CS247084B2 - Production method of 29-hydroxy-3,11-dimethylnonakosan-2- - Google Patents

Abstract

<IMAGE> The compound of the formula /I/ is prepared by a./ reacting an alkyl /2,10-dimethyl-28-octacosanoate/ of the formula /II/, <IMAGE> wherein R represents a C1-5 alkyl group and Y stands for a tetrahydropyranyl or a 2-ethoxyethyl group, with a trialkylsilylmethyl lithium in an ether-type solvent, reacting the thus-obtained intermediate of the general formula /III/, <IMAGE> wherein R1, R2 and R3 each represent a C1-4 alkyl group with an aliphatic alcohol, treating the compound of the general formula /IV/ thus obtained, <IMAGE> wherein Y is as defined above, with an acid; or b./ reacting an alkyl /2,10-dimethyl-28-octacosanoate/ of the general formula /II/ with a solution of methylsulfinylmethyde in dimethylsulfoxide in an ether-type solvent, treating the compound thus obtained with a reducing agent, e.g. aluminium amalgam, treating the thus-obtained compound of the general formula /IV/ with an acid, and separating the compound of the formula /I/ thus obtained from the reaction mixture. The compound of the formula /I/ produces a strong stimulating reaction on male German cockroach /Blattella Germanica/. Compounds of formula (II) are novel.

Description

A process for the preparation of 29-hydroxy-3,11-dimethylnonacosan-2-one of formula I

HO — CH2 — CH2) 17 o

II —CH— (CH2) 7 —CH — С — СНз

(I) is carried out by reacting the alkyl ester of 1-tetrahydropyranyloxy or 1- (2-ethoxyethyloxy) 2,10-dimethyl-28-octacosanoic acid with a trialkylsilylmethyllithium in an ether type solvent, preferably with cooling, the resulting intermediate is reacted , preferably without isolation, with an aliphatic alcohol and the resulting compound is treated with an acid to hydrolyze the ether group.

The present invention relates to a novel process for the preparation of 29-hydroxy-3,11-dimethylnonacosan-2-one. It is known that 29-hydroxy-3,11-dimethylnonacosan-2-one of formula (I)

СНз СНз

I I

HO — CH2 — CH2J17 — CH— (СН2) 7— СН — С — СНз II 0 induces a markedly strong stimulatory response to the male cockroach (Blattella Germanica).

Cockroach is an unpleasant and difficult insect of residential and commercial buildings. Old, neglected buildings that house public utilities are an ideal hideaway for various reptile insects, especially hard-to-kill cockroaches. Their reproductive cycle is short, so they reproduce rapidly and spread to new buildings.

In addition to the aesthetic point of view, the destruction of these difficult insects is caused by the direct damage caused to them. It can also transmit viral infections.

The cockroach has been destroyed by humans for centuries. Recently, pesticides have been developed which are highly toxic to cockroaches, but these pesticides often pose environmental hazards when used at effective concentrations. On the other hand, effective eradication can only be expected when toxic chemicals are applied repeatedly, because by the rapid multiplication of several (I) lo survivors, the treatment area can be reinfested in a short time.

In view of the above drawbacks, it is advantageous to use pheromone-containing traps to combat these insects. The bait of sex pheromones for cockroaches placed in traps is not toxic to taller animals or human beings. With these traps it is possible to trap cockroaches that have not been killed by chemical toxic substances, so that the reproduction of these insects can be prevented.

Nishida et al. (R. Nishida, H. Fukami and S. Ishii: Experientia 30, 978 [1974]; Appl. Ent. Zool. 10, 10 [1975]; R. Nishida, T. Sato, Y. Kuwahara, H. Fukami a

S. Ishii, J. Chem. Ecol. 2, 449 [1976]; Agr. Biol. Chem. 40, 1407 [1976]] have been concerned with the extraction of penguin pheromones. Two components identified as 29-hydroxy-3,11-dimethylnonacosan-2-one of formula I and 3,11-dimethylnonacosan-2-one of formula XI,

O

II

CH 3 - [CH 2 J 17 -CH- (CH 2) 7 —CH — C — CH 3

I I

CH3 CH3

Both of these compounds induce a reaction in adult males, manifested by stretching the wings and changing the direction of movement. The compound of formula I has been shown to be more active.

