DE3424328A1 - METHOD FOR THE PRODUCTION OF 3,11-DI- (METHYL) -NONAKOSAN-2-ON AND 2,10-DI- (METHYL) -OCTAKOSANIC ACID ALKYLESTER AND METHOD FOR THE PRODUCTION OF THE LATTER - Google Patents

Abstract

The invention relates to a process for the preparation of 3,11-di- (methyl) -nonakosan-2-one of the formula in which a) 2,10-di- (methyl) -octakosansäurealkylester of the general formula II with trialkylsilylmethyllithiums to form intermediates of the general formula IIIa are reacted and these intermediates are reacted with aliphatic alcohols or b) 2,10-di- (methyl) -octakosansäurealkylester of the general formula II in solvents of the ether type with a solution of methylsulfinyl methide in dimethyl sulfoxide to the intermediates of the general formulas IIIb are reacted and this is treated with reducing agents and the 3,11-di- (methyl) -nonkosan-2-one of the formula I obtained in this way is isolated from the reaction mixture. The invention also relates to the new intermediate products 2,10-di- (methyl) -octakosansäurealkylester of the general formula II for carrying out this process and a process for preparing these intermediates.

Description

(Cover sheet)

The invention relates to a new process for the production of 3,11-di- (methyl) -nonakosan-2-one as well as 2,10-di- (methyl) -octakosansäurealkylester which are new intermediates and a process for the production of the latter.

As is known, the 3,11-di- (methyl) -nonakosan-2-one exercises the formula I.

has an attractive effect on the male individuals of the German cockroaches (Blatta Germanica), which are annoying parasites, that is to say that it is the sex pheromone of this insect and is therefore suitable for trapping these insects in pheromone traps.

The sex pheromone of the German cockroach (Blatta Germanica) was derived from the sexually mature females of Nishida and co-workers (R. Nishida, H. Futami and S. Ishii: Experientia 30 [1974], 978; Appl. Ent. Zool. 10 [1975]) , 10; R. Nishida, T. Sato, Y. Kuwahara, H. Futami and S. Ishii: J. Chem. Ecol., 2 [1976], 449; Agr. Biol. Chem., 40 [1976], 1 407) isolated. It was found that the sex pheromone extract has 2 components, namely the 3,11-di- (methyl) -nonakosan-2-one of the formula I and the 29- (hydroxy) -3,11-di- (methyl) -nonakosan-2-one 2-one of the formula XII,

contains. The two compounds cause a characteristic sex pheromone reaction in male individuals of the German cockroach, with 29- (hydroxy) -3,11-di- (methyl) -nonakosan-2-one of the formula XII exerting a stronger effect. (K. Mori, T. Suguro and S. Masuda: Tetrahedron 37 [1981], 1,329). The 4 possible optical isomers of the two pheromones were synthesized. The natural substances correspond to a (3S, 11S) configuration. The sexual attractiveness of the 4 optical isomers is almost the same.

The 3,11-di- (methyl) -nonakosan-2-one of the formula I was developed by Nishida and coworkers (R. Nishida, H. Fukami and S. Ishii: Appl. Entomol. Zool. 10 [1975], 10) synthesized from acetoacetic ester. According to this process, an anion is formed from acetoacetate and sodium ethylate, which anion is reacted with 1,6-di- (bromo) -hexane to form 2- [6 '- (bromo) -hexyl] -3- [oxo] -butyric acid ethyl ester. This compound is hydrolyzed with an aqueous hydrogen bromide solution and decarboxylated by heating. The 1- (bromine) -8- (oxo) -nonane obtained in this way is reacted with octadecylene-triphenyl-phosphorane and the 1- (bromine) -8- (methyl) -hexakos-8-ene obtained with the from 2- ( Methyl) acetate acetic ester and potassium tert-butoxide converted anion. The 2,10-di- (methyl) -2- (acetyl) -octakos-11-enoic acid ethyl ester obtained in this way is hydrolyzed with an acid, and the carboxylic acid obtained is 2,10-di- (methyl) -2- (acetyl) -octakos -11-enoic acid decarboxylated and the 3,11-di- (methyl) -2- (oxo) -nonakos-11-ene obtained by catalytic hydrogenation into the pheromone compound 3,11-di- (methyl) -nonakosan-2-one of formula I converted.

According to Schwarz and co-workers (M. Schwarz, JE Oliver, PE Sonnet: J. Org. Chem. 40 [1975], 2 410), the 3,11-di- (methyl) -nonakosan-2-one of the formula I is eliminated Hexane-1,6-diol produced as a starting material. This is first converted into 6- (chloro) -hexan-1-ol and then into the corresponding tetrahydropyranyl ether, which is reacted with sodium iodide and sodium cyanide in dimethyl sulfoxide. The 7- (tetrahydropyranyloxy) -heptanoic acid nitrile thus obtained is reduced with lithium diethoxyaluminum hydride and the 7- (tetrahydropyranyloxy) -heptanal obtained is reacted with [1- (methyl) -nonadecylidene] - [triphenyl] -phosphorane. The 8- (methyl) -hexakos-7-en-1- (yl-tetrahydropyranyl) -ether obtained in this way is catalytically hydrogenated and the 8- (methyl) -hexakosan-1- (yl-tetrahydropyranyl) -ether which is formed is reacted with triphenylphosphine dibromide . With the 8- (methyl) -hexakosanylbromide thus obtained, the anion formed from [2- (oxo) -butylidene] - [triphenyl] -phosphorane and butyllithium is alkylated and the resulting [3,11-di- (methyl) -2- (oxo) -nonacosylidene] - [triphenyl] -phosphorane is converted into the 3,11-di- (methyl) -nonakosan-2-one of the formula I by alkaline hydrolysis.

Following the procedure of Burgstahler and co-workers

(AW Burgstahler, LO Weigel, WJ Bell and MK Rust: J. Org. Chem. 40 [1975], 3 456) is the pheromone 3,11-di- (methyl) -nonacosan-2-one of the formula I from small Epsilon-Caprolactam produced as a raw material. The small epsilon-caprolactam is treated with hydrogen bromide and sulfuric acid and the 6- (bromo) -hexanoic acid formed is esterified. The ethyl 6- (bromo) -hexanoate obtained in this way is reacted with the anion formed from acetoacetate and sodium ethylate, whereupon the ethyl 7- (ethoxycarbonyl) -8- (oxo) -nonanoate obtained is hydrolyzed with an acid and the carboxylic acid obtained 7- (carboxy) -8- (oxo) -nonanoic acid is decarboxylated regarding its 7-carboxy group by heating. The 8- (oxo) -nonanoic acid thus obtained is esterified and the 8- (oxo) -nonanoic acid methyl ester obtained is reacted with octadecylidene-triphenyl-phosphorane. The methyl 8- (methyl) -hexakos-8-enoate obtained in this reaction is catalytically hydrogenated and the methyl 8- (methyl) -hexakosanoate obtained is reduced with lithium aluminum hydride. The 8- (methyl) -hexakosan-1-ol obtained is reacted with hydrogen bromide and the 8- (methyl) -hexakosanylbromide obtained is treated with the anion formed from methylmalonic acid diethyl ester. The 2- (ethoxycarbonyl) -2,10-di- (methyl) -octakosanäthylester is hydrolyzed with an acid, the carboxylic acid 2- (carboxy) -2,10-di- (methyl) -octakosansäure regarding its 2-carboxy group decarboxylated and the 2,10-di (methyl) octacosanoic acid obtained is converted into the desired pheromone 3,11-di (methyl) nonacosan-2-one of the formula I by reaction with methyl lithium.

