DE1814875A1 - Process for the preparation of epoxy compounds - Google Patents

Description

Dr. rrs-v! -v: jrer

PATENiAN WALTE

I DEC 79BB

RAN 6101 / 18-01

F. HofFmann-La Roche & Co. Aktiengesellschaft, Basel / Switzerland

Process for the production of epoxy compounds

The present invention relates to a process for the preparation of epoxy compounds of the general formula

B.
in which R is hydrogen or lower alkyl,

X one of the groups

-G = IT; -COOR ₁ ; -GON ^ ^c or -CHgOR

S denotes in which R, hydrogen, lower alkyl, phenyl or optionally ^{lower alkyl-substituted aminoalkyl, R 1} ^ lower alkyl, phenyl or optionally lower alkj ^ is-substituted aminoalkyl, Rp and R, individually hydrogen or

Cou / 10/24/68 909828/1702

lower alkyl. or together with the nitrogen atom a 5- or 6-membered heterocyclic radical, which may contain oxygen, nitrogen or sulfur as a further heteroatom, and A. and -3 are individually hydrogen or together a carbon-carbon bond or an oxygen bridge denote, where, if at the same time R is hydrogen and A and 3 together are a carbon-carbon bond, R ₁ and R ^ represent an alkyl group with at least 2 carbon atoms, phenyl or optionally lower alkyl-substituted aminoalkyl.

2i-ne alkoxycarbonyl group X is primarily a lower alkoxycarbonyl group with up to β carbon atoms, such as the kethoxy, ethoxy or isopropoxycarbonyl group, in particular the methoxy or ethoxycarbonyl group. An aminocarbonyl group X can be replaced by lower alkyl with up to 6 Carbon atoms, for example, be mono- or di-substituted by methyl, ethyl, isopropyl, in particular by methyl. Also the pialkylaminoaikyl groups. & -, and R ^1. , contain primarily lower alkyl radicals with up to 6 carbon atoms, such as methyl, ethyl, Ιεο- · propyl. The substituents R « ^unc ^ ^ *, including the nitrogen atom, can represent a saturated 5- or 6-membered heterocyclic radical which, if appropriate, can contain nitrogen, oxygen or sulfur as further heteroatoms. as

909828/1702. '

BAD OFUGtNAL

•. . 18U875

Examples of this can be mentioned v / earth the pyrrolidino-, Piperi-.dino-, Pyrimidino or horpholino residue.

If χ denotes an alkoxymethylene group, the alkoxy radical primarily represents a lower alkoxy group with up to δ carbon atoms, such as ζ.3. the kethoxy, ethoxy or isopropoxy group, in particular the kethoxy group. The substituent R can also be primarily lower alk ^{I 1-} I rait up to δ carbon atoms, - vie ζ.3. Designate ethyl, ethyl, isopropyl.

As a representative representative of those which can be produced according to the invention Connections can e.g. 3. ' to be named:

10, ll-epoxy-3,7 »ll-trimethyl-trideca-2,6-diene-1-acid methyl ester

10, ll-epoxy-3,7, ll-trimethyl-trideca-2,6-diene-1-acid ethyl ester

10,11-epoxy-lI, N-diethyl-3,7,11-trimethyl-dodec- ä

2-cis / trans-en-1-acid amide 10,11-epoxy-N, N-diethyl-3,7,11-trimethyl-2-cis / trans, ö-trans'-dodeca-diene-l-acid amide 10,11-epoxy-N, N-diethyl-3 »7,11-trimethyl-2-cis / trans, ö-cis-dodeca-diene-l-acid amide

909828/1702

0ÄD ORfQfNAL

6.7; 10, ll-Diepoxy-E-, N ~ diethyl-3,7,11-trimethyl-6,7-trans-dodec-2-cis / trans-en-1-acid amide.

The inventive method is characterized in that that a compound of the general formula "

" ^υ II

in which H has the meaning given above and λ * and 3 ¹ individually denote hydrogen or together a carbon-carbon bond ",
with a phosphorane of the general ^: formula

5., ^R 6

or with a phoephine oxide of the general formula

P-CH ₉ -X ¹

in which X ^{1 is} one of the groups

-CSäiT; -COOR 'or -COIfC

III

90 9 8 28/1702

denoted in which R »lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R _p and R_ individually hydrogen or lower alkyl, or

together with the nitrogen atom a 5- or 6-membered heterocyclic radical, which acts as a further heteroatom. May contain oxygen, nitrogen or sulfur, R., Rj- and R, - aryl or dialkylamino, and Rj and B ₃ aryl, alkoxy or aryl-. represent oxy,

converts, if an alkoxycarbonyl group is present is converted into an aminocarbonyl group and the product obtained is converted into an epoxide,

or that a compound of the general formula II is converted into an epoxide and with a phosphine oxide the general Formula IV implements, ·.

or that a compound of the formula 'II with acetylene in Brings reaction, the product obtained is partially hydrogenated and either in the presence of an alkanol and an acid Subjected to allyl rearrangement or converted into a primary halide with allyl rearrangement and either with an alkali metal alkoxide converts and the product obtained is converted into an epoxide, or with an alkali metal alkanoate and the err held product in any order converted into an epoxy and hydrolyzed and then the obtained primary Reacting alcohol with an alkyl halide, and that a compound of the formula I obtained in which X is an alkoxycarbonyl group

909828/1702
aar * nfeWÄ «

denotes, if desired saponified ''. ·

The starting compounds used in the process according to the invention of the formula II are partly known compounds, which can be produced in a manner known per se. Characteristic starting substances are e.g.

- 6,10-Dimethyl-unaeca-5,9-dien-2-one [geranylacetone J. .- 6, lG-D: unethyl-aodeca-5, .9-diene / -2-one · ■

- 6 _f 10-2imethyl-undec-9-en-2-oa [gitronellylacetone]

• The phosphoranes of the formula III which can be prepared from the corresponding phosphonium salts can carry aryl or dialkylamino radicals. The aryl radicals marked R., H ₁ - and Sg generally include all known aryl radicals, ζ.3, mononuclear radicals such as

• ■■■. (,

Phenyl, substituted phenyl such as SoJ.yl, xylyl, mesityl, p-I'lethoxyphenyl or polynuclear radicals such as kaphthyl _; Anthryl, phenanthryl, azulyl and others * ·. . ■

• ■

The dialkylamino radicals R ^, R ™, Rg situ preferably lower dialkylamino radicals With up to 4 carbon atoms each, such as dimethyl, diethyl or di-isopropyl amino »

The implementation of the starting compounds of formula II with a phosphorane of the formula III is preferably in the presence catalytic amounts of an organic acid, preferably in the presence of acetic acid or benzoic acid in the presence of a solvent such as benzene, toluene, diethylformaiaia, 1,2-dimethoxyethane

90.9828 / 1702: '· ·

BADOfUGtNAL

or dioxane somewhere between the head temperature and the boiling point of the solvent lying temperature range carried out.

The phosphine oxide of the formula IV can carry aryl, alkoxy or aryloxy radicals. The aryl radicals denoted by B ₇ and R _Q can, like the radicals R 1, iU and Hg in the phosphoranes of the formula III, be mononuclear or polynuclear, substituted or unsubstituted aryl radicals. Of the alkoxy radicals, lower alkoxy radicals with up to 4 carbon atoms are ζ.3. Kethoxy, ethoxy or isopropoxy preferred. Of the aryloxy radicals are in particular phenoxy groups, which are represented by various radicals such as z.3. Alkyl, alkoxy, halogen, bialkylamine, nitro can be substituted one or more times, preferably.

The implementation of an optionally epoxidized starting compound of the formula II with a phosphine oxide of the formula IV is in the presence of a Sase, preferably in the presence of a. " inert organic solvent, e.g. 3. in the presence of sodium hydride in a solvent such as benzene, toluene, dimethylformamide, tetrahydrofuran, dioxane or 1,2-dimethoxyethane, or in Gegert waiting of an alkali metal alcoholate in an alkanol, e.g., 3rd in the presence of liatriuamethylate in methanol, in a between 0 and the room temperature temperature range carried out.