Later the Seas and Associates [K. The Sea,

T. Sururo and S. Mashda: Tetrahedron 37, 1329 (1981)] synthetically prepared all of the possible stereoisomers of both pheromone components. Natural pheromones were found to have a (3S, 11S) configuration.

The compound of formula I was first prepared by Nishida and co-workers [R. Nishida, T. Sato, Y. Kuwahara, H. Fukami, and S. Ishii: Agr. Biol. Chem. 40 (7), 1407 (19715)]. The starting compound was ethyl acetate of methyl acetic acid. The Anton obtained in the reaction of this compound with the potassium butylate target is reacted with 1,6-dibromohexane. The resulting 8-bromo-2-acetyl-2-methyloctanoic acid ethyl ester is hydrolyzed and then decarboxylated to give 9-bromo-3-methylnonan-2-one. This ketone is converted to its ethylene ketal which is reacted with an anion obtained from ethyl acetoacetate. The thus obtained ethylene (XI) acetal of 2-acetyl-9-methyl-10-oxoundecanoic acid ethyl ester is subjected to alkaline hydrolysis followed by decarboxylation. To the resulting 2-methyldodecane-2,1-dione-2-ethylene acetal was added 18-tetrahydropyranyloxyoctadecylmagnesium bromide, obtained in 4 reaction steps from 1,18-dihydroxyoctadecane. The resulting 1,1,1-dimethyl-11-dimethyl-11-hydroxy-29-tetrahydropyranyloxynonacosan-2-one ethylene acetal is dehydrated and the resulting 3,11-dimethyl-29-hydroxy-11-nonacosen-2-ol is catalytically hydrogenated to give the ferro component of formula I .

In the method of Burgstahler and colleagues [A. W. Burgstahler, L.O. Weigel, Μ. E. Sanders, C.G. Shaefer, W.J. Bell and S.

B. Vuturo, J. Org. Chem. 42, 566 (197 *)], 4-bromo-1-butanol benzyl ether is reacted with lithium acetylide in the presence of ethylenediamine. The resulting lithium salt of the acetylene derivative is alkylated with 1.12-4-iodo-dodecane. 1-Bromo-18-benzyloxy-13-octadecin is obtained, which is converted to the appropriate phosphorane. In the subsequent step of the synthesis, the hypophosphite is added

S is reacted with 9-bromnonan-2-one by Wittig reaction. The resulting brominated compound is used to alkylate the anion formed from 2- (4-t-acetate) with sodium hydride. Subsequent catalytic hydrogenation yields 3,11-dimethyl-3-ethoxycarbonyl-29. -hydroxynonacosan-2-one, which by hydrolysis and decarboxylation affords the desired compound of formula I.

Later, Burgstahler and co-workers elaborated an improved process for preparing a compound of formula I [A. W. Burgstahler, Μ. E. Sanders, C.G. Shaefer and L.O. Weigel: Synthesis, 405 (1977)]. They used a phase transfer methylation of benzyl acetate, in the presence of tetra-n-butylammonium bisulfate catalyst, to obtain benzyl 2-methyl-3-oxobutyrate, which was then re-alkylated with 26-benzyloxy-8-methyl-8-hexacosene. 21-ynyl bromide to give 2-acetyl-2,10-dimethyl-28-benzyl-oxy-10,10-octacosene-12-benzyl ester. This compound is then catalytically reduced and the resulting 2-acetyl-2,10 dimethyl-4-hydroxyoctacosanesellone is decarboxylated to give the pheromone component of formula I.

