JPS6064942A - Manufacture of 3,11-dimethyl-2-nonacosanone - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a new process for the production of 3,11-dimethyl-2-nonacosanone.

It is known that 3,11-dimethyl-2-nonatsusanone having formula (1) exhibits an extremely strong irritant response to male German cockroaches.

The German cockroach is a nuisance pest to residential and commercial buildings. Old, neglected buildings containing public facilities provide ideal hiding places for many species of crawling insects, especially the difficult-to-kill cockroaches. Because its breeding season is short, it quickly spreads and appears in new residential areas.

In addition to the aesthetic considerations that account for the eradication of this pest, the direct harm caused by it cannot be ignored either. Additionally, it may spread viral infections.

The German cockroach has been a target for human eradication for centuries. Recently, insecticides have been developed that have high toxicity to cockroaches, but such insecticides often pose an environmental hazard when used at effective concentrations. On the other hand, effective eradication can only be expected if chemical poisons are applied frequently. This is because the rapid reproduction of a few surviving pests can reinfect the area in a short time.

Due to the aforementioned difficulties, in order to combat this pest,
It is advantageous to use traps containing pheromones. The sex pheromone traps are not toxic to higher animals, namely humans. By these means, pests that have survived despite eradication by chemical poisons can be trapped, thus preventing their emergence.

Nishida et al. (R, N15hida, H, Fukant
& S., Iahii, :Experientia 3
0 e 978 (1974); Appl, Ent.

Zool, Dan, 10 (1975); R, N15hid
a, T, 5ato+Y, Kuwabara, H,F
ukami & S+l5hii: J, Chem.

Ecol, 2, 449 (1976); Agr, B.
iol, Chem, 40. .

1407 (1976)] reported on the extraction of German cockroach pheromones. From the epidermal wax of sexually mature females, they have the formula (1) 3,11-dimethyl-2
-nonacosanone and 29-hydroxy-3,11-dimethyl-2- having the formula CI-3CH3
Two components identified as nonacosanone were isolated.

Both compounds elicit wing flotation and reorientation responses from adult males.

Later, Mori et al. [: IC, Mori + T, Sugar
o&s.

Mahda: Tetrabcldron 37+
1329 (1981)) synthesized all possible stereoisomers of both heptaromone components. Natural hepteromones were shown to be of the (3S, IIS) configuration.

The compound having formula (1) is described by Nishida et al. (R,N15hi
da+H, Fukami & S, l5hii: A
ppl, Entomol.

Zool, *Lot 10 (1975))
first synthesized. They used ethyl acetoacetate as a starting material. Condensation reaction of it with 1,6-dibromohexane is accomplished in alkaline solution to give the corresponding bromoketoester, which is hydrolyzed followed by spontaneous decarboxylation in concentrated hydrobromic acid, gave 1-bromo-8-oxononane. The latter was reacted with occudenlene-triphenylphosphoryl to give l-bromo-8-methyl-8-hexanol, which was then reacted with excess ethyl methyl acetoacetate in the presence of potassium tert-butoxide. did. The thus obtained ethyl (2,10-tmethyl-
2-acetyl-11-octacosenoate) was hydrolyzed and then decarboxylated, and the thus obtained 3,11-dimethyl-2-oxy-11-nonacosene was subjected to catalytic hydrogenation to form the formula ( It was converted to the following compound.

Another method [: M, Schwarz+ J, E,
01iver & P, E, 5onnet: J,
Org, Chem, 40+2410 (1975)]
According to 1,6-hexanediol was used as the starting material. 6-chlorohexyltetrahydro-
Converted to 2-pyranyl ether, which was reacted with sodium iodide and sodium cyanide in dimethyl sulfoxide. Reaction of the 7-titrahydrobilanyloxyhebutanenitrile thus obtained with lithium jetoxyaluminum hydride gave the corresponding aldehyde. Witsch reaction between the latter compound and (1-methylnonadecylidene)triphenylphosphorane probably gives a cis and trans mixture of 8-methyl-7-hexacosenylte[lahydropyranyl ether, which can be hydrogenated. 8-methyl hexacosanyl tetrahydropyranyl ether is obtained. This latter was reacted with triphenylphosphine/dibromide to form the thus sheathed l-bromo-8-methylhexacosane with the anion formed from (2-oxoptylidene)triphenylphosphorane and butyllithium. react with. The thus obtained 3,1l--)methyl-2-oxynonacoside/triphenylphosphorane is hydrolyzed to give the desired formula (I
) was obtained.