According to the procedure of Rosenblum and coworkers (LD Rosenblum, RJ Anderson and CA Henrick: Tetrahedron Letters 1976, 419) the 3,11-di- (methyl) -nonakosan-2-one of the formula I is made from the phenyl ester of thiononadecanoic acid as starting material manufactured. 6- (Chlor) -hexanol is masked with ethyl vinyl ether and then treated with an alkyllithium and copper (I) iodide. The cuprate reagent thus obtained is reacted with a thiononadecanoic acid ester and the 7- (oxo) -pentakosan-1-ol thus obtained, protected by a 1- (ethoxyethyl) group, is treated with a phosphorane obtained from a methyl triphenylphosphonium salt. The 7- (methylene) -pentakosan-1-ol thus obtained protected by a 1- (ethoxyethyl) group is catalytically hydrogenated and the 7- (methyl) -pentakosan-1- obtained protected by a 1- (ethoxyethyl) group ol converted into 7- (methyl) -pentakosan-1-ol by acid treatment. The latter compound is reacted with methanesulfonyl chloride (mesyl chloride) and the methanesulfonylate (mesylate) obtained is treated with lithium bromide. The 7- (methyl) pentakosanyl bromide obtained is in the presence of dilithium copper tetrachloride with 3 - {[1 '- (ethoxy) ethoxy] prepared from 1- (hydroxy) -2- (methyl) -butan-3-one in 2 stages. -2- [methyl] -butyl} -lithium reacted, whereupon the 2- [1 '- (ethoxy) ethoxy] -3,11-di- [methyl] nonacosane obtained is treated with an acid. The 2- (hydroxy) -3,11-di- (methyl) -nonacosan obtained in this way is converted into the pheromone 3,11-di- (methyl) -nonakosan-2-one of the formula I by oxidation with chromic acid.

According to the method of Place and coworkers (P. Place, ML Ronmestant, J. Gore: Tetrahedron 34 [1978], 1931) the 3,11-di- (methyl) -nonakosan-2-one of the formula I is produced from vinylallenes . Methyl vinyl ketone is reacted with acetylene and the 3- (hydroxy) -3- (methyl) -pent-1-en-4-yne obtained is treated with hydrochloric acid. From the 1- (chloro) -3- (methyl) -pent-2-en-4-yne obtained, the corresponding magnesium (vinyl) - (methyl) -allen is formed with ether with magnesium. This compound is reacted with acrolein, the alcoholic hydroxyl group of the 4- (ethynyl) -4- (methyl) -3- (hydroxy) -hexa-1,5-diene obtained is and the protected derivative obtained is alkylated with hexadecanyl bromide at -30 ° C. The 4- (vinyl) -3- (hydroxy) -4- (methyl) -dokos-1-en-5-yne obtained in this way is heated to boiling in diglyme and converted into 6- (methyl ) -tetrakos-5-en-7-in-1-al converted. This aldehyde is alkylated with an alkyl lithium which was prepared by opening the hydrochloric acid ring of the small alpha-acetyl-small gamma-butyrolactone, protecting the carbonyl group and reacting the 4- (ethylenedioxo) -3-methyl-1-chloropentanes with butyl lithium . The hydroxyl group of the 3,11-di- (methyl) -2- (ethylenedioxo) -6- (hydroxy) -nonakos-10-en-12-ines obtained in this way is reduced by reduction of the methylsulfonylated with zinc in dimethoxyethane in the presence of sodium iodide (mesylated) derivative removed. The 2- (ethylenedioxo) -3,11-di- (methyl) -nonakos-10-en-12-yne thus obtained is catalytically hydrogenated and finally the acetal protective group is removed by acidic treatment.

According to the method of Seidel and Schäfer (W. Seidel, HJ Schäfer: Chem. Ber. 113 [1980], 451), the pheromone component 3,11-di- (methyl) -nonakosan-2-one is produced with the aid of key electrochemical steps . The starting material used is 2-butyl-butyl ester, which is reacted with octadecylmagnesium bromide in the presence of copper (I) chloride. The 3- (methyl) -henicosanoic acid sec-butyl ester obtained in this way is hydrolyzed with an alkali to give 3- (methyl) -henicosanoic acid, whereupon this is subjected to coelectrolysis with 5,5-di- (methoxy) -valeric acid. The 6- (methyl) -tetracosanoic acid methyl ester obtained is hydrolyzed with a base to give 6- (methyl) -tetracosanoic acid. This is converted into the desired 3,11-di- (methyl) -nonakosan-2-one of the formula I by coelectrolysis with 5- (methyl) -6- (oxo) -heptanoic acid.

{The 5- (methyl) -6- (oxo) -heptanoic acid was obtained by alkylating methyl acetoacetate with ethyl 4- (bromine) -butyrate to give ethyl 5- (methyl) -5- (carbethoxy) -6- (oxo) -heptanoic acid and the following Hydrolysis and decarboxylation affecting the 5-carboxyl group.}

Mori and coworkers (K. Mori. S. Masuda, T. Suguro: Tetrahedron Letters 1978, 3 447; Tetrahedron 37 [1981], 1 329) succeeded in the stereocontrolled synthesis of each of the 4 stereoisomers of the sex pheromone components 3,11-Di - (methyl) -nonakosan-2-one of the formula I or 29- (hydroxy) -3,11-di- (methyl) -nonakosan-2-one of the formula XI. The key step of this synthesis consists in the implementation of a chiral p-toluenesulfonate {tosylate} [in the case of the pheromone 3,11-di- (methyl) -nonakosan-2-one of the formula I of 5R- or 5S- (methyl) -trikosanyl -p-toluenesulfonates and in the case of the pheromone 29- (hydroxy) -3,11-di- (methyl) -nonakosan-2-one of the formula XII of 5R- or 5S- (methyl) -23- (benzyloxy) -tricosine -8-yl-p-toluenesulfonates] with the Grignard reagent formed from 4R- or 4S- (methyl) -hex-5-enyl bromide in the presence of dilithium copper tetrachloride. The anti-Markovnyikov hydration of the terminal double bond of the 4 stereoisomeric 3,11-di- (methyl) -nonacosenes is then carried out by treatment with mercury (II) acetate and subsequent removal of the mercury with sodium borohydride. The secondary alcohol obtained is converted into the desired 3,11-di- (methyl) -nonakosan-2-one of the formula I by oxidation with chromium (VI) oxide.

