IL31224A - 1-methoxy-3,7,11-trimethyl-10,11-epoxydodeca-2,6-diene and derivatives thereof and their preparation - Google Patents
1-methoxy-3,7,11-trimethyl-10,11-epoxydodeca-2,6-diene and derivatives thereof and their preparationInfo
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- IL31224A IL31224A IL31224A IL3122468A IL31224A IL 31224 A IL31224 A IL 31224A IL 31224 A IL31224 A IL 31224A IL 3122468 A IL3122468 A IL 3122468A IL 31224 A IL31224 A IL 31224A
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- 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
- C07D303/18—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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C07—ORGANIC CHEMISTRY
- 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
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- C07—ORGANIC CHEMISTRY
- 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
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- 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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- 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
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
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- 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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- 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
- C07D303/40—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
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- 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
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Epoxy Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Earth Drilling (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Securing Of Glass Panes Or The Like (AREA)
Description
31224/2 -ηρτΐ7-»ρρικοκ-1 ,1O- »na»"tB- 1 , 7, 3-»op κηa-1 onaam ivm-iVim. ΐκ»τ-6,2 l*M0 lio3Qr-3»7»il-rlffiothyi^lO,ll~epQxy*dodeea«* 2,6-diene and derivatives thereof and their preparation SPARAMEDICA AO C/ 29443 - ■ · \ The present invention is concerned with epoxy compounds of the general formula · in which A plus B and C plus D each signify an oxygen bridge, or A plus B signifies a carbon- carbo bond and C plus D signifies an oxygen bridge, or A plus B signifies an oxygen bridge and C plus D signifies a carbon-carbon bond, with the proviso, that in each case the larges groups on the 2- and 3-position carbon atoms have cis/trans, cis or trans configuration and the largest groups on the 6- and 7-position carbon atoms have cis configuration, and with a process for the manufacture thereof.
In accordance with the process of the invention, pound of the formula is subjected to an allylic rearrangement by reaction with methanol in the presence of an acid, whereupon the resulting ether is converted into an epoxide, or %&s-b a compound of the formula II is converted into a primary halide with allylic rearrangement and V · an epoxide and hydrolysed in any sequence, and the resulting primary alcohol is reacted with a methyl halide and that, if desired, a mixture of 6,7- and 10,11-epoxy compounds is split up.
The starting compounds of formula II can be prepared, for example, by reacting cis-geranylacetone with acetylene in the presence of sodium amide in liquid ammonia and partially hydrogenating the triply unsaturated compound obtained with the help of a partially inactivated catalyst, for example a quinoline-deactivated lead/palladium catalyst* When the cis-nerolidol obtained is reacted with methanol in the presence of an acid, there is obtained with allylic rearrangement the desired methyl ether, which by treatment with a peracid or a mixture of li-bromosuccinimide and water , can be concerted (in the latter case via the resulting bromhydrin) into an epoxide.
It is advantageous to work in the cold, especially at a temperature in the range of from 0° to 20°0* Suitable acids include, for example, sulfuric acid and p-toluenesulfonlc acid. The presence of a solvent which is immiscible with the reaotion mixture can be of advantage.
In addition to N-bromosuccinlmide/water, there can be employed as oxidation agent organic peracids such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid' or perphthallc acid.
The cis-nerolidol obtained can also be halogenated with allylic rearrangement, the halogenide obtained reacted with an alkali metal methylate and the product converted into an epoxide by means of peracid treatment or N-bromosuccinimide/ •water treatment as mentioned 'above* ' As halogenating' agent* th·ere Is preferabl employed a phosphorus halide* especially phosphorus tribroraide.- The reaction of the halogenating agent with the cis-nerolidol is carried out in the cold 1·β· especially at a temperature of from -10° to +5° C.