Seas and collaborators [K. Sea, S. Mosuda, T. Sugara: Tetrahedron Leters, 3444 (1978); Tetrahedron, 37 1329 (1981)] published a method for the sterically-controlled synthesis of all possible stereoisomers of 29-hydroxy-Zinc-dimethyl-non-naphtha] v210'1 of formula I and

3, 11-dimethylnonacosan-2-one of formula XI. The main step of their synthesis is the coupling of the chiral tosylate - in the case of the pheromone component of formula I, 5R- or 5S-methyl-23-benzyloxy-8-lricosinyl ttilate - with a chiral Grignard reagent prepared from 4R- or 4S. For the preparation of 4R-methyl-5-hexenyl bromide, one of the components of the coupling reaction, 3R-7-methyl-4-epoxy-1-heptene is oxidized with acid to form the corresponding aldehyde, which is then reduced with lithium aluminum hydride. The 4R-methyl-5-hexanol thus obtained is converted to the corresponding tosylate, which is treated with lithium bromide in acetone, and the 7-phenyl-4R-methylhexanoic acid ester is reacted with chromium trioxide to produce the semi-ester. subjected Hunsdiecker reaction to form methyl-4B nmihvl _{brom'hexankyselinv-8-one} which is reacted with O-nitroselenofenolem. Selenvlov group of the compound thus formed is removed by an oxidation treatment. Thus, the resulting olefinic acid is reduced with lithium aluminum hydride to produce the corresponding alcohol, the tosylate is converted to 4S-methyl-5lhexenvlbromid conventional manner.

In addition to the 4R- or 4S-methyl-15-hexenylbromide thus formed, S- or R-23-benzyloxyyltricos-8-ynyl tosylate is used as a further component in the coupling. To prepare R-tosylate, tetradradan-1,4-diol is converted to the corresponding monobenzyl ether. The tosylate of this compound is treated with lithium bromide to give 14-benzyl 10X716- (1,3 -nyl bromide) to give the corresponding iodide by halogenation with sodium iodide. The alkylated product is epoxidized with m-chloroperbenzoic acid and oxidation of the epoxide thus formed with periodic acid yields 4R-methyl-21-benzyloxy-7-heneicosine.RTM. -benzvloxy-8-tricosinol, which is converted to the tosylate in a conventional manner.

To prepare S-23-benzyloxy-5-methyltricos-8-ynyl tosylate, 7-fermyl-15S-methylheptyl acetate is converted into an olefin by Wittig reaction. Addition of bromine followed by cleavage affords 7-hydroxy-5S-methylheptylacetylene which is alkylated with 14-benzyloxy-adiranyl bromide. Acid treatment of the compound affords N-benzyloxy-S-methyltricosyl-4-inol, which is converted to the desired tosylate.

To prepare all possible stereoisomers of the pheromone component of formula (I), R- or S23-benzyloxy-5-monohyllricos-8-ynyl-tosylate is coupled with a Grignard reagent prepared from R- or S- (-) methylhexene-5-ll-bromide.

For both pheromone components (formulas I and XI), the compounds of the (3S, 11S) configuration proved to be identical to the natural cockroach lure. There were no significant differences in the biological activity of the individual stereoisomers.

The known processes for the preparation of the pheromone component of the formula I described are disadvantageous and uneconomical due to the large number of difficult and lengthy reaction steps and the cost of the reactants.

The purpose of the invention is to provide a more economical process for the production of the pheromone component of formula I, which is easier to carry out on an industrial scale.

According to the invention, the 29-hydroxy-3,11-dimethylnonacosan-4-one of formula (I) is prepared from the novel 2,10-dimethyl-11,2-octacosanil alkyl ester of formula (II) below.

YO - CH 2 - (CH 2) 16 - CH 2 - CH - (CH 2 ') 7 - CH - COOR

I I

CH3 CH3

In which

R is C 1 -C 5 alkyl;

Y represents a tetrahydropyranyl or 2-ethoxyethyl radical.