The 5R- (methyl) -trikosanyl-p-toluenesulfonate used as starting material in the production of the pheromone 3,11-di- (methyl) -nonakosan-2-one of the formula I is produced as follows: R - (+) - citronellic acid is made with lithium aluminum miniumhydrid reduced to R - (+) - citronellol, the p-toluenesulfonate of which is reacted with sodium iodide in acetone. The R - (+) - citronellyl iodide obtained in this way is converted into 5R, 10-di- (methyl) -dec-9-enoic acid by a malonic acid synthesis, which with lithium aluminum hydride to the corresponding alcohol 5S, 10-di- (methyl) -dec -9-en-1-ol is reduced. This is acetylated, the 5S-10-di- (methyl) -dec-9-enyl acetate obtained is oxidized with m-chloroperbenzoic acid to give the corresponding epoxide and the epoxide obtained is cleaved with periodic acid. The 7- (formyl) -5S- (methyl) -heptyl acetate obtained is reacted with triphenyl-pentadecenyl-phosphorane in a Wittig reaction. The olefin obtained is catalytically hydrogenated and the 5R- (methyl) -tricosanol obtained is p-toluenesulfonated.

To produce the antipode p-toluenesulfonate 5S- (methyl) -trikosanyl-p-toluenesulfonate, hexadec-1-yne is alkylated with R - (-) - citronellyl iodide. The 2,6S- (methyl) -tetrakos-2-en-9-yne thus obtained is oxidized with m-chloroperbenzoic acid and periodic acid in the manner described for the preparation of the other antipode. The 4S- (methyl) -dokos-7-ynal obtained is reduced with lithium aluminum hydride to the corresponding alcohol 4S- (methyl) -dokos-7-ynol, from which first the corresponding p-toluenesulfonate and then with potassium cyanide the corresponding nitrile 4S- ( Methyl) -dokos-7-incarboxonitrile is formed. This is subjected to an alkaline hydrolysis, the resulting carboxylic acid 4S- (methyl) -dokos-7-incarboxylic acid or, in other words, 5S- (methyl) -trikos-8-yn acid is reduced and finally catalytically hydrogenated. The desired 5S- (methyl) -tricosanol obtained is converted into the p-toluenesulfonate in a manner known per se.

The other component of the synthesis, the 4R- (methyl) -hex-5-enylbromide, is prepared as follows: 3R, 7-di- (methyl) -6,7- (epoxy) -hept-1-en is made with superiodic acid split, the resulting aldehyde 4R- (methyl) -hex-5-enal is reduced with a metal hydride and the resulting 4R- (methyl) -hex-5-enol is first converted into p-toluenesulfonate and then reacted in acetone with lithium bromide. To produce the antipode 4S- (methyl) -hex-5-enylbromide, methyl 7- (phenyl) -4R- (methyl) -hexanecarboxylate is oxidized with chromium (VI) oxide. The 4S- (methyl) -6- (bromo) -hexanoic acid methyl ester is produced from the silver salt of the dicarboxylic acid half ester obtained in a Hunsdiecker reaction. This is reacted with o-nitro-seleno-phenol, whereupon the selenyl group is removed in an oxidative manner. The methyl 4S- (methyl) -hex-5-enoate obtained is reduced with lithium aluminum hydride and the 4S- (methyl) -hex-5-enol obtained is converted into the desired 4S- (methyl) -hex via the p-toluenesulfonate as above -5-enyl bromide transferred.

Both in the case of the 3,11-di- (methyl) -nonakosan-2-one of the formula I and in the case of the 29- (hydroxy) -3,11-di- (methyl) -nonakosan-2-one of the formula XI, the synthesized compounds with (3S, 11S) configuration are identical to naturally occurring substances. However, no significant difference was found by the authors in the biological activity of the various stereoisomers.

The above known processes for preparing the 3,11-di- (methyl) -nonakosan-2-one of the formula I, however, have the disadvantages of the high expenditure associated with the preparation of the starting materials and the large number of reaction stages.

The invention is based on the object, while eliminating the disadvantages of the prior art, a process for the preparation of 3,11-di- (methyl) -nonakosan-2-one of the formula I, which starting from more easily accessible and easier to prepare starting materials and simpler and is to be carried out with fewer reaction steps, as well as to create new intermediates for its implementation and its production.

The above has surprisingly been achieved by the invention.

It was found, surprisingly, that the 3,11-di- (methyl) -nonakosan-2-one from the new 2,10-di- (methyl) -octakosansäurealkylester of the general formula II,

wherein

R represents an alkyl radical with 1 to 5 carbon atom (s),

can be produced more easily and with fewer steps than by the known processes.

The invention therefore relates to a process for the preparation of 3,11-di- (methyl) -nonakosan-2-one of the formula I,

which is characterized in that

a) 2,10-Di- (methyl) -octakosansäurealkylester of the general formula II,

wherein

R represents an alkyl radical with 1 to 5 carbon atom (s), in solvents of the ether type with trialkylsilylmethyllithiums

to intermediate products 1- (trialkylsilyl) -3,11-di- (methyl) -

-nonakosan-2-one of the general formula IIIa,

wherein

R [deep] 1, R [deep] 2

and R [deep 3 is an alkyl radical with 1 to 4 each

Mean carbon atom (s),

are implemented and these intermediates with

aliphatic alcohols with 1 to 4 carbon atom (s)

implemented or

b) 2,10-Di- (methyl) -octakosansäurealkylester of the general formula II, wherein

R is set as above,

in solvents of the ether type with a solution of methyl

sulfinyl methide in dimethyl sulfoxide to the intermediate products

Sodium salts of 1- (methylsulfinylmethyl) -2,10-di- (methyl) -

-octacosanoic acid alkyl ester or

1- (methylsulfinylmethyl) -3,11-di- (methyl) -nonkosan-2-one

of the (general) formulas IIIb,

wherein

R is set as above,

are implemented and this is treated with reducing agents and the 3,11-di- (methyl) -nonakosan-2-one of the formula I obtained in this way is isolated from the reaction mixture in a manner known per se.

The alkyl radical (s) with 1 to 5 or 1 to 4 carbon atom (s) for which R or R [deep] 1, R [deep] 2 and R [deep] 3 can or can, can or can be straight-chain or branched. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl radicals.

In both of the variants a) and b) of the above process according to the invention, it is not necessary to use the intermediates 1- (trialkylsilyl) -3,11-di- (methyl) -nonakosan-2-ones of the general formula IIIa or sodium salts of 1- Isolate (methylsulfinylmethyl) -2,10-di- (methyl) -octakosansäurealkylester or 1- (methylsulfinylmethyl) -3,11-di- (methyl) -nonakosan-2-one of the formula IIIb.