909828/1702

BATH

In a preferred embodiment, for example, the connection of the formula II with a phosphine oxide of the formula IY in the presence * of 2 moles of sodium hydride in abs. Bioxane implemented, with excess Katriuiahydrid dur.ch addition of abs, ethanol destroyed will. '

Compounds of the formula I in which X is a tertiary amicLo group represents, are by condensation of a compound of formula II with a [tert-amido-methylj-phosphorane der'.Formel III accessible. Compounds of the formula I in which X is a tertiary amido group or a primary or secondary amido group represents, can be prepared in such a way that a compound of the formula II is either directly treated with an amide of the Formula IV converts and epoxidized, or first epoxidized and then with a Mid of the formula IV, or that one an ester obtained by reacting a compound of the formula II with an ester of the compounds III or IV in a known manner White, e.g. saponified by treatment with aqueous, alcoholic sodium hydroxide solution, the free acid obtained by the action of a Halogenating agents such as thionyl chloride into the acid halide related dfc and this with ammonia or with a mono- or converting di-substituted arain to the desired amide and epoxidized.

90982 8/17 02 BAO ORiGINAL

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, for example in the presence of Katriuniamid in liquid ammonia, which. obtained tri-unsaturated compound with the help of a partially inactivated catalyst, for example with the help of a quinoline-deactivated lead / palladium catalyst, "partially. hydrogenated and the product obtained is either subjected to an allyl rearrangement in the presence of an alkanol in an acid medium, or with allyl rearrangement by halogenation in This halogen compound can then be reacted with an alkali metal alkoxide and epoxidized with the aid of a peracid or with N-bromosuccinimide / water. However, the halogen compound obtained can also be reacted with an alkali metal alkanoate and either with the aid of a peracid or epoxidize with N-bromosuccinimide / water and then saponify or first saponify and then epoxidize with the aid of a peracid.The primary alcohol obtained in both cases can then be tetrahydrofuran in the presence of a base, preferably in the presence of sodium hydride in a solvent such as dioxane n, 1,2-dimethoxyethane or in the presence of an alkali metal alkanolate in an alkanol in a temperature range between 0 ° and room temperature with an alkyl halide, for example with ethyl iodide.

909828/1702

18U875.

The starting compound of the formula II or the product formed by reacting a compound of the formula II with a phosphorane of the formula III or a phosphine oxide of the formula IV can be obtained by treatment with an oxidizing agent, preferably by treatment with N-bromosuccinimide / water or with an organic peracid be epoxidized. In addition to N-bromosuccinimide / water, particularly suitable oxidizing agents are, for example, peracetic acid, perbenzoic acid, m-chloroperbenzoic acid or perphthalic acid. The epoxidation is expediently carried out by dissolving the compound in question in an inert solvent, in particular in a halogenated hydrocarbon such as methylene chloride or chloroform, and treating it with a peracid in a temperature range between 0 and room temperature, or in the compound in question in V / ater suspended and. treated with such an amount of an inert solvent, eg dioxane, 1,2-dimethoxyethane Tetrahydrofuran'oder that a homogeneous, concentrated solution is formed, and to this solution in portions at a temperature between 0 ° and room temperature N-bromosuccinimide entering temperature range. The resulting bromohydrin can be converted smoothly into the epoxide by the action of alkalis, in particular by the action of sodium ethylate in ethanol. . The particular advantage of this method is that only the terminal double bond in terpenoid polyenes is oxidized .

909828/1702

BATH ORIGINAL

The process products of formula I are suitable for combating by S.

In addition to most of the previously known pesticides which, as contact or feeding poisons, kill, paralyze or drive away the animals, the compounds of J? Orü; el I which can be prepared according to the invention intervene in the hormonal system of the animal organism a. In insects, for example, the transformation to the image is disturbed. The generation sequence is interrupted and the animals are killed indirectly. For vertebrates, the process products are practically non-toxic. The toxicity of the compounds of the formula Ί in vertebrates is over 1000 mg / kg body weight. The new compounds are also easily broken down. The risk of an accumulation is therefore excluded. The Veralirensprodukte can therefore be used safely to control pests 4HMkMHMBk in IMMMy animals, plants, supplies and textiles.

The products of the process are particularly suitable for combating invertebrates. As will be explained in more detail below, an active ingredient concentration of 0.01 to 0.1% is generally sufficient to ensure the desired effect.

909828/1702

BAD ORIGH ^ t ^: ^ O

The active ingredients can be used, for example, in the form of emulsions, suspensions, dusts, solutions or aerosols. In "special" sections, the objects to be protected, e.g. foodstuffs, seeds, textiles and the like, can also be impregnated directly with the relevant active ingredient or with a solution of the active ingredient. The active ingredient can also be used in a form which only releases the active ingredient through the action of external influences, for example in contact with moisture or only in the animal's body itself. It is also possible to use the process products in a mixture with other known pest control agents.

In the test reports listed below are ' some exemplary embodiments described in more detail.

909828/1702 BATH

Example 1"

39 »2 g of β, 10-diinethyl-undec-9-en-2-one [citronellylacetone] are _{mixed with a solution of 44 f} 8 g of [ethoxycarbonyl-methyl] diethoxy-phosphine oxide in 200 ml of abs. Ethanol mixed, cooled to 0-5 ° C and dropwise with a solution of 4.6 g of sodium in 100 ml of abs. Ethanol added. The mixture is stirred for 2 hours at room temperature, then poured onto Sis and extracted exhaustively with ether. The combined ether extracts are washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. Kp .; · ^- 92-94? 0 / 0.05 üiorr,

20 g ^ »Till

ethyl ester are dissolved in 200 ml of methylene chloride, cooled to 0-5 ⁰ C and gradually added to 16 g of m-chloroperbenzoic acid. The mixture is stirred for 45 minutes at 0 °, shaken twice with 1N hydroxide solution and ice water, then washed neutral with water, dried over sodium sulfate and evaporated. The remaining 10, ll-I2poxy-3,7, ll-trimethyl-dodec-2-cis / tran3-en-lic acid ethyl ester boils at 122-124 ° 0 / 0.1 Torr after rectification.

909828 / T702 ' ßAD ORIGINAL

Example 2

32.8 2 ois / trans 6,10-diraethyr-dodeca-5,9-dien-2-one [geranylacetone E] are mixed with a solution of 33 g of [kethoxycarbonyl-methyl-diethoxy-phosphine oxide in 350 ml of dimethylformamide . The reaction mixture was ^{cooled to 0-1 0} C ', dropwise with a solution of 3, above-mentioned sodium in 38 ml of abs. Of methanol, for 3 hours at 4O ⁰ C overnight, then poured onto 3IS and exhaustively with petroleum ether [low boiling] .. Diever- extracted. The combined extracts are washed neutral with a saturated aqueous solution of sodium chloride, dried over sodium sulfate and evaporated. The remaining cis / trans 3,7,11-trimethyl- >< trideca-2,6,10-trien-1-acid methyl ester is purified by distillation. Ep .: III ° C / 0.2 2orr;

• 20 g cis / trans 3,7, ll-2riiaethyl * -trideca-2,6,10-triene-l ~ acid methyl esters are dissolved in 300 ml of ethylene chloride Chilled 0 ° and gradually with 15.8 g of m-chloroperbenzoic acid offset. The mixture is stirred for 90 hours at 0 °, twice shaken with 1 η sodium hydroxide solution and läiswasser, then with .. water washed neutral, dried over sodium sulfate and evaporated. The remaining cis / trans 10, ll-epoxy-3,7, ll-trimethyl-trideca-2, ö-diene-l-acid methyl ester boils after two Ilekti- " fixation at 107-108 ° C / 0.04 Torr.