The above obtained halogenide can however also be converted to an ester b reaction . with an alkali metal alkanoate* especially with an alkali metal salt of a lower alkanoic acid having 1-6 carbon atoms, such j as for example sodium acetate* and the ester may either be converted to an epoxide by treatment with a peracid or by treatment with a mixture of N-bromosuccini-mide and water followed by conversion of the resulting bromhydrin, and then hydrolysed to the corresponding alcohol, or first hydrolysed and' then epoxldise'd by treatment with a peracid.
In either case, the alcohol obtained is thereafter methylated to form the desired epoxy compound of formula I· The methylation is suitabl carried out at room temperature in the presence of a base in an inert solvent, preferably in the presence of sodium hydride in dioxane. Of the methylhalides suitable as methylating agent, methyl iodide is preferred.
The epoxidation is convenientl carried out by dissolving the respective compound in an inert Solvent, especially a halogenated hydrocarbon such as methylene chloride or chloroform, and treating the solution at a temperature between 0°C and room temperature with an above mentioned peracid. Alternatively* the respective compound may be suspended i water and displaced with an amount of an inert solvent, e.g. dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, such that a homogenous concentrated solution results, Ib-bromosuccinimide being added portionwise to this solution at a temperature of from 0 to room temperature. The resulting bromhydrin can be readily converted to the epoxide by reaction with alkali, particularly sodium methylate in methanol.
The particular advantage of the N-brontosuecinimide method lies in the fact that only the terminal double bond is oxidised, whereas epoxidation with organic peracids (if 1 mole of peracid is used) results instead in a mixture of 6,7- and 10,11-epoxides. If one reacts 2 moles of peracid with 1 mole of the respective compound the 6,7»10,ll-diepoxide is obtained.
The compounds of formula I are suitable for the control of pests . In contrast ; — ;— to most of the pest-control agents known hitherto, which kill, cripple or drive away the animals as contact- or feed-poisons, the compounds of formula I obtainable by the process of the invention interfere with the hormonal system of the animal organism. In insects the trans ormation into,for example , the imago is disturbed. The sequence of generations is interrupted and the animals are indirectly killed. The compounds are practically non-toxic to vertebrates, the toxicity of the compounds of formula I in vertebrates being over 1C00 mg/kg body weight. Moreover, the new compounds are readily degraded and the risk of accumulation is therefore excluded. The compounds can therefore unhesitatingly be employed for the control of pests in animals, plants, provisions and textiles. ^ii- 31224/2 V The compounds are especially suitable for the control of invertebrate animals. As is more precisely set out hereinafter, in general an active substance concentration of 0.01 to 0.1$¾ is already sufficient to ensure the desired effect.
The active substances can, for example, be employed in the form of emulsions, suspensions, dusting agents, solutions or aerosols. In special cases, the matter which is to be protected (e.g. foodstuffs, seeds or textiles) can also be directly impregnated with the active substance in question or with a solution of the active substance.
The active substance can, moreover, also be employed in a form which only releases the active substance by the action of external influences (e.g. in contact with moisture) or only in the animal body itself. It is also possible to use the compounds of formula I in admixture with other known pest-control agents.
Compounds closely related to those encompassed by formula I above are known from e.g. Life Sciences 23 3 (1965). The epoxy farnesyl derivatives disclosed therein are, however, of inferior activity in the Tenebrio molitor test when compaued with instantly claimed compounds.
The following Examples illustrate the invention.
Example 1 Cis-geranylacetone is condensed with sodium acetylide in liquid ammonia in a manner known per se. The resulting cis dehydronerolidol is subsequently partially hydrogenated to cis-nerolidol. 300 g of 5,7»ll-triraethyl-dodeca-l,'6-cis --'-lO-trien-3-ol (cis-nerolidol] are mixed with 8l0 ml of petroleum ether [boiling range 0- 5°C] and 31.5-ml of pyridine and treated dropwise at -5 to 0°C within 2 hours with- 159 g of phosphorus trihromide . i 180 ml of petroleum ether [boiling range 40-4-5eC]# The reaction mixture is further stirred at -5 to O°C for $0 minutes, then poured onto ice and, , after a further JO minutes, treated with 1500 ml of ether.