The method according to the invention is characterized by:

YO — CH2— (CH2J17 — CH— (CH2) 7--

AND

CH 3 wherein each of R 1, R 2 and R 3 is C 1 -C 4 alkyl and

Y is as defined above, wherein the alkyl ester of formula II, wherein R and Y are as defined above, is reacted with a trialkylsilylmethyllithium in an ether type solvent, preferably under cooling, to form the intermediate of formula III

ORl

II /

CH — C — CH2 — Si — R2 ·

AND\

CH3R3 (III) is reacted, preferably without isolation, with an aliphatic alcohol and the resulting compound of formula IV

O

II

YO-CH 2 - (CH 2) 17 -CH- (CH 2) 7 -CH-C-CH 3

I I

CH3 CH3 in which

Y is as defined above, treated with acid, and the compound of formula I obtained is isolated from the reaction mixture.

In the process of the invention, the compound of formula (II) is reacted with a trialkylsilylmethyllithium in an ether type solvent, preferably under cooling. The intermediate of formula (III) thus formed need not be isolated and can be further reacted in the reaction mixture in which it is formed with an aliphatic alcohol, preferably methanol. The protecting group of the compound of formula (IV) thus obtained may be removed by treatment with an acid, for example p-toluenesulfonic acid.

The compound of formula (I) formed by the described reaction can be isolated from the reaction mixture by known methods, for example by distillation or chromatography.

The compounds of formula (II) used as starting materials in the synthesis described have not been described in the literature. Two procedures have been developed for their preparation. In the first one, 10-undecenic acid, an inexpensive commercial product, is reacted with an alkyl lithium, the dianion formed is alkylated with methyl iodide and the resulting 2-methyl-10-undecenic acid of formula V (IV)

CH 2 = CH- (CH 2) 7 —CH — COOH

AND

CH 3 (V) is converted to the corresponding ester. Treatment of this ester with hydrogen peroxide in the presence of a catalytic amount of a palladium salt gives a compound of formula VI

CH3-C- (CH2) 7-CH-COOR

II I

O СНз (VI) in which

R represents an alkyl group.

This compound is reacted with a hypophosphite prepared from a phosphonium salt of formula VII (C 6 H 5) 3 P + -CH 2 - (CH 2) 16 -CHa-OY X (VII) in which:

X is halogen and

Y represents a tetrahydropyranyl or 2-ethoxyethyl radical, by treatment with a strong base, preferably butylthium. The compound of formula (VIII) thus formed

YO-CH 2 - (CH 2) 16 -CH = C- (CH 2) 7 —CH — COOR

CH3

CH3 (VIII)

347084 for the preparation of compounds of formula II, the 10-oxoundecanoic acid ester is reacted with a phosphonium salt derived from a phosphonium salt of formula VII. The compound of formula (IX) in which:

R and Y, as defined above, are subjected to catalytic reduction to give a compound of formula II.

According to the second procedure, elaborated

YO-CH 2 - (CH 2 J 16 -CH = C- (CH 2) 8 -COOR.

CH3 (IX) in which it is catalytically reduced to yield Y and R are as defined above, a compound of formula X

YO — CH2— (CH2) 17 —CH— (CH2) 8 —COOR

AND

CH3 (X) wherein

Y and R are as defined above, which is hydrolyzed to the corresponding carboxylic acid. This acid is converted to dianion by treatment with a strong base, preferably methyllithium. Subsequent reaction with methyl iodide provides the compound of formula II.

The trialkylsilylmethyllithium used in the process of the invention is prepared from a trialkylsilylmethyl halide by treatment with lithium metal.

The invention is illustrated by the following non-limiting example.

Example

Preparation of 29-hydroxy-3,11-dimethylnonacosan-2-one and Preparation of 18- (2-tetrahydropyranyloxy) -octadecanyltriphenylphosphonium iodide (Formula VII wherein X-J, Y = tetrahydropyranyl) ai) 3.0 g (0) The 18-chlorooctadecanol was dissolved in 20 ml of anhydrous benzene and 1.0 g (0.012 mol, 1.1 ml) of dihydropyran and 0.05 g of p-toluenesulfonic acid were added thereto, followed by stirring for 4 hours. hours at room temperature, then diluted with ether, washed successively with 5% sodium bicarbonate solution, water and brine, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was distilled.