909828/1702 BAD ORlOiNAt

Example 5

18.8 g [Aethoxycarboriylnnethylj-diathoxy-phOGphinoxyd consisting be entered .innerhalb 25 'minutes at 2NC-25 ° C into a suspension of a 56.7 i "dispersion of 3i39g Ratriumhydrid in Kineralöl and 120 ml of diethyl ether. As soon as the evolution of hydrogen has come to a standstill, 17.9 g of S, 10 -3 po>: y-6,10-dimethyl-aodec-5-en-2-one in 20 ml of diethyl ether M are added within 30 minutes at 20-25 ° C added dropwise. The reaction mixture is stirred for 2 hours at 20-50 ° C., then poured into water and extracted with ether. The ethereal phase is washed with water, dried over sodium sulfate, filtered and evaporated under reduced pressure. The remaining 10, ll-3poxy-3 »7, ll-irimethyl-trideca-2,6-diene-1-acid ethyl ester is purified by rectification.

. In an analogous way one obtains when using

9, 10-epoxy-6, 10-dimethyl-dodec-S-en - ^ - one or 5 »6; 9,10-diepoxy-S, 10-dimethyl-dodec-2-one

by reacting with [cyano-methylj-diethoxy-phosphinoxide the 10, llrBpoxy-3 _v 7> ll-triniethyl-trideca-2,6-diene-l-nitrile or the 6.7; 10, ll-diepoxy-3, 7,11-trinethyl-tridee-2-en-1-nitrile.

909828/1702

^V - ^r "■" - .V ^Λ ' ^: _ ".' BAD OBIQ (NALV

jit ■ 18U875

Example 4

19 »6 g of 6,10-dimethyl-undec-9-en-2-one [citronellylacetone] together with 35 g of [ethoxycarbonyl-methylJ-triphenylphosphorane and 3 g of benzoic acid in 100 ml of abs. Benzene dissolved. That '. The reaction mixture is heated under reflux conditions for 22 hours while gassing with nitrogen, then evaporated, taken up in 500 ml of 80 tiger kethanol and extracted exhaustively with hexane. The combined extracts are washed with an ice-cold saturated aqueous sodium hydrocarbonate solution and with water, then dried over sodium sulfate and evaporated. The remaining 3,7,12-trimethyl-dodeca-2-cis / trans, 10- dienoic acid ethyl ester is purified by distillation. Zp .: 89-9O ⁰ C / 0.02 Torr. · ■

15 g of 3,7, ll-trimethyl-doaeca-2-cis / trans-lC-diene-l-acid ethyl ester are in 500 ml 0.5 η 50 # aqueous, ethano-. added sodium hydroxide solution and stirred for 5 days at room temperature. The reaction mixture is then diluted with 1000 ml v / water, extracted twice with ether, the aqueous alkaline Solution acidified with 3N hydrochloric acid and exhaustively with tether extracted. The combined extracts are saturated with one aqueous sodium chloride solution washed neutral, dried over sodium sulfate and evaporated. The one left behind 3,7, ll-trimethyl-dodeca-2-cis / trans, 10-diene-l-acidc is made by Purified distillation. Bp ^: 128 ° C / 0.1 Torr.

909828/170 2 BATH

14.8 g of 3,7Al -'- ^L' i " ^ira 3tlayl ~ dodeca-2-cis / tran3,10-d.ien-l-5 acid are mixed with 4.92 g of pyridine and 50 ial of absolute ether and mixed under 9.5 S thionyl chloride is added dropwise to ice cooling. The internal temperature should not rise above 6 ° C. The reaction mixture is then stirred for 50 minutes at 35 ° C. The pesticides which separate out are filtered off and washed with ether. The ether phase is evaporated. The residue is taken up in approx. 100 ml of ether and, while cooling with ice, 21.9 g of diethylamine in 40 ml of ether are added dropwise. After 30 minutes the mixture is poured onto 3is and extracted exhaustively with ether. The combined extracts are washed with a saturated sodium hydrogen carbonate solution, dried over sodium sulfate and evaporated. Any remaining ¹ N, ii-diethyl-3,7, ll-i; rimethyl-dodeca-2-cis / trans, 10-diene-1-acid amide is purified by distillation. Bp. 130 ° O / E, O5 Torr.

16.1 g of K ", IT-diethyl-3> 7, ll-trimethyl-dodeca-2-cis / xrans, 10- λ dien-1-acid amide are dissolved in ISO ml of methylene chloride, cooled to 0 ° and gradually added 11.4 g of m-chloroperbenzoic acid are added. The mixture is stirred at 0 for 1 hour, then ice-cold 1 η sodium hydroxide solution and then with saturated sodium chloride

solution washed, dried over sodium sulfate and evaporated. The remaining 10, H-Bpoxy-IT, K-diethyl-3,7,11-trimethyldodec-2-cis / trans-en-1-acid amide After rectification, it boils at 150 ° C / O, 06 Torr. ^

90 9828/170 2

... 1614875

In an analogous way one obtains when using:

3,7, ll-trimethyl-doaeca-2-cis / trans, 10-diene ~

1-acid, thionyl chloride and ammonia das 3> 7, ll-trimethyl-dodeca-2-cis / trans, 10-d.ien-

■ 1-acid arid urid from this by epoxidizing. 10, ll-epoxy-3 »7,11-trimethyl ~ dodec-2-cis / transene-1-acid amide. Bp. 180 ° C / 0.05 Torr (Kugelrohr dist.)

or when using. ·

β, 10-dimethyl-dodec-9-en-2-one
and subsequent epoxidation

the 10,11-epoxy-N, N-diethyl-3,7ι11-trimethy1-trideca-2-en-l-acid amide.

Example 5

9.6 g of sodium hydride (50 fo in mineral oil) are washed twice with 50 ml of hexane and, after addition of 70 ml of abs. 19.5 g of diethylphosphonoacetamide in 50 ml of dioxane were added dropwise to dioxane at 10-12 ° C. and the mixture was then stirred for 1 γ hours at room temperature. The reaction mixture is cooled to 10-12 and at this temperature ⁰ O tröpfenweise with 19.4 g 6,10-dimethyl-undeca-5-trans-9-dien-2-one (trans-geranyl acetone) was added. After stirring for 20 hours at room temperature, the mixture is carefully mixed with 6 ml of glacial acetic acid while cooling with ice in order to destroy excess sodium hydride, then poured into 500 ml of sodium chloride solution and extracted with ether

.909828 / 1702 BATH

and worked up. By chromatography with hexane-Essigester (1: 1) on silica gel chromatography with high vacuum distillation obtained 3> 7, ll- ^t rimethyl-dodeca -2-cis / trans, trans-6, 10-trien-l-amide (20.6 g) boils after the distillation at 127-129 ° C / 0.001 Torr. The compound can be converted into the lOjll-epoxy ^^ ll-trimethyl-dodeca ^ -cis / trans ^ ö-transdien-1-acid amide by bpoxidation.

In an analogous way one obtains when using: ™

Sodium hydride (50 fo in mineral oil), diethylphosphono-N-isobutyl-acetamide and 6,10-dimethyl-undeca-5-trans-9-dien-2-one

(trans-geranylacetone)
N-isobutyl-3 »7, ll-trimethyl-dodeca-2-cis / trans, 6-trans, 10-triene-1-acid amide; Bp 137-139 ° C / O, 005 torr.

and from this, by epoxidation, the 10, ll-epoxy-N-isobutyl-3,7, ll-trimethyl-dodeca-2-cis / trans , 6-trans-diene-1-acid amide

when using:

Sodium hydride (50 fo in mineral oil), diethylphosphono-N, H-diethylacetamide and 6,10-dimethyl-undeca-5-trans-9-dien-2-one (trans-geranylacetone)

the N, N-diethyl-3,7, ll-trimethyl-dodeca-2-cis / trans, 6-trans, 10-triene-l-acid amide; Bp 115-117 ° G / O, 0.15 torr.