The petroleum ether/ether phase is separated off, successively washed with water and with a saturated aqueous sodium hydrogen carbonate solution, dried ove sodium sulphate and evaporated initially at °C under reduced pressure, then dried under high vacuum. The residual crude l-bromo-357,ll-trimethyl-dodeca- ■' -2-cis/trans, 6-cis, 10-triene can.be further processed as follows without further purification: A) to l-methoxy-3>7, ll-trimethyl-dodeca-2-cis/transy 6-cis,10-triene, or B) to l-acetoxy->>7>ll-trimethyl-dodeca-2-cis/trans>6-cis,10-triene, A) 550. g of l-bromo-5,7,ll-trimethyl-dodeca-2-cls/trans,t 6-cis,10-triene are added dropwise with ice-cooling to a solution of 32 g of sodium in 640 ml of abs. methanol. In so doing, the internal temperature should not exceed 20°C. The reaction mixture is subsequently stirred at room temperature for 16 hours j heated to boiling temperature under" . reflux conditions for 1 hour, then cooled, poured onto ice and exhaustively extracted wit petroleum e her [boiling range 4-0-45wC]. The combined extracts are washed neutral, dried over sodium sulphate and evaporated. The residual 1-methoxy-~3 , 7?ll-trimethyl~dodeca~2- cis/trans,6-cis, -triene is purified by distillation. B.p. : 92-94
B) 365 g of l-bromo- , 7,ll-trimethyl-dodeca-2-cis/trans, 6-cis, 10-triene together with 208 g of anhydrous potassium acetate are heated in 2400 ml of acetone for 24 hours under reflux conditions. The potassium bromide which precipitates on cooling is filtered off and the filtrate is evaporated.
The residual l-acetoxy-3,7,ll-trimethyl-dodeca-2-cis/trans, 6-cis, 10-triene (226 g) after dis4--" llation boils at 116- The l-methoxy-3,7,ll-trimethyl-dodeca-2-cis/trans,6-cis, 10-triene mixture can be separated up by fractional distillation into l-methoxy-3,7,ll-trimethyl-dodeca-2-cis, 6-cis,10-triene and l-methoxy-3,7,ll-trimethyl-dodeca-2-trans,6-cis, 10-triene (bp. 94.5°C/0.15 Torr.), which can be epoxidised according to the methods hereinafter described. g of l-methoxy-3,7,ll-trimethyl-dodeca-2-trans, 6-cis, 10-triene in 100 ml of methylene chloride are cooled to 0°C, treated portionwise with 4.4 g of m-chloroperbenzoic acid, stirred at 0°C for 11/2 hours, then successively washed with 1-N-caustic soda and water, dried over sodium sulphate and evaporated. The residual 10,ll-epoxy-l-methoxy-3,7,ll-trimethyl-dodeca-2-trans,6-cis-diene can be separated from the corresponding 6,7-epoxy compound present by fractional distillation, b.p. 93-94.5°C/0.002 Torr.
The l-methoxy-3,7,ll-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 as follows: 18.6 g. of N-bromosuccinimide is added portionwise within 30 minutes and at a temperature of 0-3°C to a homogeneous solu-. tion of 23.6 g of l-methoxy-3,7,ll-trimethyl-dodeca-2-cis/trans, 6-cis,10-triene, 40 ml of distilled water and 230 ml of tetra-hydrofuran. The mixture is stirred for 5 hours at 0-3°C, poured into 2000 ml of saturated sodium chloride solution, extracted with hexane and worked up. By chromatography with hexane-ethyl trimethyl-dodeca-2-cis/trans,6-cis-diene are obtained, b.p. 115°C/0.001 Torr; n ° = 1.5216.