Yield: 3.5 g (90 ° / o)

Melting point: 124-126 ° C at 20 Pa

IR (thin layer: 1025, 720 cm ^-1)

1 H-NMR (CDCl 3): δ

3.25 to 4.0 (4H, m, -CH 2 -O),

3.52 (2H, t, I = 7Hz, —CH2-C1),

4.57 (1H, m, -O-CH-O)

Analysis for C23H45O2Cl (389.067)

Calculated:

H, 11.66; Cl, 9.11;

Found:

% C, 71.21;% H, 11.51;

O R1 a2) 1.95 g (0.005 mol) of 18-chlorooctadecanyltetrahydro-2-pyranyl ether are dissolved in 15 ml of methyl ethyl ketone, 1.12 g (0.0075 mol) of sodium iodide is added and the mixture is heated at reflux for 20 hours. . The mixture was cooled, the precipitated salt was filtered off and the filtrate was evaporated under reduced pressure. The residue was dissolved in ether, washed successively with water, 5% sodium bisulfite solution and brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure; The crude 18-iodooctadecanyltetrahydro-2-pyranyl ether was purified by chromatography using a 10: 1 mixture of benzene and acetone.

Yield: 1.9 g (90%)

Thin layer chromatography: Rf = 0.55 (10: 1 benzene / acetone)

IR (thin layer): 1025 cm @ -1. @ 1 H-NMR (CDCl3): .delta

1.15 to 2.0 (38H, m, —CH2—),

3.05-4.0 (6H, m, -CH 2 O, —CH 2 -J),

3.09 (2H, t, J = 6Hz, -CH 3 -J),

4.44 (1H, m, O-CH-O)

1.15 to 2.0 (38H, m, —CH2 -),

4 7 О 4

Analysis for C23H45O2J (480,518)

Calculated:

H, 9.44; J, 26.41;

Found:

% C, 57.63;% H, 9.52;% J 26.12.

аз) A mixture of 2.4 g (0.005 mol) of 18-iodooctadecanyltetrahydropyran-2-yl ether with 1.31 g (0.005 mol) of triphenylphosphine was heated in 50 ml of anhydrous acetonitrile for 50-70 hours. Then the solvent was evaporated under reduced pressure. The remaining, honey-like product is decanted several times with ether, then the solvent is removed under reduced pressure and the product is dried.

Yield: 2.2 g (60%) of a setting oil

IR (thin film):

590, 1110, 730, 690 cm ^{-1 X} H-NMR (CDC13):

1.1-2.0 (38H, m, —CH2—),

3.1 to 4.1 (6H, m, - CH2 --O, - CH2 --P),

4.56 (1H, m, O-CH-O),

7.5 to 8.2 (15H, m, aromatic)

Analysis for C41H60O2PJ (742.614)

Calculated:

H, 8.14; P, 4.17; J, 17.08; Found:

% C, 66.41;% H, 8.25;% P, 4.06;

b) Preparation of 2,10-dimethyl-28- (2-tetrahydropyranyloxy) -10-octacosyl acid methyl ester (of formula VIII, wherein R = N, Y = tetrahydropyranyl)

7.4 g (10 mmol) of 18- (2-tetrahydropyranyloxy) -octadecanyltriphenylphosphonium iodide are dissolved in 60 ml of anhydrous tetrahydrofuran, cooled to 10 degrees Celsius and 10 mmol of butyllithium (16%) are added under cooling under inert gas. solution in hexane (6.3 mL). The cherry red solution was stirred at 10 ° C for 30 minutes, and a solution of 2.2 g (10 mmol) of 2-methyl-10-oxoundecanoic acid methyl ester (Formula VI in which R = СНз) at 10 ° C was added over 30 minutes. ml of anhydrous tetrahydrofuran. The reaction mixture was stirred for an additional 5 hours at room temperature. Then 10% ammonium chloride solution is added, the mixture is extracted with petroleum ether, the organic phase is washed successively with 5% sodium hydrogen carbonate solution, water and brine, dried over magnesium sulfate and evaporated. Approximately 3.5 g of crude product is obtained.