In yet another method, Burgstahl
er et al. (A, W, Burgstahler+
L, O, Weigel + W, J, Beil & M, Ru5t: J, Org, Chem.

40, 3456 (1975)) used ε-caprolactone as a starting material. Treatment of them with hydrogen bromide and concentrated sulfuric acid gave 6-promohexanoic acid. This acid diesterification provided ethyl 6-bromohexanoate, which was reacted with the nadosome enolate of acetoacetate to yield ethyl (7-ethoxycarbonyl-8-oxononononyi 1.).

This latter compound was hydrolyzed and decarboxylated to 8-oxononanoic acid. Treatment of those methyl esters in a polar solvent with Witsch's reagent derived from octadecyltriphenylphosphonium bromide gave methyl-8-methyl-8-hexacosanol. This is hydrogenated to the corresponding saturated nistyl which, after reduction with lithium aluminum hydride to 8-methyl-1-hexacosanol and conversion to the corresponding bromide, is used to give diethylmethylmalonate. Alkylated. Hydrolysis of the diester obtained and decarboxylation of the acid thus obtained gave 2110-dimethyl-octacosanoic acid, which was treated with methyllithium to yield the target compound having formula (1).

Rosenblum et al.
m+R,J.

Anderson+ C, A, Henrik: Te
trahedron Letters 419 (1976
):], 3.11-dimethyl-2-nonacosanone was synthesized from S-phenylnonadecanethioate. The di-6-[(1-ethoxy)ethoxy]hexyl@rl salt reagent of lithium was prepared from the ethoxyethyl ether of 6″'-chlorohexanol, which was reacted with 5-phenyl nonadecane thioate to give 7 -Oxopentacosane-1
-He threw an oar. Reaction of the ketoacetal with triphenylphosphonium methylide in tetrahydrofuran produced the corresponding methylene acecool, which was catalytically hydrogenated and then hydrolyzed with a catalytic amount of P-)luenesulfonic acid. The 7-methylpentacosan-1-ol thus obtained was reacted with mesyl chloride and triethylamine, and the mesylate was treated with lithium bromide to yield 7-dimethylpentacosanyl bromide. The latter compound was converted in two reaction steps to 3-4(1-
ethoxy)ethoxy-2-methylbutyllithium This coupling reaction
It was carried out in the presence of copper tetrachloride. The thus obtained 2-[(1-ethoxy)-ethoxy)-3'*11-dimethylnonacosane conversion was treated with trichloroacetic acid. Oxidation of the thus obtained 2-hydroxy-3゜11-dimethylnonacosane with Jones reagent is expressed by the formula (1).
A pheromone component with

Place et al. (P+P1ace+ M, L, Ronm
estant+J, Gore; Tetrahadr
Vinylarenes were used for the synthesis of compounds with formula (1) according to the method of J.D. on + 34+ 1931 (1978)). 3-Hydroxy-3-methyl-1-penten-4-yne obtained from methyl vinyl ketone and acetylene is treated with hydrogen chloride to obtain 1-chloro-3-methyl-2-penten-4-yne. This was converted with magnesium to the corresponding magnesium vinyl methyl arene.

This latter was reacted with acrolein to give the 4-ethynyl-4-methyl-3-hydroxy-1,
Protecting the alcohol hydroxy group of 5-hexadiene,
The compound was alkylated with hexadecanyl bromide at -30°C. The thus obtained 4-allyl-3-,hydroxy- in diethylene glycol dimethyl ether
Boiling 4-methyl-1-tocosen-5-yne undergoes an Oxy-Cope rearrangement reaction to form 6-methyl-5-ene-7-yne.
He returned to Inchidracosanal. The latter aldehyde together with butyllithium (4-ethylenedioxo)-3-
Alkylated with alkyl lithium obtained from methyl-1-chloropentane.

The hydroxy group of the thus obtained 3,11-dimethyl-2-ethylenedioxy-6-hydroxy-10-nonacomon-12-yne was reduced by zinc reduction of the mesyl derivative in dimethoxyethane in the presence of sodium iodide. It was removed by doing so.

Thus obtained (2-ethylene dioxo)-3.

Hydrogenation of 11-dimethyl-10-nonacomon-12-yne afforded a compound having the natural formula (1) by removing the acetal protecting group.

Seidel &Sch'Mfer (W. Sei
del, H. J.