A solution of 1.12 g of sodium dissolved in 25 ml of abs. methanol is added dropwise at 0-3°C to a solution of 16.3 g of 10-bromo-ll-hydroxy-l-methoxy-3, 7 , 11-trimethyl-dodeca 2-cis/trans,6-cis-diene in 25 ml of abs. methanol. The mixture is stirred for a further 30 minutes, then poured into 100 ml of saturated sodium chloride solution, extracted with hexane and worked up. By distillation, 10.4 g of pure 10,11-epoxy-l-methoxy-3,7,ll-trimethyi-dodeca-2-cis/trans,6-cis-diene are obtained, b.p. 92-94°C/0.002 Torr.; n ° e 1.4721.
Example 2 The l-acetoxy-3,7, ll-trimethyl-dodeca-2-cis/trans, 6-cis 10-triene obtained according to Example 1 can be, if desired , before further working up, split up by fractional distillation into l-acetoxy-3, 7 ,ll-trimethyl-dodeca-2-cis , 6-cis , 10-triene and l-acetoxy-3» 7 , ll-trimethyl-dodeca-2-trans , 6-cis , 10-triene as follows : .19.6 g of N-bromosuccinimide are added portionwise at 0-3°C within 30 minutes to a homogeneous solution of 26.4 g of l-acetoxy-3,7, ll-trimethyl-dodeca-2-cis/trans, 6-cis, 10-triena 715 ml of tetrahydrofuran and 200 ml of water. The mixture is stirred for 5 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 of pure lO-bromo-ll-hydroxy-l-acet.oxy-3,7 l-trimethyl-dodeca-2-cis/trans,6-cis-diene are obtained.
. A solution of 2.64 g of sodium dissolved in βθ ml of abs. methanol is added dropwise over a period of >0 minutes and at 0-3°C to a solution of 20.7 g of 10-bromo-ll-hydroxy-l-acetoxy-3,7* ll-trimethyl-dodeca-2-cis/trans,6-cis-diene in βθ ml of abs. methanol. The mixture is stirred for j50 minutes at 2°C and for 2 l/4 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. 99-101°C/0.001 Torr. were obtained.
The same compound can also be prepared starting from l-acetoxy-3>7*ll-trimethyl-dodeca-2-cis/trans>6-cis,10-triene by epoxidation with a peracid to 10,ll-epoxy-l-acetoxy-;5,7,ll-trimethyl-dodeca-2-cis/trans,6-cis-diene, which is thereafter saponified to the desired primary alcohol.
Example 3 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-3,7Al-trimethyl-dodeca-2-cis/trans,6~ . cis-dien-l-ol. The mixture is stirred for 2 hours at room 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 g of pure 10,ll-epoxy-l-methoxy-3,7,ll-trimethyl-dodeca-2-cis/trans, 6-cis-diene are obtained, b.p. 92-94°C/0.002 Torr; n^° = 1.4721.
Example 1. g of cis-nerolidol is added to 60 ml of 5 methanolic sulfuric acid and allowed to stand at room temperature for 64 hours . The reaction mixture is thereafter poured into water and extracted with petroleum ether (boiling range 40-60°C).
The extract is washed first with a saturated aqueous sodium bicarbonate solution and then with a saturated aqueous sodium chloride solution, dried over sodium sulfate arid evaporated.
The residual l-methoxy-3,7,ll-trimethyl-dodeca-2-cis/trans, 6-cis,10-triene(b.p. 92-94. °C/0.015 Torr) can be oxidised, as described in Example 1, to a mixture consisting of 10,ll-epoxy-l-methoxy-3,7,ll-trimethyl-dodeca-2-cis/trans , 6-cis-diene and 6,7-epoxy-l-methoxy-3,7,ll-trimethyl-6,7-cis-dodeca-2-cis/trans, 10-diene,. which can, if desired, by separated into the individual components by fractional distillation.