The crude product can also be isolated by diluting the reaction mixture with 100 mL of hexane followed by flash chromatography on a short silica gel column. Evaporation of the solution under reduced pressure gave about 2 to 2.5 g of crude product which could be purified by column chromatography eluting with benzene / acetone (10: 0.5).

Yield: 1.2 g (21%) of a colorless oil

TLC: Rf = 0.6

IR (thin film):

1735 (CO), 1460, 1375, 1160, 1030 cm ^{<-1 X} H-NMR (CDC13): δ

1.0 to 1.8 (54H, m, CH 2 -, 2-NH),

1.8 to 2.1 (4H, m, -CH2-C =),

2.3 (1H, m, CH - COO),

3.25 to 4.1 (4H, m, —CH2O-),

3.68 (3H, s, s),

4.5 εζ 4.65 (1H, m, O — CH — O),

5.1 (lH, m, -CH =)

Analysis for СзеНбвО4 (564.94)

Calculated:

% C, 76.54;% H, 12.13;

Found:

76.67% C, 11.95% H.

c) Preparation of 2,10-dimethyl-28- (2-tetrahydropyranyloxy) -octacosanoic acid methyl ester (of formula II, wherein R = N = Y = tetrahydropyranyl)

0.56 g (1 mmol) of 2,10-dimethyl-28- (2-tetrahydropyranyloxy) -10-octacosenoic acid methyl ester is dissolved in 20 ml of anhydrous methanol, and the solution is added to a suspension of 0.3 g of catalyst under an inert gas atmosphere. of palladium on activated carbon in 10 ml of anhydrous methanol.

The reaction mixture was stirred at room temperature under a hydrogen atmosphere. After filtering off the catalyst, the filtrate was evaporated.

Yield:

0.53 g (96%) of a colorless oil

IR (thin film):

1735 (CO), 1460 cm ^{1 X} H-NMR (CDC13): <5

0.82 (3H, d, I = 6Hz, 10-OD),

1.0 to 1.8 (58H, m, —CH2—, 2-N2),

2.3 (1H, m, CH - COO),

3.2 to 4.1 (4H, m, -CH 2 O),

3.65 (3H, s, S, N)

4.5 to 4.65 (1H, m, O-CH-O)

247 13

Analysis for C36H70O4 (566,958)

Calculated:

% C, 76.26;% H, 12.44;

Found:

% C, 76.05;% H, 12.53.

d) Preparation of 3, 11-dimethyl-29- (2-tetrahydropyranyloxy) nonacosan-2-one of the general formula IV, wherein Y = tetrahydropyranyl residue)

To 10 ml of common ether is added 0.12 g (20 mmol) of lithium dispersed in 0.4 g of acid (containing 30% lithium). 0.30 g (2.5 mmol, 0.34 ml) of trimethylsylmethyl chloride was added to the mixture under an inert gas atmosphere, and the mixture was heated at reflux for 2.5 hours. After cooling, the suspension is allowed to settle and the remaining lithium is separated from the trimethylsilylmethyllithium solution by extruding the solution with an inert gas into another vessel. Then, a solution of 0.5 g (1 mmol) of 2,10-dimetayl-28- -2‘-tetahydro-propoxy-oxy-octanoic acid methyl ester in 5 ml of anhydrous ether was added to the solution at 0 ° C. The reaction mixture was stirred at 0 ° C for 2 hours, then 2 ml of anhydrous methanol was added under cooling, and the mixture was stirred at room temperature for 1.5 hours. After addition of water, the mixture was extracted with ether, the ether solution was washed with ammonium chloride solution, water and brine, dried over magnesium sulfate and evaporated under reduced pressure. 0.5 g of crude product is obtained, which is purified by chromatography (using a 10: 0.2 mixture of benzene and acetone).