909828/1702 BAD OSf®fN * ÜQ cm

90

and from this by epoxidation, as is carried out in Example 6,

10,11-Bpoxy-H, K-diethyl-3,7,11-trimethyl-dodeca-2-cis / trans, 6-trans-diene-1-acid amide.

9098 2 8/1702 BAD ORIGINAL

·. 18U875

Example 6

To 7.3 g of the obtained according to Example 5 li _t N-diethyl-3 * 7, lltrimethyl-2-cis / trans, trans-6, 10-dodecatrien-l-acid amide, s in 50 ml of tetrahydrofuran and 10 ml of distilled V / ater be at 0-5 ⁰ C portionwise 4.7 g of N-bromosuccinimide was added and then stirred for 6 hours at this temperature. The reaction mixture is then poured into a saturated sodium chloride solution, extracted with hexane and worked up. Chromatography with hexane-ethyl acetate (1: 1) on silica gel gives pure Ν, N-diethyl-10-bromo-II-hydroxy-J, 7, II-trimethyl-2-cis / trans, 6-trans-dodecadiene-1 acid amide obtained.

2.22 g of this compound are in 3 parts abs. Registered methanol, dissolved at 0-3 ° C dropwise with a solution of 131 mg of sodium and dissolved in 3 ml of abs. Methanol added. The mixture is stirred for γ hours, poured onto 250 ml of saturated sodium chloride solution, extracted with hexane and worked up. The 10, ll-epoxy-W, N-diethyl-3,7, ll-trimethyl-2-cis / trans purified by distillation , 6-trans-dodecadien-1-acid amide boils at 140 C / 0.015 Torr.

2-Β / 17ΧΓ2

In an analogous way one obtains when using:

- 6,10-dimethyl-undeca-5-cis-9-dien-2-one (cis-geranylacetone) the corresponding 2-cis / trans, 6-cis-amides and

from this via the 2-cis / trans, 6-cis-bromohydrin compounds the 10, ll-epoxy-3 »7, ll-trimethyl-2-cis / trans, 6-cis-"

dodecadiene-1-acid amide,,.

the 10, ll-Bpoxy-N-isobutyl-3,7, ll-trimethyl-2-cis / trans,

ö-cis-dodecadiene-l-acid amide and 10,11-epoxy-N, N-diethyl-3,7,11-trimethyl-2-cis / trans, ö-cis-dodecadiene-1-acid amide; Bp. 140-145 ° C / O.OO5 Torr (Kugelrohrdest.)

n ^ ° = 1.4924

or when using :

6, lO-Dimethyl-dodeca-5 , 9-dien-2-one das lOjll-Epoxy ^^ ll-trimethyl-trideca ^ ö-dien-

1-acid amide,
the 10, ll-epoxy-N-isobutyl-3,7,11-trimethyl-trideca-

2,6-diene-l-acid amide and
the lO ^ l-epoxy-NjN-diethyl - ^^ fll 2,6-diene-l-acid amide.

909828/170 2

"**" ■ 18U875

Example 7

In a homogeneous solution of 4.86 g of 6, 10-i> imethyl-undeca-5-trans-9-dien-2-one (trans geranylacetone), 10 ml of dist. Water and 50 ml of tetrahydrofuran are added in portions at 5 ° C. 4.7 g of N-bromosuccinimide. The reaction mixture is stirred for a further 3 hours at 5 ° C. and then for 19 hours at room temperature, poured into a saturated sodium chloride solution, extracted with hexane and worked up. Chromatography with hexane-ethyl acetate (1: 1) on silica gel gives 2.8 g of pure trans-9-bromo-10-hydroxy-6,10-dimethyl-5-undecen-2-one; Bp 104-107 ° C / 0.001 Torr (dec.) Nj " ⁰ = 1.5000

In a solution of 50.9 g of trans-g-bromo-10-hydroxy-öjlO-dimethyl-5-undecen-2-one in 87.5 ml of aos. Methanol is a solution of 4.03 g of sodium in 87.5 ml of abs within 45 minutes at 0-3 ° C. Added dropwise methanol. The reaction mixture is stirred for a further 30 minutes, then poured into 1000 ml of a 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), purified by distillation, boils at 79-80 ° C / 0.08 Torr; n ^ ⁰ = 1.4638.

5f47 g of sodium hydride (50 μS in mineral oil) are added twice with 50 ml of abs. Washed hexane and after adding 30 ml of abs. Dioxane at 10-12 ⁰ C dropwise with 11.2 g of diethylphosphono-

909828/1702

acetamide in 3O ml abs .- ^ ioxane (dissolved hot) added. The reaction mixture is stirred L4 hours at room temperature and then at 10-12 ⁰ O lo-dimethy1-5-undecene-2-one was treated dropwise with 12 g of trans-9,10-Spoxy-6, were added. The mixture is stirred for 20 hours at room temperature, while being cooled with ice, 5 ml of abs. Ethanol added to destroy the excess sodium hydride, poured into a saturated saline solution, extracted with ether and worked up. The lC, ll-epoxy-3,7, ll ~ 't ^r i ^me ' t ⁿ yl-2-cis / transjö-trans-dodecadiene-1-acid amide (11 g) boils at 155 ° C / 0.005 torr.

In an analogous manner, if sodium hydride is used (50 fo in mineral oil),
Diethylphosphono-N-isobutyl-acetamide and trans-9, 10-epoxy-6,10-dimethyl-5-undecen-2-one des 10, ll-epoxy-N-isobutyl-3,7,11-trimethyl-2- cis / trans, 6-trans-dodecadiene-1-acid amide; Bp 162 ° C / 0.01 torr.

when using

Sodium hydride (50 % in mineral oil),
Diethylphosphono-NjN-diethyl-acetamide and trans-9> 10-epoxy-6,10-dimethyl-5-undecen-2-one aas 10,11-epoxy-N, N-diethyl-3,7,11-trimethy1- 2-cis / trans, 6-trans-dodecadiene-i-acid amide; Bp 140 ° C / O.O15 torr.

909828/1702

when using

6,10-dimethyl-undeca-5-cis-9-dien-2-one

(cis-geranylacetone)
via cis-9> 10-epoxy-6,10-dimethyl-5-undecen-2-one

(cis-geranylacetone epoxide) 10, ll-epoxy-3,7, ll-trimeth.yl ~ 2-cis / trans,

ö-cis-dodecadiene-l-acid amide, the lO, ll-epoxy-] üi-isobutyl-3> 7, ll-ti ^< iniethyl-2-cis / trans,

o-cis-dodecadiene-l-acid amide and the lOjll-epoxy-NjK-diethyl ^^ Al-trimethyl-2-cis / trans, 6-cis-dodecadiene-l-sa.ureamide

or when using

6, lO-dimethyl-dodeca-5,9-dien-2-one · 9 »l ° - ^B POxy-6,10-dimethyl-5-dodecen-2-on-the lOjll Bpoxy-j ^ fll-trimethyl -trideca-a ^ -

diene-1-acid amide, |

the lDjU-B

deca ~ 2,6-diene-1-acid amide and the lCllT-epoxy-N ^ -diethyl-SfVfll deca-2,6-diene-l-acid arid.