Example 5 . 9 g of 1-methoxy- 3 »7 ,ll-trimethyl-dodeca-2-cis/trans , 6-cis,10-triene is added to 100 ml of methylene chloride, cooled to 0°C and treated portionwise with stirring with 16.4 g of m-chloroperbenzoic acid (79 f°) . The reaction mixture is stirred for 2 hours at V washed with ice cold 1 n caustic soda and a saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. The residual 6,7fl0,ll-diepoxy-l-methoxy-3,7,ll-'tri--methyl-6,7-cis-dodec-2-cis/trans-ene is purified by chromatography on silica gel (elution agent hexane - ethyl acetate l;l) b.p. 120°C/0.28 Torr; nj° = 1.4672.
Example 6 Discs of woollen material [diameter 30 mm] are soaked with a solution of 10, ll-epoxy-l-methoxy-3, 7 ,11-trimethyl-dodeca-2-trans,6-cis-diene in acetone and each disk is stocked with larvae of the clothes moth' fTineola biselliellal . The larvae placed onto untreated woollen material develbp into caterpillars which pupate normally and thereafter form moths. Caterpillar-formation and pupation in the larvae placed onto treated woollen discs are interrupted. mg of active Number of Number of Number Rate substance per living moultings of of woollen disc caterpillars moths damage ( o 0 22 0 0 1 3 47 3 35 Control 0 1 17 9 80 Example 7 Corrugated cardboard strips [20 x 50 mm] are soaked with an acetone solution of 10, ll-epoxy-l-methoxy-3, 7, 11-trimethyl-dodeca-2-trans , 6-cis-diene and stocked with ready-to-pupate larvae of the codling moth fCarpocapsa pomonellal. The larvae placed onto untreated cardboard creep into the cavities of the corrugated cardboard, spin themselves in and release the moth after 14 days. Caterpillar-formation and pupation of the larvae placed onto treated cardboard are disturbed. mg of active Number of Number of moths substance per caterpillars and cardboard strip pupae normal dead normal deformed 0 5 0 0 1 2 5 0 1 0.1 1 1 0 5 Control 0 15 Example 8 100 g of wheat grains are soaked with an acetone solution of 10, ll-epoxy-l-methoxy-3 , 7 , ll-trimethyl-dodeca-2-trans , 6-cis- diene, dried and infected with 100 corn beetles fCalandra granaria1. After 14 days, the beetles are sieved off and observed for 6 weeks. The beetles fed with untreated grains reproduce normally. The beetles fed with active substance-containing grains display distinct developmental disturbances.
Young bean plants are strongly infected with greenfly fNeomyzus circumflexus1 -and sprayed with an acetone solution of 10 , ll-epoxy-l-methoxy-3 , 7 , ll-trimethyl-dodeca-2-trans , 6-cis- diene. The mortality of the fly is determined after 2 days.
Active substance Mortality concentration in f 0.1 15 0.01 8 Control 0 5 Example 10 Ready-to-pupate larvae of the housefly ΓMusea domestical are placed on a mixture consisting of bran, milk powder, yeas and 10 ,ll-epoxy-l-methoxy-3 ,7 , 11-trimethyl-dodeca-2-trans , 6-cis-diene. The larvae pupate and, after a few days, release the flies. Larvae which have been placed onto active substance-free medium develop normally and display no disturbance in egg-laying.
Larvae on active substance-containing medium have an increased mortality. mg of active substance Hatching Egg- per cml of larval feed rate in # laying 4 35. 0 Control 0 78 46 Example 11 Colorado beetles in the last larval-stage are on two-consecutive days are each sprayed with a 0.1 i<> solution in acetone of 10, ll-epoxy-l-methoxy-3, 7,ll-trimethyl-dodeca-2-trans, 6-cis-diene and fed with potato leaves.