Yield:

0.26 g -45%) colorless oil

IR (thin layer):

705-CO), 1460, 1080, 1030 cm ^-1

@ 1 H-NMR (CDCl3): .delta

0.82-3H, d, J = 6Hz, 11-CH 2),

1.05 · -3H, d, J = 7Hz, 3-CH 3),

1.1-1.2 -55H, m, -CH2-), 2.05-3H, s, CH3, CO),

2.4 (1H, m, CHCO),

3.2 to 4.1 (4H, m, -CH 2 O),

4.5 to 4.65 (1H, O-CH-O, m)

Analysis (C36H70O2 -550.25)

Calculated:

% C, 78.48;% H, 12.80;

Found:

% C, 78.22;% H, 12.61.

e) Preparation of 22-hydroxy-3,11-dimethyl-nonacosan-2-one of formula I)

0.05 g of p-toluenesulfonic acid is dissolved in a mixture of 5 ml of methanol with 0.5 ml of water. 0.27 g (-0.5 mmol) is added to the solution)

3,11-Dimethyl-22 (2-tetrahydropyranyloxy) -nonacosan-2-one and the reaction mixture was stirred at 60 ° C for 4 hours. After cooling, the solvent was removed under reduced pressure, the residue was dissolved in ether, washed successively with 5% sodium bicarbonate solution, water and brine, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. 0.22 g of crude product is obtained, m.p. 34-38 ° C, which can be recrystallized from petroleum ether at -20 to -30 ° C.

Melting point:

to 42 [deg.] C. [according to literature -A. W. Burgstahler et al., J. Org. Chem.

42, 566, 1277) 41-43 ° C]

IR (thin layer):

350 (OH), 1715 (CO), 1040 cm @ -1 ^{( 1} H-NMR-CDCl3): .delta

0.82-3H, d, J = 6Hz, 11-CH 3),

1.04 -3H, d, J = 7Hz, 3-CH 3),

1.1 to 1.6 -49H, m, -CH 2 -),

2.01-3H, s, CH 3 CO),

2.34 (1H, m, CH - CO),

3.52 -2H, t, J = 6Hz, -CH 2 O)

Analysis for C31H62O2 (466.84)

Calculated:

% C, 72.76;% H, 13.32;

Found:

% C, 72.62;% H, 13.61.

Claims (3)

OBJECT OF THE INVENTION A process for the preparation of 29-hydroxy-3,11-dimethylnonacosan-2-one of formula I O II НО — CH2— (CH2) 17 — CH— (CH2) 7 — CH — С — СНз I I (I) characterized in that the substituted 2,10-dlmethyl-28-octacosanoic acid alkyl ester of formula (II) is: YO — CH2 - (CH2) 16 — CH2-CH- (С) 7 — CH — COOR In which it is reacted with a trialkylsilylmethyllithium in an ether type solvent, preferably under R represents an alkyl group having 1 to 5 cooling, the resulting intermediate of general carbon atoms and formula III Y represents a tetrahydropyranyl or 2-ethoxyethyl radical, ORi II / YO - CH ₂ - (CH ₂ ) 17 - CH - (CH 2) 7 - CH - S - CH 2 - Si - R 2 I I \ C III (III) wherein each of R 1, R 2 and R 5 is C 1 -C 4 alkyl and Y is as defined above, reacted, preferably without isolation, with an aliphatic alcohol and the resulting compound of formula IV O - || YO — CH _and - (CH2) 17-CH- (CH2) 7 —CH — С — СНз I I СНз СНз (IV) in which Y is as defined above, treated with acid, and the resulting compound of formula I is isolated from the reaction mixture. 2. A process according to claim 1 wherein the trialkylsilylmethyllithium is trimethylsilylmethyllithium. 3. The process of claim 1 wherein the aliphatic alcohol is methanol. Severography, n. Race 7, Most Price 2,40 Kčs