909828/1702

■ Κ ■■■

■ Example 8

73.7 g of 6,10-dimethyl-undeca-5-trans-9-dien-2-one [geranylacetone] and 86.3 g [ethoxycarbonylnnethylJ-dietoxy-phosphine oxide are dissolved in 360 ml of abs, ethanol, to 0-5 ⁰ C- cooled, dropwise with a solution of 8.75 g of sodium in 190 ml of abs. Ethanol added, stirred for 2 hours at room temperature, then poured onto Sis and extracted exhaustively with ether. The combined extracts are washed neutral with a saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. The remaining ⁷ S _f 7 ₁ ll-trimethyl-dodeca - ^ - cis ( 22 #) / bgn (18Si), 6 ~ trans, 10-triene-1-acid ethyl ester is purified by distillation. Kp .: 125-126 ⁰ C / 0,4.Sorr. The compound can be converted into the 10, ll-Bpoxy-3,7, ll-trimethyl-dodeca-2-cis ( 22 ^ ) / trans ( 78 % ) _t 6-trans-diene-1-acid ethyl ester by epoxidation. '

In an analogous manner, one obtains with use; of 6, 10-dimethyl-undeca-5,9-dien-2-one by reaction with [Oyano-methylj-diethoxyphosphinoxyd and subsequent epoxidation 10, ll-epoxy-3,7,11-trimethyl-dodeca-2,6-dienl-nitrile bssw.

6.7 f 10, ll-diepoxy-3 »7» ll-trimethyl-dodec-2-en-1-nitrile.

90982 8/170 2
BATH ORIGINAL

Example 9

19.2 g of sodium hydride (50? O in mineral oil) are washed twice with 100 ml of hexane, after adding 200 ml of abs. Tetrahydrofuran was ^{cooled to 0-10 0} G and 44.8 g of [ethoxycarbonyl-methylj-diethoxy-phosphine oxide were added dropwise. The mixture is stirred for Iy hours at room temperature, gradually mixed with 38.8 g ^, lO-dimethyl-indeca-S-trans-S-dien-2-one (trans-G-eranylacetone) at 5-15 °, Stirred for 20 hours at room temperature and then carefully with 30 ml abs. Ethanol added to destroy the excess of lithium hydride. The reaction solution is then poured into 2000 ml of saturated sodium chloride solution, extracted with ether, washed, dried and evaporated. The remaining 3,7,11-trimethyl-dodeca-2-ois ( 30? O ytrans ( 70 ° ^C. ). 6-trans, 10-trien-ethyl ester boils after the distillation at il5-117 ° C./0.02 Torr. , Yield 68 fe _t ^ Ie compound can be obtained by epoxidation in the 10, ll-i.poxy-3,7, ll-trimethyl-dodeca-2-cis (£ 30) / trans (70 <$>) b-trans- diene-1-acid ethyl ester are converted.

In an analogous way, by converting trans— Geranylacetone with various phosphine oxides of the general formula

^{2 2 5}

RO
0

909828/1702

18U875

in tetrahydrofuran in the presence of sodium hydride, the 3,7,11-trimethyl-dodeca-2-cis / trans, 6-trans, 10-triene-1-acid ethyl ester or the lOjll epoxy - ^^ ll-trimethyl-dodeca - ^ - cis / trans ^ - trans-diene-l'-acid ethyl ester with the following 2-cis / trans-composition.

H Phenyl ice cream trans Yield of 2-cis /
trans mix 2-chloro-p'henyl 40 60 75 # 2-3? Luoro-phenyl 42 58 60 f> 2-bromo-phenyl 44 56 · 65 ft 2-methoxyphenyl 44 56 64 1o 2,4-dichloro-phenyl 32 68 69 Io 4-nitro-phenyl "45 55. 73 io 3-Mtro-phenyl 46 54 59 io 2,6-dichloro-phenyl 4.4 36 65 io 26th 74 .30 i *

^ i ₆ preferred solvents are tetrahydrofuran , dioxane and 1,2-dimethoxyethane.

9 0 9 8 2 8/17 0 2

■ - 18U875

Example IQ

45 g of 3> 7, ll-trimethyl-dodeca-2-cis / trans, 6-trans, 10-trien-1-acid ethyl ester are added in 1500 ml of 0.5 η 50 consecutive aqueous, ethanolic sodium hydroxide solution for 48 hours Stirred at 50 ° C. The reaction mixture is then diluted with 3000 ml of water, extracted twice with ether, the aqueous alkaline solution is acidified with 2N hydrochloric acid while cooling with ice and extracted exhaustively with% ether. The combined extracts are washed neutral with a saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. The 5,7,11-trimethyl-dodeca-a-cis / trans, 6-trans, 10-trienoic acid that remains is purified by distillation. B.p .: 129-130 ° C / 0.1 torr.

33, 8 g 3t 7, ll-trimethyl-dodeca-2-cis / trans, 6-trans, IQ-trien-1-oic acid are with 11.4 g of pyridine and 120 ml of abs. Aether is mixed and 23.8 g of thionyl chloride are added dropwise while cooling with ice. The internal temperature should not ^{rise above 6 0} O during this process. The reaction mixture is then heated to 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 again in about 250 ml of abs. Aether added, and while cooling with ice dropwise with 50 g of diethylamine in about 100 ml of abs. Aether displaced. The solution is filtered blank after 1 hour and; washed successively with cold 2η-hydrochloric acid, with a saturated, aqueous sodium chloride solution, then

90 9828 / Ί702

18U875

dried over sodium sulfate and evaporated IT, N-diethyl-317, II-trimethyl-dodeca-2 ~ cis / trans, 6-trans, 10-triene-1-acid amide is purified by distillation, boiling point: 125? C / O, O5 Torr.

15 g of "N, IT-diethyl-3» 7 »ll-trimethyl-dQdeca-2-cis / trans, 6-trans, 10-triene-l-acid amide are dissolved in 150 ml of methylene chloride, cooled to 0 ° and gradually after 23.8 g of m-chloroperbenzoic acid are added. The mixture is stirred for 1 hour at 0 °, then poured into ice-cold 1 η sodium hydroxide solution and extracted exhaustively with methylene chloride. The extract is washed with 1 η sodium hydroxide solution and saturated sodium chloride solution , and evaporated dried over sodium sulfate. The residual 6,7 f10,11-diepoxy-N, N-diethyl-3, 7, ll-trimethyl-6, 7-trans-dodec 2 ~ cis / trans-en-l ~ Acid amide boils at 159 ° C / 0 _r 15 after rectification

In an analogous manner, if '6', 10 ~ bi & ethyl-dodeca-5 _> 9-dien-2-one is used, the 10jll-epoxy ^ N-diethyl ^^ rll-trimethyl is obtained

2 _r 6- ⁱ "diene-acid amide or
the 6 _r 7; ^; 10, ll-Dlepoxy-Ii ^

trid ^: ec- ⁱ 2-en-l-säu! reamid.

7D2

Example 11

Cis-geranylacetone is used in a manner known per se Sodium acetylide condensed in liquid ammonia. The resulting cis-dehydro-nerolide oil is then partially to hydrogenated cis-nerolidol.

300 g of 3,7, ll-trimethyl-dodeca-l, 6-cis, 10 - trien-3-ol [cis-Nerolidol] will ml with 810 ml of petroleum ether [boiling range 40-45 ⁰ C] and 31 »5 pyridine mixed and at -5 to 0 G added dropwise within 2 hours with 159 g of phosphorus tribromide in 180 ml of petroleum ether [boiling range 40-45 ° C.]. The reaction mixture is stirred for a ^{further 30 minutes at -5 to 0} ° C., then poured onto ice and, after a further 30 minutes, 1500 ml of ether are added. The Petroläther- / ether phase is separated, washed successively with V / ater and λ with a saturated aqueous sodium bicarbonate solution, dried over sodium sulfate evaporated and initially at 30 G under reduced pressure, then under high vacuum. The crude l-bromo-3,7 »ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene that remains can be used as follows without further purification

A) to 1-ethoxy-3,7, ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-trien or

B) to the l-acetoxy ^^ ill-trimethyl-dodeca ^ -cis / trans, 6-cis, 10-trien

further processed v / earth.