Rather, it is more favorable to react them further in the reaction mixture without isolation with the aliphatic alcohols or reducing agents.

The trialkylsilylmethyllithiums used as starting materials in variant a) of the above process according to the invention can have been prepared by reacting trialkylsilylmethyl halides with metallic lithium. In this variant a) of the above process according to the invention, the trialkylsilylmethyllithium used is advantageously trimethylsilylmethyllithium.

In variant a) of the above process according to the invention, the reaction of the alkyl 2,10-di- (methyl) -octakosansäurealkylester of the general formula II with the trialkylsilylmethyllithiums is expediently carried out with cooling.

Preferably, in variant a) of the above invention According to the process, the aliphatic alcohol used is one having 1 or 2 carbon atom (s), in particular methanol.

The methylsulfinyl methide (with another name dimsyl sodium) used as starting substance in variant b) of the process according to the invention has the formula and is contained, for example, in the book "The rule of the Hungarian chemical nomenclature and orthography", Akademieverlag, Budapest, 1972.

In variant b) of the above process according to the invention, aluminum amalgam is preferably used as the reducing agent. This can have been produced from aluminum and mercury (II) chloride in a manner known per se.

The methylsulfinyl methide used as starting substance in variant b) of the above process according to the invention can have been prepared from dimethyl sulfoxide with strong bases, expediently sodium hydride, at temperatures below 70.degree.

Isolation of the 3,11-di- (methyl) -nonakosan-2-one of the formula I obtained according to one of the variants a) and b) of the above process according to the invention from the reaction mixture can be carried out by means of known procedures, such as distillation and / or chromatography, be performed.

The 2,10-di- (methyl) -octakosansäurealkylester of the general formula II used as starting materials in the above process according to the invention are new compounds not described in the literature. You can choose from the easily accessible commercial product undec-10-enoic acid of the formula IV

getting produced.

These new intermediate products 2,10-di- (methyl) -octakosansäurealkylester of the general formula II open a new way by a chemically unique process for the production of the end product 3,11-di- (methyl) -nonakosan-2-one of the formula I that is technically advanced.

The invention therefore also relates to alkyl 2,10-di (methyl) octacosanoate of the general formula II, wherein

R represents an alkyl radical with 1 to 5 carbon atom (s).

The invention also relates to a process for the preparation of these 2,10-di- (methyl) -octakosansäurealkylester of the general formula II according to the invention, which is characterized in that

A) a) Undec-10-enoic acid of the formula IV

initially in the presence of a palladium salt as

Catalyst with hydrogen peroxide to 10- (oxo) -undecanoic acid

oxidized and this to a 10- (oxo) -undecanoic acid alkyl ester

the general formula

V,

wherein

R is set as above,

is esterified or

b) Undec-10-enoic acid of the formula IV first esterified to give an alkyl undec-10-enoate

and this in the presence of a palladium salt as

Catalyst with hydrogen peroxide to 10- (Oxo) -undecan-

acid alkyl esters of the general formula V,

wherein

R is set as above,

is oxidized,

as well as according to one of the above variants a) or b)

obtained 10- (oxo) -undecanoic acid alkyl esters of the general

Formula V with a phosphorane, which is derived from the phospho-

nium salt [octadecyl] - [tri- (phenyl)] - phosphonium halide

the general formula

VI,

wherein

X halogen means

has been made with a strong base for

corresponding 10- (methyl) -octakos-10-enoic acid alkyl ester

the general formula VII,

wherein

R is set as above,

is implemented, this by catalytic reduction in the corresponding 10- (methyl) -oktakosansäurealkylester

the general formula VIII,

wherein

R is set as above,

is transferred, this is hydrolyzed, the obtained

Carboxylic acid 10- (methyl) octacosanoic acid with a strong

Base is converted into a dianion, the dianion formed with

Methyl iodide is methylated and finally the resultant

Carboxylic acid 2,10-di (methyl) octacosanoic acid is esterified

or

B) from undec-10-enoic acid of the formula

IV

formed a dianion with a strong base and this with

Methyl iodide to form 2- (methyl) -undec-10-enoic acid of the formula IXa

is methylated

as

a) this 2- (methyl) -undec-10-enoic acid initially to one

2- (Methyl) -undec-10-enoic acid alkyl ester of the general formula IXb, esterified and this in the presence of a palladium salt

with hydrogen peroxide to the corresponding 2- (methyl) -

-10- (oxo) -undecanoic acid alkyl esters of the general formula X,

wherein

R is set as above,

is oxidized or

b) said 2- (methyl) -undec-10-enoic acid initially in

Presence of a palladium salt with hydrogen peroxide

oxidized to 2- (methyl) -10- (oxo) -undecanoic acid and this

to a 2- (methyl) -10- (oxo) -undecanoic acid alkyl ester of

general formula

X,

wherein

R is set as above,

is esterified

as well as that obtained according to one of the above variants a) or b)

2- (Methyl) -10- (oxo) -undecanoic acid alkyl esters of the general formula X

with a phosphorane, which is made from a phosphonium salt

[Octadecyl] - [tri- (phenyl)] - phosphonium halide of the general

formula VI, in which

X halogen means

has been made with a strong base, to the corresponding

2,10-Di- (methyl) -octakos-10-enoic acid alkyl ester of the general

formula XI,

wherein

R is set as above,

implemented and this is reduced catalytically.

In the last-mentioned process according to the invention, preference is given to the oxidation of the undec-10-enoic acid of the formula IV [variant A) a)] or the undec-10-enoic acid alkyl ester [variant A) b)] or the 2- (methyl) -undec -10-en-acid alkyl ester [variant B) a)] or 2- (methyl) -undec-10-enoic acid [variant B) b)] is used as the palladium salt palladium acetate.

It is also preferred in the last-mentioned process according to the invention to use methylsulfinyl methide as the strong base with which the phosphorane has been prepared from the phosphonium salt {[octadecyl] - [tri- (phenyl)] - phosphonium} halide of the general formula VI.

Furthermore, it is preferred in the last-mentioned process according to the invention the catalytic reduction of the 10- (methyl) -octakos-10-enoate of the general formula VII [variant A)] or of the 2,10-di- (methyl) -octakos-10-enoate of the general formula X [variant B)] to be carried out in the presence of a palladium / carbon catalyst.

It is also preferred in the last-mentioned process according to the invention to use an alkyllithium as the strong base for converting 10- (methyl) octacosanoic acid [variant A)] or undec-10-enoic acid of the formula IV [variant B)] into a dianion.