Concentration of Pupation retardation Metamorphosis active substance [for each 10 animals disturbance the number which have [number of dead not pupated after or crippled beet- 3 days] les from each ten animals] —6 2 ca. 10"" g/cm 5 6 0 0 0 Example 12 ~x g of 10fll-epoxy-l-methoxy-3,7,ll-trimethyl-dodeca 2-trans, 6-cis-diene are dissolved in acetone and with the help of an accurate pipette in each case dripped on to 10. Vanessa larvae shortly before pupation. The metamorphosis progress of the treated animals is compared with that of untreated animals ] In each case ca. 50 eggs of the meal-moth Ep_hestia kuhniellal are laid on disks of blotting paper, sprayed with an acetone solution of a mixture of 10,ll-epoxy-l-methoxy-3,7,ll- trimethyl-dodeca-2-cis/trans , 6-cis-diene and 6 , 7-epoxy-l-methoxy 3»7,ll-trimethyl-6,7-cis-dodeca-2-cis/trans,10-diene and maintained at 25°C for 4. days. The ovicidal activity is determined by reference to the number of normally hatched larvae.
Concentration of Number of Number of Mortality active substance . eggs larvae o "4 56 0 100 10~5 65 2 63 10~6 60 47 22 0 without acetone 52 49 6 0 without acetone 47 43 8 with acetone 49 46 7 0 with acetone 50 47 6 31224/2
Claims (1)
1. CLAIMS Epoxy compounds of the general formula in which A plus B and C plus each signify a oxygen bridge or A plus B signifies a bond and 0 plus D nifies an oxygen or A plus B signifies an oxygen bridge and C plus D signifies a with proviso that in each case the largest groups on the and carboriatoms have cis or trane configuration and the largest groups on the and carbon atoms have cis 3 trans 1 6 10 Process for the production of an epoxy compound according to Claim 1 wherein a compound of the formula is subjected to an allylic rearrangement by reaction with methanol in the presence of an whereupon the resultin ether is converted into an or that a compound of the formula II is converted into a primary halide with allylic rearrangement and the halide is then reacted with an metal methylate and the product obtained converted to an or with an alkali metal alkanoate and the product obtained converted to an epoxide and hydrolysed in any and the resulting primary alcohol is reacted with a methyl halide and if a mixture of and compounds is split Process according to Claim wherein is reacted with methanol in the presence of an preferably sulfuric acid or and the ether obtained is to an Process according to Claim wherein is halogenated with a phosphorus preferably phosphorus and the halogenide obtained is reacted with an alkali metal preferably sodium and the resulting ether is converted to an Process according to Claim wherein is halogenated with a phosphorus halide preferably phosphorus and the halogenide obtained is reacted with an alkali metal alkanoate in an inert solvent preferably with potassium acetate in the ester obtained in optional converted to an epoxide and and thereafter the alcohol obtained is reacted with a preferably methyl in the presence of a preferably sodium and in an inert preferably Process for the production of epoxy compounds of the general I defined in Claim substantially as described with reference to the foregoing Examples 1 to Process for the manufacture of wherein a compound according to Claim 1 added as active ingredient to an solid or liquid carrier of the type used in such Process according to Claim wherein is used as active ingredients Process according to Claim wherein is used as active agent containing as ingredient an epoxy compound according to Claim agent according to Claim wherein the active ingredient is agent according to Claim wherein the active ingredient is insufficientOCRQuality