909828/1702

* ι

. 18U875

A) 350 Q l-bromo-3,7, ll ~ 't ^ i ^m ethyl-dodeca-2-cis / trans, 6-cis, ■ 10-triene are converted into a solution of 32 g of sodium in 640 ml with ice cooling Section. A.ethanol dripped in. The internal temperature should not exceed 20 G. The reaction mixture is then stirred for 16 hours at room temperature, heated for 1 hour under reflux conditions at the boiling point, then cooled, poured onto ice and exhaustively extracted with petroleum ether [boiling range 40-45 ⁰ Cj. The combined extracts are washed neutral, dried over sodium sulfate and evaporated. The remaining l-ethoxy-3,7, ll-trimethyl-dodeca-2-cis / trans> 6 ~ cis, 10-triene is purified by distillation. Kp.:95-97°c/O,l

B) 363 g of l-3rom-3 »7, ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-tr.ien are refluxed together with 208 g of anhydrous potassium acetate in 2400 ml of acetone for 24 hours. The potassium bromide which precipitates out on cooling is filtered off. The filtrate is evaporated. The residual 1-acetoxy-3, l _f ll-trimethyl-dodeca ^ -cis / Transjö-cis, 10-triene (226 g) boiling after distillation at 116-119 ° C / O.O3 Torr.

The l-ethoxy-3 »7, ll-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene mixture can be converted into

1-Aathoxy-3,7, II-trimethyl-dodeca-2-cis, 6-cis, 10-triene and l-ethoxy-3,7, ll-trimethyl-dcdeca-2-trans, 6-cis, 10-triene

909828/1702 BADORfGINAi.

the l-acetoxy-3,7, ll-trimethyl-dodeca ~ 2-cis / trans, 6-cis, 10-triene

l-acetoxy-3,7, ll-trimethyl-dodeca-2-cis, 6-cis, 10-triene and l-acetoxy-3,7,11-trirae thyl-dodeca-2-trans, 6-cis, 10-triene separated, and into the corresponding

2-cis, 6-cis- or 2-trans, 6-cis-10-, II-epoxy-farnesyl ethyl ether, 2-cis, 6-cis- or 2-trans, -6-cis-10, II-epoxy-farnesyl acetate and ^ 2-cis, 6-cis- or 2-trans, 6-cis ~ 10, ll-3poxy-farnesol compounds be transferred.

5.4 g of 1-ethoxy-3.7 _t ll-trimethyl-dodeca-2-trans, 6-cis, 10-triene in 100 ml of methylene chloride are cooled to -0 °, and 4 »4 g of m-chloroperbenoic acid are added in portions , Stirred for 1 g hours at Ü, then washed successively with 1 IT sodium hydroxide solution and water, dried over sodium sulfate and evaporated. The remaining 10, ll-Bpox3 / -l-ethoxy-5,7, ll-trimethyl-dodeca-2-trans, 6-cis-diene is separated from portions of the corresponding 6,7-epoxy compound by fractional distillation. 94 ° C / O, O5 torr. ■

The l-ethoxy-3,7, ll-trimethyl-dodeca-2-trans, 6-cis, 10-triene can also be converted into the corresponding with the help of N-bromosuccinimide 10,11-Bpoxyverbindungen are converted.

909828/1702 BATH

18H875

Example 12

In a homogeneous solution of 26.4 g of l-Acetoxy-3.7.11 "" triraethyl-dodeca ^ -cis / trans ^ o-ciöjlO-trien, 715 ml tetrahydrofuran and 200 ml of water at 0-3 ° C within 30 minutes 19, o g of N-bromosuccinimide entered in portions. The mixture is stirred for 5 hours, then poured into a saturated saline solution, extracted with hexane and worked up. By chromatography with hexane -15 ^ ether on silica gel are 22.5 g pure 10-bromo-ll ~ hydroxy ~ l-acetoxy ~ 3,7, ll-trimethyl-dodeca-2-cis / trans, 6-cis-diene obtain.

In a solution of 20.7 g of 10-Brora-11-hydroxy-1-acetoxy-3,7, ll-trimethyl-dodeca-2-cis / trans, 6-cis-diene in 60 ml of abs. Methanol is a solution of 2.64 g of sodium dissolved in 60 ml of abs at 0-3 ° C. for 30 minutes. Added dropwise methanol. The mixture is stirred for 30 minutes at 2 ⁰ O 2 and I / 4 hours at room temperature, poured into .a Hatriumchloridlösung, extracted with hexane, worked up and distilled. There are 12.8 g Xy ^, 7 Al- /

S °

^ Bp 99-101 C / 0.001 Torri, obtained.

C ₀ The same compound can also be used starting from 1-Acetoxycn ♦

ο 3 »7, U-trimethyl-dodeca-2-cis / trans, 6-cis, 10-triene through. Bpoxidize with a peracid to 10, ll-3poxy-l-acetoxy-3 »7, lltrimethyl-dodeca ^ -cis / trans ^ -cis-diene, which is then saponified to the desired primary alcohol, are produced,

BAD ORIOlNAL

3 (T

Example 15

2.4 g of sodium hydride ($ 50 in mineral oil) are washed twice with 20 ml of hexane, after adding 50 ml of abs. Dioxane cooled to 10-12 ⁰ C and treated dropwise with 11.9 g of 10,11-epoxy-3,7, ll-trimethyl-dodeca-2-cis / trans, cis-6-dien-l-ol was added. The mixture is stirred for a further 2 hours at room temperature, cooled to approx. 10-15 ° C, 8 g of ethyl iodide are added dropwise, stirred for 16 hours at room temperature, then poured into a saturated saline solution, extracted with hexane and worked up. Chromatography with hexane / 15 ° ethyl acetate on silica gel and subsequent distillation gives 10.5 g of pure a 10, ll-epoxy-1-ethoxy-3,7,11-trimethyl-dodeca-2-cis / trans, 6-cis diene received..Sdp. 93 ° C / O, 0.5 torr .; n ^ ° = 1.4710. '

If in example 13 the ethyl iodide is replaced by 9 g propyl iodide, in an analogous way, 10jll-Spoxy-1-propoxy- | is obtained

3,7, ll-trimethyl-dodeca-2-cis / trans, 6-cis-diene; n ^ ⁰ - 1.4703.

In an analogous manner, starting from - trans-geranylacetone via trans-nerolidol is obtained the l-bromo-3,7,11-trimethyl-dodecarS-cis / trans, 6-trans, 10-triene,

by treating with sodium ethylate or potassium acetate in _t

909828/1 702

18H87S

the l-ethoxy-3,7,11-trimethyl-dodeca ^ -cis / trans,

e-trans, 10-trien or
l-acetozy-5,7, ll-tri2iethyl-dodeca-2-cis / trans, 6-trans, 10-triene

can be transferred. These two compounds can optionally after separation of the 2-cis / trans mixtures through Rectification by treatment with peracids or by terminal oxidation with N-bromosuccinimide

10,11-epoxy-1-ethoxy-3,7,11-trimethy1-dodeca-2-cis / trans, 6-trans-diene
or to

the 10, ll-epoxy-1-acetoxy-3,7,11-trimethyl-dodeca- 2-cis / trans, 6-trans-diene

eiDOxydiert, then to the 10 , ll-epoxy-3,7,11-trimethyl-dodeca-2-cis / trans, ö-trans-dien-l-ol

hydrolyzed and with sodium hydride and ethyl iodide to the 10, ll-Bpoxy-l-ethoxy-5,7,11-trimethyl-dodeca-2-cis / trans, 6-trans-diene

etherified xierden.

909828/1702

In an analogous manner, starting from

6, 10-dimethyl-dodeca-5,9-dien-2-one

the 3,7, ll ~ trimethyl-trideea-l, 6,10-trien-3-ol and from this the lO, ll-Spoxy-trimeth3'-l-trideca-2,6-dien-l-ol or the lOjll-Epoxy-l-methoxy-fbzw. 1-ethoxy) -3,7,11-tri-

methyl-trideca-2,6-diene and
the ojTflOjll-Diepoxy-1-methoxy-ibzw, 1-ethoxy) -3 »7» 11-trimethyl-tridec-2-en

909828/1702

18H875

The experiments described in the examples below were carried out with the following representative representatives carried out according to the invention producible compound class.

