that a compound of formula I obtained in which X denotes an alkoxycarbonyl group is saponified if desired.
2. Process according to claim 1, wherein citronellyl- acetone is reacted with an alkoxycarbonyl-phosphorane of formula III or phosphine oxide of formula IV, the ester obtained is saponified, halogenated, treated with ammonia or with a mono- or di-alkylamine (preferably diethylamine) and converted to an epoxide. the Ν,Ν-diethyl acid amide obtained is converted to an epoxide. 4. Process according to claim 1, wherein geranyl acetone is reacted with an alkoxycarbonyl-phosphorane of formula III or -phosphine oxide of formula IV, the ester obtained is saponified, halogenated, treated with ammonia or with a mono- or di-alky1amine (preferably with dietfrylamine) and converted to an epoxide. 5. Process according to Claim 1, wherein geranyl acetone : is reacted with diethylphosphono-N,N-diethylacetamide and the N,N-diethyl acid amide obtained is converted to an epoxide. 6. Process according to Claim 1, wherein geranyl acetone is reacted with acetylene and partially hydrogenated, ' the nerolidol obtained is halogenated, treated with an alkali- metal alcoholate and converted to an epoxide. 7· Process according to Claim 1, wherein geranyl acetone . is reacted with acetylene and partially hydrogenated, the nerolidol obtained is halogenated, treated with an alkali metal alkanoate (preferably potassium acetate) the product obtained converted to an epoxide, the epoxyacetate hydrolysed and the alcohol obtained reacted with an alkyl halide in the presence of a base, preferably in the presence of sodium hydride in an inert solvent (preferably dioxan). ' 10,ll-Epoxy-3,7*ll-trimethyl-trideca-2 6-dien-^ oic acid methyl ester. 36.6,7;10,ll-Diepoxy-N,N-diethyl-3,7 ll-trimethyl-
IL31196A 1967-12-18 1968-12-02 10,11-epoxy-3,7,11-trimethyl-dodec-2-enoic acid,corresponding esters,amides,alcohols and nitriles and their preparation IL31196A (en)

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CH1779667A CH508613A (en) 1967-12-18 1967-12-18 Process for the preparation of epoxy compounds

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IL31224A IL31224A (en) 1967-12-18 1968-12-04 1-methoxy-3,7,11-trimethyl-10,11-epoxydodeca-2,6-diene and derivatives thereof and their preparation

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CH544488A (en) 1974-01-15
BE725578A (en) 1969-06-17
GB1263651A (en) 1972-02-16
ES361552A1 (en) 1971-06-16
SE376919B (en) 1975-06-16
IL31224A0 (en) 1969-02-27
GB1250647A (en) 1971-10-20
BE725579A (en) 1969-06-17
IE32588B1 (en) 1973-09-19
BR6804902D0 (en) 1973-03-08
SE362245B (en) 1973-12-03
NL6818162A (en) 1969-06-20
NO124992B (en) 1972-07-03
GB1257431A (en) 1971-12-15
BR6804901D0 (en) 1973-03-08
IT947013B (en) 1973-05-21
CA942764A (en) 1974-02-26
TR16999A (en) 1974-03-28
DE1814875A1 (en) 1969-07-10
CH508613A (en) 1971-06-15
IE32897B1 (en) 1974-01-09
DK124332B (en) 1972-10-09
IE32897L (en) 1969-06-18
IT988509B (en) 1975-04-30
PH9348A (en) 1975-10-06
AT291674B (en) 1971-07-26
IL31224A (en) 1973-05-31
CS154600B2 (en) 1974-04-30
FR1599304A (en) 1970-07-15
DK126940B (en) 1973-09-03
FR1599302A (en) 1970-07-15
CH544487A (en) 1973-11-30
NO126226B (en) 1973-01-08
IE32588L (en) 1969-06-18
DE1814872A1 (en) 1969-07-03
AT294489B (en) 1971-11-25
GB1255650A (en) 1971-12-01
IL31196A0 (en) 1969-02-27
GB1256653A (en) 1971-12-15
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NL6818045A (en) 1969-06-20

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