The invention is explained in more detail using the following example.

example

3,11-di (methyl) nonakosan-2-one

(Formula I)

It is made by adding 2.0 g (16 millimoles) of trimethylsilylmethyl chloride to a mixture of 0.05 g (8 millimoles) of lithium in 25 ml of anhydrous ether in an argon atmosphere, then heating the mixture to boiling for 4 hours and then cooling the Solution obtained at 0 ° C solution a solution of 1.5 g

(3.2 millimoles) 2,10-di- (methyl) -octacosanoic acid methyl ester (formula II) with R = methyl radical in 5 ml of anhydrous ether was added dropwise. The mixture is stirred or shaken for 4 hours at 0 ° C., whereupon 5 ml of methanol are added with cooling and the mixture is stirred or shaken for a further 2 hours. The reaction mixture is poured into ice-cold water and extracted with ether and the ethereal solution is washed with water and a saturated sodium chloride solution, dried over magnesium sulfate and evaporated. The residue is purified by column chromatography. So 0.75 g of 3,11-di- (methyl) -nonakosan-2-one is obtained in the form of an oil. Yield 52% of theory.

IR / film /: 1715 / CO /, 1460, 1450, 1380, 1220, 1170 cm [high] -1.

[high] 1H NMR / CDCl [low] 3 /: 0.84 / 3H, t, J = 7Hz, CH [low] 3 /, 1.03 / 3H, d, J = 6Hz, CH [low] 3 /, 1.15-1.9 / 49H, m, 24 CH [deep] 2, CH /, 2.02 / 3H, s, CH [deep] 3CO /, 2.3 / 1H, m, CH /.

The methyl 2,10-di- (methyl) -octakosansäuremethylester used as starting material was prepared by one of the following two procedures.

Procedure A)

a) 10- (oxo) -undecanoic acid (formula V with H instead of R)

1.0 g of palladium chloride and 1.0 g of crystalline copper / II / chloride are dissolved in a mixture of 50 ml of purified dimethylformamide and 7.5 ml of water, whereupon the solution is heated to 100 ° C. in an oxygen atmosphere. The introduction of the oxygen flow is continued and the solution, which is stirred at 100 ° C., becomes inside

A solution of 9.0 g / 0.049 mol / undec-10-enoic acid and 10 ml of purified dimethylformamide were added dropwise over 2 hours. The reaction mixture is stirred for a further 3 hours at 100 ° C. while passing in oxygen, cooled and poured into water. The mixture is extracted four times with a total of 200 ml of ether, the combined ethereal solutions are washed with water, dried and the solvent is distilled off. The yellow crystalline residue is recrystallized from n-hexane. 4.4 g of the compound mentioned in the title are obtained, yield 45%. Yellow crystals.

F .: 57-59 ° C / according to the literature: 58-60 ° C R.E. Bowman, J. Chem. Soc. 1950, 322 /.

IR / KBr /: 1720, 1705 / CO /, 1460, 1440, 1420, 1360, 1280, 1240, 1205, 1140 cm [high] -1.

[high] 1H NMR / CDCl [low] 3 /: 1.35 / 12H, m, 6 CH [low] 2 /, 2.14 / 3H, s, CH [low] 3 /, 2.35 / 4H , br q, 2CH [deep] 2 /, 9.5 / 1H, br s, COOH /.

Ms: M [high] + 200/1 /, m / z 182/2 /, 125/8 /, 97/8 /, 71/13 /, 57/53 /, 54/36 /, 44/100 /.

b) 10- (Oxo) -undecanoic acid methyl ester (Formula V with R = CH [deep] 3)

I) 10.0 g / 0.05 mol / 10- (oxo) -undecanoic acid (formula V with H instead of R) are added to an ethereal solution of 3 g / 0.07 mol / diazomethane at 0 ° C. with stirring, whereupon the solution is stirred for half an hour at 0 ° C. The solvent is distilled off and the residue is subjected to vacuum distillation. 9.3 g of the compound mentioned in the title are obtained in the form of a colorless liquid, yield 87%.

Boiling point: 158-160 ° C / 1.3 kPa [10 mm Hg] (according to literature:

133-135 ° C / 0.26 kPa [2 mm Hg]; A. Citterio and E. Vismara, Synthesis 1980, 751).

IR / film /: 1730, 1715 / CO /, 1460, 1430, 1360, 1230, 1150 cm [high] -1.

[high] 1H NMR / CCl [low] 4 /: 1.3 / 12H, m, 6 CH [low] 2 /, 2.05 / 3H, s, CH [low] 3 /, 2.25 / 4H , br q, 2 CH [deep] 2 /, 3.58 / 3H, s, OCH [deep] 3 /.

Ms: M [high] + 214/11 /, m / z 183/28 /, 157/47 /, 125/85 /, 97/38 /, 87/29 /, 83/26 /, 74/29 /, 58/73 /, 55/100 /, 41/91 /.

II) 0.5 ml of sulfuric acid is added to a solution of 13.5 g of 10- (oxo) -undecanoic acid in 100 ml of anhydrous methanol and the solution is heated to the boil for 4 hours. The solvent is distilled off under reduced pressure, the residue is taken up in 100 ml of ether, the ethereal solution is washed with water and dried over anhydrous magnesium sulfate. The solvent is distilled off and the residue is subjected to vacuum distillation. 12.0 g of a substance identical to the product prepared according to Section I) are obtained, yield 83%.

c) {[Octadecyl] - [tri- (phenyl)] - phosphonium} bromide

(Formula VI with X = Br)

10.0 g / 0.03 mol / stearyl bromide and 8.0 g / 0.03 mol / triphenylphosphine are dissolved in 20 ml of anhydrous benzene and the solution is refluxed for 48 hours. The solvent is distilled off, the residue is triturated with 20 ml of anhydrous ether, the crystalline substance is filtered off and washed with anhydrous ether. 14.06 g of the compound mentioned in the title are obtained in the form of a white crystalline substance, yield 79%.

[high] 1H NMR / CDCl [low] 3 /: 0.85 / 3H, t, J = 6Hz, CH [low] 3 / 1.28 / 32H, m, 16 CH [low] 2 / 3.6 / 2H, m, CH [deep] 2 / 7.75 / 9H, m, arom. Pr./, 8.0 / 6H, m, arom. Pr./.

d) 10- (methyl) -octakos-10-enoic acid methyl ester

(Formula VII with R = CH [deep] 3)

0.8 g / 0.033 mol / sodium hydride is added to 20 ml of anhydrous dimethyl sulfoxide, whereupon the mixture is stirred in an argon atmosphere at 70 ° C. for one hour. The solution is cooled to room temperature, whereupon a solution of 16.0 g / 0.027 mol / [octadecyl] - [tri- (phenyl)] - phosphonium bromide (formula VI with X = Br) in 80 ml of anhydrous dimethyl sulfoxide is added dropwise with vigorous stirring will. The reaction mixture is stirred for half an hour at 40-50 ° C., cooled to room temperature and a solution of 4.5 g / 0.021 mol / 10- (oxo) -undecanoic acid methyl ester [formula V with R = CH [deep] 3 ] in 10 ml of anhydrous dimethyl sulfoxide was added with vigorous stirring. The reaction mixture is stirred vigorously for 8 hours at room temperature. After adding 30 ml of distilled water, the mixture is extracted three times with a total of 300 ml of n-hexane. The n-hexane extract is washed with water and a saturated sodium chloride solution, dried over magnesium sulfate and evaporated. The residue is taken up in 20 ml of n-hexane, the precipitated product is filtered, the solvent is distilled off and the residue is purified by column chromatography / silica gel 60; Benzene-methanol in a volume ratio of 10: 0.2 /. 4.44 g of the compound mentioned in the title are obtained in the form of a colorless oil, yield 47%. According to liquid chromatography, the product consists of a mixture of the E and Z isomers in a weight ratio of 3: 2.