A = 10, II-epoxy-N, N-diethyl-; 3,7, II-trimethyl-dodec-2-cis / trans-en-1-acid amide

B = 6.7; 10, ll-diepoxy-N, N ~ diethyl-3,7, ll-trimethyl-. 6,7-trans-dodec-2-cis / trans-en ~ l-acid amide,

Example 14

Iollstöff discs [diameter 50 mm] are soaked with an acetone active ingredient solution and each populated with 10 larvae of the lider duvet [Tir.cola biselliella]. The larvae, which are not exposed to the dead, develop to. Saupers that pupate undisturbed and then form butterflies. The larvae exposed to treated tfoil discs are disturbed in their formation and pupation.

mg active ingredient number number number 5 "rassrate

per V / ol disc -. . "bende keu.-". Palter in ^

R & xxnen tur.gen

A. 10
• ι H 10
1 control 0

1 14 6

9 23 5 60

22 107 0 0

14 13. 1 70

17 9 80 i

The clothes moth [Tineola biselliella] are sprayed with an aqueous suspension of the active substance, and the hatching rate of the cows is determined. ..

Concentration of active substances, hatching rate in Ji

in <fo

% A

0.01. _β 17

control 0. 95

909828/1702 ^ BADORtQlNAL

18H875

• ^ example 16 . · ■

V / ell cardboard strips [20 χ 50 mm] v / ground with oiner acetone Soaked in the active ingredient solution and treated with larvae of the Apfelvicklers [Carpocapsa pomonella] occupied. The on imbehandelterr. Larvae exposed to carton crawl into the hollows of the wall carton, spin themselves and release after 14 days Palter. The larvae exposed on treated cardboard are disturbed in their main formation and pupation.

ng active substance number of caterpillars and pupae number of palter per box - normal dead normal crippled stripes

10. 1 0 8 1 1 - 0 2-6 0

Control 0 0 0 15

Example 17

Colorado beetle [Leptinotarsa aecemlineata] beer v / ground sprayed with a 1 ^ strength acetone solution.

Active ingredient. Hatch rate in ? *

A "0

Control 100

909828/1702
BAO

^ Eisräel 18 '. ■

Young Colorado beetles [leptinotarsa deceinlineeta] are sprayed with an aqueous suspension of the active ingredient and

fed with potato pie. 2s the number of eggs laid by treated and untreated animals and the number of eggs hatched from the eggs are determined,

Active substance consensus number of your number of hatched

tration ixi% ■ th oilers · - -

^A 0.25 9 x. .- '■; 4 ·

^B 0.25 .. 87 ■. 68. '·'

Control 0 376 368.

. "Example 19

100 g egg grains each are mixed with an acetone liquid solution soaked, getrocicaet and with 100 grain beetles [Galandra granariaj infected. The beetles are sieved after 14 '.

■ ·

and watched 6 cook. The 'tan beetles filled with untreated grains reproduce normally. Pie with K (Jr-- nevn- fed beetles show clear developmental disorders.

908828 / 1.702

BAD ORlGlNAU ^ ^ ^; -

mg A. Active ingredient per
Ig wheat • 'B
Zone control OUl 5
ο,
O 3 ''

Multiplication factor

0.1 0.15

3.2 0.1

6.2

Example 20

Attrorj.diles of French beans with sars and " little yams" of the spider-tree [Tetrsnychus urticae] are sprayed with an acetone solution. After 4 mafias the mortality of the animals is determined, and after 7 accounts the anti-cidal effect is determined.

IControlls 0

Active ingredient concentration Mortality of the Eggs in % Animals , 100 0.1 100 100 0.01 100 30th 0.001 50 100 . 0.1 100 40 0.01 60 ' 0 0.01 30th

909828/1702

BATH O.

Example 21

Bean juniper plants become heavily rait aphids [iieorayzus circuniflexus] and infected with an acetonic active substance solution sprayed. After 2 days, the mortality of the lice is

Active ingredient concentration in % mortality

_A 0.1 100

ö _s oil ■ 48

"'· M · ⁶ 4

^B , Ο "16

Control 0. 5

Example 22

• Chew fly larvae [Musca donesticaj on one of ÜZLeie, milk powder, yeast and the Viirkstoff existing genic set. The larvae pupate and release according to some legends, the flies. Larvae that act on virkstof free ^ i Kediua · have been exposed, develop normally and show no disturbance in oviposition. Larvae on active ingredient haltigeia Kediuci have an increased mortality.

90 9828/1702 BAD ORKSINAt

• 18H875 HH

mg of active ingredient per hatching rate of oviposition

cml larval food in %

A '5 0 0

0.05 20 ■ 0

Control 0 ■ 78 46

909828/1 702 SAO ORIGINAL

Claims (27)