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1779667A CH508613A (en) | 1967-12-18 | 1967-12-18 | Process for the preparation of epoxy compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL31224A0 IL31224A0 (en) | 1969-02-27 |
| IL31224A true IL31224A (en) | 1973-05-31 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL31196A IL31196A (en) | 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 |
| 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 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL31196A IL31196A (en) | 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 |
Country Status (19)
| Country | Link |
|---|---|
| AT (2) | AT294489B (en) |
| BE (2) | BE725578A (en) |
| BR (2) | BR6804902D0 (en) |
| CA (2) | CA933528A (en) |
| CH (3) | CH544487A (en) |
| CS (1) | CS154600B2 (en) |
| DE (2) | DE1814875A1 (en) |
| DK (2) | DK126940B (en) |
| ES (1) | ES361552A1 (en) |
| FR (2) | FR1599304A (en) |
| GB (5) | GB1250647A (en) |
| IE (2) | IE32588B1 (en) |
| IL (2) | IL31196A (en) |
| IT (2) | IT988509B (en) |
| NL (2) | NL6818045A (en) |
| NO (2) | NO124992B (en) |
| PH (1) | PH9348A (en) |
| SE (2) | SE376919B (en) |
| TR (1) | TR16999A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL36505A0 (en) * | 1970-03-31 | 1971-11-29 | Sparamedica Ag | Pest control agents containing terpenoid and/or propargyl derivatives |
| US4456603A (en) * | 1979-08-14 | 1984-06-26 | Eisai Co., Ltd. | Polyprenylcarboxylic acid amides useful for treating liver dysfunction |
-
1967
- 1967-12-18 CH CH360370A patent/CH544487A/en not_active IP Right Cessation
- 1967-12-18 CH CH360470A patent/CH544488A/en not_active IP Right Cessation
- 1967-12-18 CH CH1779667A patent/CH508613A/en not_active IP Right Cessation
-
1968
- 1968-12-02 IL IL31196A patent/IL31196A/en unknown
- 1968-12-03 CA CA036724A patent/CA933528A/en not_active Expired
- 1968-12-03 CA CA036,725A patent/CA942764A/en not_active Expired
- 1968-12-04 IL IL31224A patent/IL31224A/en unknown
- 1968-12-05 PH PH9802*UA patent/PH9348A/en unknown
- 1968-12-08 FR FR1599304D patent/FR1599304A/fr not_active Expired
- 1968-12-12 GB GB1250647D patent/GB1250647A/en not_active Expired
- 1968-12-12 GB GB1257431D patent/GB1257431A/en not_active Expired
- 1968-12-12 GB GB1256653D patent/GB1256653A/en not_active Expired
- 1968-12-12 GB GB2455770A patent/GB1263651A/en not_active Expired
- 1968-12-12 GB GB5907168A patent/GB1255650A/en not_active Expired
- 1968-12-16 DE DE19681814875 patent/DE1814875A1/en active Pending
- 1968-12-16 NL NL6818045A patent/NL6818045A/xx unknown
- 1968-12-16 DE DE19681814872 patent/DE1814872A1/en active Pending
- 1968-12-16 IE IE1520/68A patent/IE32588B1/en unknown
- 1968-12-16 IE IE1521/68A patent/IE32897B1/en unknown
- 1968-12-17 IT IT2522268A patent/IT988509B/en active
- 1968-12-17 BR BR20490268A patent/BR6804902D0/en unknown
- 1968-12-17 IT IT2522368A patent/IT947013B/en active
- 1968-12-17 BE BE725578D patent/BE725578A/xx unknown
- 1968-12-17 DK DK617968A patent/DK126940B/en unknown
- 1968-12-17 SE SE1727168A patent/SE376919B/xx unknown
- 1968-12-17 CS CS856268A patent/CS154600B2/cs unknown
- 1968-12-17 SE SE1727268A patent/SE362245B/xx unknown
- 1968-12-17 AT AT1225568A patent/AT294489B/en active
- 1968-12-17 BR BR20490168A patent/BR6804901D0/en unknown
- 1968-12-17 DK DK617868A patent/DK124332B/en unknown
- 1968-12-17 BE BE725579D patent/BE725579A/xx unknown
- 1968-12-17 ES ES361552A patent/ES361552A1/en not_active Expired
- 1968-12-17 AT AT1225668A patent/AT291674B/en active
- 1968-12-17 NO NO5050/68A patent/NO124992B/no unknown
- 1968-12-17 NO NO05051/68A patent/NO126226B/no unknown
- 1968-12-18 TR TR1699968A patent/TR16999A/en unknown
- 1968-12-18 NL NL6818162A patent/NL6818162A/xx unknown
- 1968-12-18 FR FR1599302D patent/FR1599302A/fr not_active Expired
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