IR / film /: 1740 / CO /, 1460, 1440, 1380, 1360, 1220, 1180, 1160, 1090, 1020 cm [high] -1.

[high] 1H-NMR / CCl [low] 4 /: 0.9 / 3H, t, J = 6Hz, CH [low] 3 /, 1.26 / 42H, m, 21 CH [low] 2 /, 1 , 55 / 3H, m, CH [deep] 3 /, 1.8-2.4 / 6H, m, 3 CH [deep] 2 /, 3.55 / 3H, s, OCH [deep] 3 /, 5 , 0 / 1H, br t, J = 6Hz, C = CH /.

Ms: M [high] + 450/31 /, m / z 419/3 /, 418/8 /, 300/3 /, 295/10 /, 294/40 /, 279/13 /, 213/16 /, 212/18 /, 197/27 /, 180/31 /, 165/16 /, 157/51 /, 125/32 /, 111/30 /, 97/59 /, 85/22 /, 82/25 /, 81/35 /, 71/34 /, 69/83 /, 68/25 /, 58/80 /, 57/51 /, 56/100 /, 43/66 /.

e) 10- (methyl) -octacosanoic acid methyl ester

(Formula VIII with R = CH [deep] 3)

4.0 g of 10- (methyl) -octakos-10-enoic acid methyl ester (formula VII with R = CH [deep] 3) are hydrogenated in 200 ml of methanol in the presence of a palladium / carbon catalyst. After the theoretical amount of hydrogen has been taken up / about 210 ml, 4 hours / the catalyst is filtered off, washed with methanol, the organic phases are combined and the solvent is distilled off. The oily residue solidifies in the form of a gel. 3.85 g of the compound mentioned in the title are obtained, yield 96.3%.

IR / KBr /: 1740 / CO /, 1460, 1440, 1380, 1360, 1240, 1150 cm [high] -1.

[high] 1H-NMR / CDCl [low] 3 /: 0.88 / 3H, t, J = 7Hz, CH [low] 3 /, 1.3 / 52H, m, 24 CH [low] 2, CH [ deep] 3, CH /, 2.2 / 2H, t, J = 7Hz, CH [deep] 2 / 3.68 / 3H, s, OCH [deep] 3 /.

Ms: M [high] + 452/100 /, m / z 421/3 /, 409/5 /, 199/8 /, 172/5 /, 167/6 /, 143/19 /, 129/82 /, 111/6 /, 37/41 /, 83/20 /, 75/33 /, 74/55 /, 71/23 /, 69/27 /, 57/47 /. f) 10- (methyl) octacosanoic acid (formula VIII with H instead of R)

3.0 g of 10- (methyl) -octakosansäuremethylester (formula VIII with R = CH [deep] 3) are dissolved in a mixture of 30 ml of methanol and 15 ml of water. 3 g of potassium hydroxide are added to the solution and the mixture is stirred at 40 ° C. for 4 hours. After cooling, the mixture is acidified with hydrochloric acid and extracted three times with a total of 150 ml of ether. The ethereal solution is washed with water, dried over magnesium sulfate and the solvent is distilled off. When left to stand, the residue solidifies to a white substance. 2.7 g of the compound mentioned in the title are obtained, yield 93%.

F .: 31-32 ° C.

IR / KBr /: 1710 / CO /, 1460, 1440, 1380, 1200, 1140 cm [high] -1.

[high] 1H-NMR / CDCl [low] 3 /: 0.87 / 3H, t, J = 6Hz /, 1-1.7 / 52H, m, 24 CH [low] 2, CH [low] 3, CH /, 2.1 / 2H, m, CH [deep] 2 /.

Ms: M [high] + 438/92 /, m / z 320/12 /, 185/23 /, 167/24 /, 158/25 /, 149/11 /, 129/19 /, 97/23 /, 85/34 /, 71/53 /, 57/100 /.

g) 2,10-di (methyl) octacosanoic acid (formula II with H instead of R)

8 ml of a 2 M solution of n-butyllithium (0.72 g, 0.011 mol) in n-hexane are added to a solution of 0.85 g / 0.0083 mol / diisopropylamine in 30 ml of anhydrous tetrahydrofuran at 0 ° C. in an argon atmosphere added. The mixture is stirred at 0 ° C for 20 minutes. A solution of 1.86 g / 0.004 mol / 10- (methyl) -octacosanoic acid (formula VIII with H instead of R) in 5 ml of anhydrous tetrahydrofuran and 5 ml of anhydrous hexamethylphosphoric acid triamide is added dropwise to the mixture, whereupon the solution is a half at 5 ° C

Is stirred for hour. 0.58 g / 0.255 ml, 0.004 mol / methyl iodide is added to the reaction mixture in one portion; the temperature rises to 20 ° C. The reaction mixture is stirred for one hour at room temperature, acidified with hydrochloric acid diluted in a weight ratio of 2: 1 and extracted four times with a total of 200 ml of petroleum ether. The extract is washed with water and a saturated sodium chloride solution, dried over magnesium sulfate and the solvent is distilled off. 1.3 g of the compound mentioned in the title are obtained. Yield 68%.

IR / film /: 1705 / CO /, 1460, 1380, 1230, 1140 cm [high] -1.

[high] 1H-NMR / CDCl [low] 3 /: 0.88 / 3H, t, J = 7Hz /, 1-1.7 / 56H, m, 24 CH [low] 2, 2CH [low] 3, 2 CH /.

Ms: M [high] + 452/69 /, m / z 438/7 /, 320/5 /, 199/10 /, 143/9 /, 130/11 /, 97/17 /, 57/32 /, 85/15 /, 83/24 /, 74/100 /.

h) 2,10-di (methyl) octocosanoic acid methyl ester

(Formula II with R = CH [deep] 3)

1.0 g of 2,10-di (methyl) octacosanoic acid (formula II with H instead of R) is mixed at 0 ° C. with an ethereal solution of 0.2 g of diazomethane. The solvent is distilled off. 1 g of the compound mentioned in the title is obtained in the form of a colorless oil.

IR / film /: 1735 / CO /, 1460, 1440, 1385, 1365, 1240, 1140 cm [high] -1.