Patent claims 1. Process for the preparation of epoxy compounds of general formula CKlO in which R is hydrogen or lower alkyl, X is one of the groups -COOR ₁ ', -00Έ \ ^ά or -CH ₂ OR in which R ^ denotes hydrogen, lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R ¹ , lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R ₂ and R- individually hydrogen or lower · \ Alkyl 'or together with the nitrogen atom a 5- or 6-piece drigen heterocyclic radical, which is another ■ Heteroatom oxygen, nitrogen or sulfur it may contain represent and A and B individually what-ο ^ hydrogen or together denote a carbon-carbon bond or an oxygen bridge, where, if at the same time R is hydrogen and A and B σ> together mean a carbon-carbon bond R ^ and R'χ an alkyl group with at least 2 carbon atoms, phenyl or optionally lower alkyl represents substituted aminoalkyl, characterized in that a compound of the general formula in which R has the meaning given above and A ¹ and B ¹ individually denote hydrogen or together denote a carbon-carbon bond,
with a phosphorane of the general formula or with a phosphine oxide of the general formula in which X ^{1 is} one of the groups ; -COOR ¹ _χ or -CONt °> denotes in which R ¹ , lower alkyl, phenyl σ, or optionally lower alkyl-substituted ο - Aminoalkyl, R ₂ and R, individually hydrogen or lower alkyl, or together with the nitrogen atom a 5- or 6- III IV "" * "18U875 membered heterocyclic radical, which can contain oxygen, nitrogen or sulfur as a further heteroatom, R ^, R ₁ - and Rg are aryl or dialkylamino, and R ₇ and R _{3 are} aryl, alkoxy or aryloxy, converts, if an alkoxycarbonyl group is present converted into an aminocarbonyl group and the resulting product ™ transferred to an epoxy, or that a compound of the general formula II in a Epoxy transferred, and reacted with a phosphine oxide of the general formula IV, or that mam brings a compound of the formula II with acetylene into reaction , the obtained. Product partially hydrogenated and corresponds, either in the presence of subjecting an alkanol and an acid an allylic rearrangement or transferred under Allylumiagerung in a primary halide and 'either reacted with a Alkalimetallalkanölat and transferred to the product obtained in a Spoxyd, or reacted with an alkali metal alkanoate and the resulting The product is converted into an epoxide in any order and hydrolyzed and then the primary alcohol obtained is reacted with an alkyl halide, and a compound of the formula I, in which X denotes an alkoxycarbonyl group, is saponified if desired 909828/1702
BATH ORIGINAL 18U875 2. The method according to claim 1, characterized in that one gitronellylacetone with an alkoxycarbonyl-phosphorane of the formula III or phosphine oxide of the formula IV is reacted, the ester obtained saponified, halogenated, with ammonia or with a mono- or dialkylamine, preferably treated with diethylamine and converted into an epoxy. 3. The method according to claim 1, characterized in that Oitronellylaceton with diethylphosphono-N, N-diethyl ~ Reacts acetamide and the N, N-diethyl acid amide obtained in transferred to an epoxy. 4. The method according to claim 1, characterized in that geranylacetone is reacted with an alkoxycarbonyl-phosphorane of the formula III or -phosphine oxide of the formula IV, the ester obtained saponified, halogenated, with ammonia or with a mono- or di-alkylamine, preferably with Treated diethylamine and converted into an epoxy. 5. The method according to claim 1, characterized in that geranylacetone is reacted with diethylphosphono-NjN-diethyl-acetamide and the Ν, Ν-diethyl acid amide obtained is converted into an epoxide . 909828/1702 ORIGINAL BATHROOM 6. The method according to claim 1, characterized in that geranylacetone is reacted with acetylene and partially hydrogenated, the nerolidol obtained is halogenated with an alkali metal alkoxide treated and converted into an epoxy. 7. "The method according to claim 1, characterized in that that geranylacetone is reacted with acetylene and partially hydrogenated, the nerolidol obtained is halogenated with an alkali metal. · ' alkanoate, preferably treated with potassium acetate in acetone, the compound obtained is converted into an epoxide, the epoxy acetate hydrolyzed and the alcohol obtained in the presence of a base, preferably in the presence of sodium hydride in. an inert. Solvent, preferably in dioxane, with an alkyl halide implements. 909828/1702 . 18H875 8. Process for the manufacture of pesticides, characterized in that one or more epoxy compounds of the general formula in which R is hydrogen or lower alkyl, X is one of the groups _C == | T; -GOOR ₁ ; -CONx ² or -CH ₂ OR · _χ R ₅ denotes in which R-, hydrogen, lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R ¹ -, lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R »and R, individually hydrogen or lower alkyl or together with the nitrogen atom a 5- or 6-membered heterocyclic radical, which can contain oxygen, nitrogen or sulfur as a further heteroatom, and A and B individually denote hydrogen or together denote a carbon-carbon bond or an oxygen bridge, where, if at the same time R denotes hydrogen and A and B together denote a Carbon-carbon bond mean, R, and R'χ an alkyl group with at least 2 carbon atoms! Is phenyl or optionally lower alkyl substituted aminoalkyl, 3Q9828 / 1FQ2 18H875 as active constituents inert, suitable for the control of pests, customary in such compositions per se adds to solid or liquid carriers. 9. The method according to claim 8, characterized in that 10, ll-Bpoxy-N, lf-diet 1-3,7, ll-trimethyl-dodec-2-cis / trans-en-1-acid amide as active ingredient used. 10. The method according to claim 8, characterized in that "that one 6,7; 10, ll-Diepoxy ~ N, N-diethyl-3,7, ll-trimethyl-6,7-trans-dodec-2-cis / trans-en-l-acid m ^ .id used as an effective ingredient. 909828/1702 11. Pesticides, characterized in that that there is one or more epoxy compounds of general formula in which R is hydrogen or lower alkyl, X is one of the groups -CsN; -GOOR ₁ ; -CONf * or -CH denotes in which R, 'denotes hydrogen, lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R' lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, Rp and R- individually hydrogen or lower alkyl or together with the nitrogen atom a 5- or 6- membered heterocyclic radical, which may contain oxygen, nitrogen or sulfur as a further heteroatom, and A and B individually denote hydrogen or together a carbon-carbon bond or an oxygen bridge, where, if at the same time R 'is hydrogen and A and B together are carbon -Carbon bond, R, and R ¹ - ^ is an alkyl group with at least 2 carbon atoms, phenyl or optionally lower alkyl-substituted aminoalkyl, contains 909828/1702 BAD ORIGINAL 12. Pesticide according to claim 11, characterized in that it is the active substance ΙΟ, ΙΙ-Εροχγ-Η, Ν-diethyl-3 » 7, ll-trimethyl-dodec-2 ~ cis / trans-en-1-acid amide contains. 13. Pesticide according to claim 11, characterized in that it is 6.7 »10,11-diepoxy-N, N-diethyl-3,7,11-trimethyl-6,7-trans-dodec-2-cis as the active substance / trans-en-1-acid amide contains. 909828/1702
BATH • 18H875 14. Use of epoxy compounds of the general formula R. ■ 0 ^ 10 AI 2 in which R is hydrogen or lower alkyl, X is one of the groups -C = N; -COOR ₁ ; -CON; * or -CHgOR ^ denotes in which ^ ₁ denotes hydrogen, lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R 'lower alkyl, phenyl or optionally lower alkyl-substituted aminoalkyl, R "and R, individually hydrogen or lower alkyl or together with the nitrogen atom a 3- or 6-membered one heterocyclic radical, which can contain oxygen, nitrogen or sulfur as a further hetero atom, and A and B individually denote hydrogen or together a carbon-carbon bond or an oxygen bridge, where, when R is simultaneously hydrogen and A and B together a carbon-carbon -Bond, R ^ and R ^ represent an alkyl group with at least 2 carbon atoms, phenyl or optionally lower alkyl-substituted aminoalkyl, as pesticides. 909828/1702 18U875 15. Use of 10, ll-epoxy-N, N ^ iäthyl-3,7, ll-trimethyl-dodec-2-cis / trans-en-1-acid amide for the purpose specified in claim 14. 16. Use of 6,7; 10,1-diepoxy-N _f _N-diethyl-3 »7» lltrimethyl-6,7-trans-dodec-2-cis / trans-en-1-acid amide for the one in claim 14 stated purpose. 90 98 28/1702 17. Epoxy compounds of the general formula 0 ^ 10 in which R is hydrogen or lower alkyl, X is one of the groups -C = N; -COOR ₁ ; -GON ^ ² or -CHgOR ^ denotes in which R, hydrogen, lower alkyl, phenyl or optionally lower alkyl substituted Aminoalkyl, R 'lower alkyl, phenyl or optionally lower alkyl substituted Aminoalkyl, Rp and R_ individually hydrogen or lower alkyl or together with the nitrogen atom a 5- or 6-membered heterocyclic. A radical which can contain oxygen, nitrogen or sulfur as a further heteroatom and A and B individually or together denote a carbon-carbon bond or an oxygen bridge, if simultaneously R is hydrogen and A and B together represent a carbon-carbon bond, R, and R ^ a Alkyl group with at least 2 carbon atoms, phenyl or optionally lower alkyl-substituted Represents aminoalkyl. 909828/1 702 18U875 18. 10,11-epoxy-3,7,11-trimethyl-dodee-2-cis / trans-en-ethyl ester. ' 19.10, ll-Spoxy-3,7,11-trimethyl-tridec-2,6-diene-oleic acid methyl ester. · 20. lO, ll-epoxy-3,7, ll-trimethyl-tridec-2,6-diene-l- ■ ethyl acid ester, . ··. ■ '■ · ι 21. 10, U-Spoxy-3,7,11-trimethyl-dodec-2-cis / trans-.en'-1-acid amide. -. · 22. 10. II-Epoxy ~ N, 3J-diethyl-3, 7, II-triethyl-dodec-2-cisZ-trans-en-1-acid amide. 23. 10, ll-Spoxy-3,7,11-trimethyl ~ 2-cis / trans, 6-trarisdodeca-diene-1-acid amide, 24. 10, ll-Spoxy ~ U-isobutyl-3,7,11-trimethyl-2-cis / trans, e-trans-dodeca-diene-l-säurearaid. 25. 10,11-Bpoxy-N, li-dia
b-trans-dodecadiene-l-acid amide. 26. 10, ll-Epoxy-I, li-diethyl-3,7,11-trimethyl-2-cis / trans, • S-cis-dodeca-diene-l-acid amide. 909828/1702 18U875 27. ö ^ jlOjll-Di dodec-2-cis / trans-en ~ l-acid amide 909828/1702