[high] 1H-NMR / CDCl [low] 3 /: 0.89 / 3H, t, J = 6Hz, CH [low] 3 / 1.1-1.8 / 56 H, m, 24 CH [low] 2.2CH [deep] 3 / 3.7 / 3H, s, OCH [deep] 3 /.

Ms: M [high] + 466/100 /, m / z 435/4 /, 423/3 /, 409/7 /, 213/7 /, 186/3 /, 157/14 /, 143/10 /, 111/8 /, 97/14 /, 88/98 /, 85/13 /, 83/19 /.

Procedure B)

a) 2- (methyl) -undec-10-enoic acid (formula IXa)

100 ml of a 15% strength by weight solution of n-butyllithium (0.16 mol ) in n-hexane, whereupon a solution of 10 g / 0.054 mol / undec-10-enoic acid in 15 ml of anhydrous hexamethylphosphoric acid triamide is added to the mixture at 0 ° C. The reaction mixture is stirred at 0-5 ° C. for 20 minutes, after which the cooling is interrupted. 9.3 g / 4.1 ml, 0.065 mol / methyl iodide are added at such a rate that the temperature rises to 36 ° C. The mixture is stirred for 2 hours, poured into 60 ml of a hydrochloric acid diluted in a weight ratio of 1: 1 and extracted with ether. The ethereal extract is washed with hydrochloric acid, water, a 5% strength by weight sodium bisulfite solution, water and a saturated sodium chloride solution, dried over magnesium sulfate and evaporated. The residue is distilled off under reduced pressure. 8.5 g of the compound mentioned in the title are obtained, yield 80%.

Boiling point: 100-104 ° C / 1.3 Pa [0.01 mm Hg].

IR / film /: 1710 / CO /, 1630, 1440, 1370, 1270, 970, 905, 880 cm [high] -1.

[high] 1H NMR / CDCl [low] 3 /: 1.15 / 3H, d, J = 7Hz, CH [low] 3 /, 1.1-1.85 / 12H, m, CH [low] 2 /, 1.4-2.15 / 2H, m, CH [deep] 2 / 2.34 / 1H, t, J = 7Hz, CH /, 4.85-5.15 / 2H, m, C = CH [low] 2 /, 5.6-6.0 / 1H, m, -CH = C /.

[high] 13C-NMR / CDCl [low] 3 /: 16.8 / CH [low] 3 /, 27.2, 29.0, 24.2, 29.4,

29.6, 33.6 / CH [deep] 2 /, 33.9 / allyl-CH [deep] 2 /, 39.5 / CH /, 114.2, 139.0 / CH [deep] 2-CH /, 183.7 / CO /.

Ms: M [high] + 198/13 /, m / z 180/13 /, 153/16 /, 125/85 /, 97/20 /, 83/40 /, 73/100 /, 69/90 /, 55/85 /, 41/45 /, 27/65 /.

Analysis: on the formula C [deep] 12H [deep] 22O [deep] 2 / 198.31 /

Calculated: C: 72.68, H: 11.18;

Found: C: 72.46, H: 11.32.

b) methyl 2- (methyl) -10- (oxo) -undecanoate

(Formula X with R = CH [deep] 3)

I) 28.5 g / 0.025 mol / 30% by weight - hydrogen peroxide, 0.085 g / 0.0001 mol / palladium / II / acetate and 10.0 g / 0.05 mol / 2- (methyl) -undec -10-enoic acid are dissolved in 80 ml of acetic acid, whereupon the solution is stirred for 6 hours at 80 ° C. and cooled. After adding 40 ml of water, the mixture is extracted with ether, the ethereal solution is washed with water and a saturated sodium chloride solution, dried over sodium sulfate and evaporated under reduced pressure. 10 g of the brown crude 2- (methyl) -10- (oxo) -undecanoic acid (formula X with H instead of R) are obtained.

IR / film /: 1710 / CO /, 1460, 1230 cm [high] -1.

[high] 1H NMR / CDCl [low] 3 /: 1.12 / 3H, d, J = 7Hz, CH [low] 3 / 1.1-1.8 / 12H, m, 6 CH [low] 2 /, 2.1 / 3H, s, CH [deep] 3 /, 2.3 / 3H, m, CH [deep] 2, CH /.

II) The crude 2- (methyl) -10- (oxo) -undecanoic acid obtained as above is dissolved in 70 ml of anhydrous methanol. After adding 0.2 ml of normal sulfuric acid, the solution is heated to boiling for 8 hours. The mixture is cooled, neutralized with solid sodium bicarbonate, the solvent was evaporated under reduced pressure and the residue was taken up in ether. The ethereal solution is washed with a 5% strength by weight sodium bicarbonate solution, water and a saturated sodium chloride solution, dried over anhydrous magnesium sulfate and evaporated. The residue is subjected to vacuum distillation. 6.0 g of the compound mentioned in the title are obtained in the form of a pale yellow oil, yield 53%.

Boiling point: 146 ° C / 0.1 kPa [0.8 mm Hg].

IR / film /: 1740, 1710 / CO /, 1460, 1440, 1360, 1185, 1155 cm [high] -1.

[high] 1H NMR / CDCl [low] 3 /: 1.0-1.9 / 12H, m, 6CH [low] 2 /, 1.1 / 3H, d, J = 7Hz, CH [low] 3 /, 2.05 / 3H, s, CH [deep] 3CO /, 2.3-2.45 / 3H, m, CH [deep] 2, CH /, 3.65 / 3H, s, OCH [deep] 3 /.

Analysis: on the formula C [deep] 13H [deep] 24O [deep] 3 / 228.34 /

Calculated: C: 68.38, H: 10.59;

Found: C: 68.21, H: 10.45.

c) 2,10-Di- (methyl) -octakos-10-enoic acid methyl ester

(Formula XI with R = CH [deep] 3)

2.2 g of sodium hydride / 0.073 mol, an 80% by weight oily suspension / are added to 50 ml of anhydrous dimethyl sulfoxide and the mixture is stirred at 70 ° C. in an argon atmosphere until the evolution of hydrogen has ended / about 40 minutes /. The solution is cooled to room temperature and a solution of 40.0 g / 0.067 mol / [octadecyl] - [tri- (phenyl)] - phosphonium bromide (formula VI with X = Br) in 250 ml of anhydrous dimethyl sulfoxide is added. The mixture is stirred at 40 ° C for half an hour and cooled to 20 ° C. A solution of 12.0 g / 0.056 mol / 2- (methyl) -10- (oxo) -undecanoic acid methyl ester (formula X with R = CH [deep] 3) and 20 ml of anhydrous dimethyl sulfoxide is added dropwise. The reaction mixture is stirred for 6 hours at room temperature, poured onto ice and extracted three times with a total of 600 ml of n-pentane. The n-pentane solution is washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The remaining crude ester is purified by column chromatography. 6.7 g of the compound mentioned in the title are obtained, yield 47.9%. According to liquid chromatography, the product consists of a mixture of the E and Z isomers in a weight ratio of 3: 2.

IR / film /: 1735 / CO /, 1460, 1640, 1380, 1360, 1230, 1180, 1060, 990 cm [high] -1.

[high] 1H NMR / CCl [low] 4 /: 0.9 / 3H, t, J = 7Hz, CH [low] 3 / 1.15 / 3H, d, J = 6Hz /, 1.2-1 , 8 / 42H, m, 21 CH [deep] 2 / 1.4-2.3 / 5H, m, 2CH [deep] 2, CH /, 3.55 / 3H, s, OCH [deep] 3 /, 5.0 / 1H, m, CH = C /.

d) methyl 2,10-di (methyl) octacosanoate

(Formula II with R = CH [deep] 3)

A solution of 4.0 g of 2,10-di- (methyl) -octakos-10-en-acid methyl ester (formula XI with R = CH [deep] 3) in 200 ml of anhydrous methanol is in the presence of 0.5 g of a Hydrogenated palladium / charcoal catalyst. After the theoretical amount of hydrogen has been taken up / about 200 ml, 6 hours / the catalyst is filtered off, washed several times with methanol and the methanolic solutions are combined and concentrated. 3.8 g of a product are obtained / yield 95% / which is identical to the compound prepared according to procedure A), section h).

Claims (8)

1.) Process for the preparation of 3,11-di- (methyl) -nonakosan-2-one of the formula I, characterized in that one a) 2,10-Di- (methyl) -octakosansäurealkylester of the general formula II, wherein R represents an alkyl radical with 1 to 5 carbon atom (s), in solvents of the ether type with trialkylsilylmethyllithiums to intermediate products 1- (trialkylsilyl) -3,11-di- (methyl) - -nonakosan-2-one of the general formula IIIa, wherein R [deep] 1, R [deep] 2 and R [deep 3 is an alkyl radical with 1 to 4 each Mean carbon atom (s), converts and these intermediates with aliphatic Converts alcohols with 1 to 4 carbon atom (s) or b) 2,10-Di- (methyl) -octakosansäurealkylester of the general formula II, wherein R is set as above, in solvents of the ether type with a solution of methyl sulfinyl methide in dimethyl sulfoxide to the intermediate products Sodium salts of 1- (methylsulfinylmethyl) -2,10-di- (methyl) - -octacosanoic acid alkyl esters or 1- (methylsulfinylmethyl) -3,11-di- (methyl) -nonakosan-2-one of the (general) formulas IIIb, wherein R is set as above, converts and treats this with reducing agents and the 3,11-di- (methyl) -nonakosan-2-one of the formula I obtained in this way isolated from the reaction mixture in a manner known per se. 2.) Process according to claim 1, characterized in that the intermediates 1- (trialkylsilyl) -3,11-di- (methyl) -nonakosan-2-ones of the general formula IIIa or sodium salts of 1- (methylsulfinylmethyl) -2 , 10-di- (methyl) -octakosansäurealkylestern or 1- (methylsulfinylmethyl) -3,11-di- (methyl) -nonakosan-2-one of the general formula IIIb is reacted further in the reaction mixture without isolation. 3.) Process according to claim 1 a) or 2, characterized in that the trialkylsilylmethyllithium used is trimethylsilylmethyllithium. 4.) Process according to claim 1 a), 2 or 3, characterized in that the reaction of the 2,10-di- (methyl) -octakosansäurealkylester of the general formula II is carried out with the trialkylsilylmethyllithiumen with cooling. 5.) Process according to claim 1 a) or 2 to 4, characterized in that the aliphatic alcohol used is methanol. 6.) Process according to claim 1 b), characterized in that aluminum amalgam is used as the reducing agent. 7.) 2,10-Di- (methyl) -octakosansäurealkylester of the general formula II, wherein R represents an alkyl radical with 1 to 5 carbon atom (s). 8.) Process for the preparation of the compounds according to claim 7, characterized in that one A) a) Undec-10-enoic acid of the formula IV initially in the presence of a palladium salt as Catalyst with hydrogen peroxide to 10- (oxo) -undecanoic acid oxidized and this to a 10- (oxo) -undecanoic acid alkyl ester the general formula V, wherein R is as defined in claim 1 or 7, esterified or b) Undec-10-enoic acid of the formula IV, first esterified to give an alkyl undec-10-enoate and this in the presence of a palladium salt as Catalyst with hydrogen peroxide to 10- (Oxo) -undecan- acid alkyl esters of the general formula V, wherein R is as defined in claim 1 or 7, oxidized, as well as according to one of the above variants a) or b) obtained 10- (oxo) -undecanoic acid alkyl esters of the general Formula V with a phosphorane, which is derived from the phospho- nium salt [octadecyl] - [tri- (phenyl)] - phosphonium halide the general formula VI, wherein X halogen means has been made with a strong base for corresponding 10- (methyl) -octakos-10-enoic acid alkyl ester the general formula VII, wherein R is as defined in claim 1 or 7, converts this into the corresponding 10- (methyl) -octakosansäurealkylester the general formula VIII, wherein R is as defined in claim 1 or 7, transferred, this hydrolyzed, the carboxylic acid obtained 10- (methyl) -octacosanoic acid with a strong base in a Dianion converted, the dianion formed with methyl iodide methylated and finally the carboxylic acid obtained in this way 2,10-di (methyl) octacosanoic acid esterified or B) from undec-10-enoic acid of the formula IV forms a dianion with a strong base and this with Methyl iodide to form 2- (methyl) -undec-10-enoic acid of the formula IXa methylated as a) this 2- (methyl) -undec-10-enoic acid initially to one 2- (Methyl) -undec-10-enoic acid alkyl ester of the general formula IXb, esterified and this in the presence of a palladium salt with hydrogen peroxide to the corresponding 2- (methyl) - -10- (oxo) -undecanoic acid alkyl esters of the general formula X, wherein R is as defined in claim 1 or 7, oxidized or b) said 2- (methyl) -undec-10-enoic acid initially in Presence of a palladium salt with hydrogen peroxide oxidized to 2- (methyl) -10- (oxo) -undecanoic acid and this to a 2- (methyl) -10- (oxo) -undecanoic acid alkyl ester of general formula X, wherein R is as defined in claim 1 or 7, esterified as well as those obtained according to one of the above variants a) or b) 2- (Methyl) -10- (oxo) -undecanoic acid alkyl esters of the general formula X with a phosphorane, which is made from a phosphonium salt [Octadecyl] - [tri- (phenyl)] - phosphonium halide of the general formula VI, in which X halogen means has been made with a strong base, to the corresponding 2,10-Di- (methyl) -octakos-10-enoic acid alkyl ester of the general formula XI, wherein R is as defined in claim 1 or 7, implemented and reduced this catalytically.