Schufer: Chem. Ber. Li. 3,4
51 (1980)), the basic steps for producing a pheromone component having formula (I) are as follows: 6-methyltetracosanoic acid and 5-methyltetracosanoic acid
- iron coelectrolysis with methyl-6-oxhebutanoic acid. They started with sec-butyl-(2-butenoate), which was reacted with octadecylmagnesium bromide in the presence of cupric chloride. The secondary butyl-(3-methylheneicosanoate) thus obtained was subjected to hydrolysis to defeat the corresponding enemy.

This was then subjected to iron electrolysis together with 5,5-dimethoxyno4lerianic acid. The methyl-(6-methyltitracosanoate) thus obtained was subjected to alkaline hydrolysis to give the corresponding acid. This compound was obtained through alkylation with ethyl 4-bromobutyrate followed by depotentifying redexyl reaction.
5-methyl-6 derived from methylacetoacetate
- Iron electrolyzed with oxtuhbutanoic acid to obtain a compound having formula (1).

Mori et al. (K. Mori+ S. Mosuda+
T. Sugara: Tetrahedron Let
tera+ 3444 (1978); Tetrahed
ron+ 37e 1329 (1981): l is the formula (
1) and all possible stereoisomers of 3t11-dimethyl-2-nonacosanone with the formula HEL and 29-hydroxy-3*1t-&methyl-2nonacosanone with the formula HEL have been published. The basic step for their synthesis is the presence of dilithium copper tetrachloride and, in the case of the chiral tosylate pheromones of set (I), respectively 5R- and 5S-methyltricosanyl tosylate- and its 11 respectively 4R - and 4S-methyl-5-hexenyl bromide 19 is pulled with a chiral Grignard reagent made into 4. To prepare 5R-methyltricosanyl tosylate, R+)- Citronel acid was reduced to R-(→-citronellol with lithium aluminum hydride. The tosylate was converted to R-(→-citronellyl iodide) with sodium iodide. By standard malonic acid ester synthesis. Then, it was converted to 5P, , 10-dimethyl-9-decenoic acid via malonate.This was reduced to the corresponding alcohol with lithium and aluminum hydride, and its acetylation was carried out to form 5S,
10-dimethyl-9-decenyl acetate was obtained. Oxidation of the latter with m-chlorobenzoic acid and oxidation of the epoxide thus obtained with periodic acid gives 7-formyl-5s
- gave methylheptyl acetate. Witsch reaction between this latter compound and triphenylpentadecenylphosborane gave the olefinic alcohol. This was hydrogenated through mother radium to give 5R-methyltricosanol. The corresponding tosylate was prepared in the usual manner.

To prepare the enantiomer tosylate, it was alkylated with 1-hex+y''syn@R-(→-citronellyl iodide. Oxidation with acid gives 4g-methyl-
7- Strengthened dococinal.

Reduction of this with lithium aluminum hydride converted the alcohol thus obtained to the corresponding tosylate, which reaction with potassium cyanide gave the corresponding 2) IJ. Alkaline hydrolysis, reduction of the acid thus obtained and subsequent catalytic hydrogenation provided the desired 5S-methyltricosanol.

The corresponding tosylate was prepared in a conventional manner.

4-R-Methyl-5-hexenyl bromide and other components for the synthesis were prepared from 3R17-tumethyl-6°7-epoxy-1-heptene. Their oxidation with periodic acid gave the corresponding aldehydes, which were reduced with lithium aluminum hydride to give 4R-methyl-5-hexanol. The corresponding tosylate was treated with lithium bromide in acetone. To prepare the enantiomer of the compound thus obtained, 7-phenyl-4R-methylhexane ester was reacted with chromium oxide to form the half-ester. The silver salt was subjected to a 7 sonicator reaction to give methyl (4S-methyl-6-bromohexanoate). This is reacted with O-nitroselenophenol, and the selenyl group of the compound thus present is removed by oxidative elimination, thus ? The N-olefinic acid was reduced with lithium aluminum hydride to give the corresponding alcohol, and the tosylate was converted to 4s-methyl-5-hexenyl bromide in the usual manner.

To prepare stereoisomers of the compound having formula (1), Grignard reagents derived from 4R- and 4s-methyl-5-hexenyl bromide, respectively, were
It was combined with R- and 5s-methyltricosashield sylate. The reaction was carried out in the presence of dilithium copper tetrachloride. Marknikov hydration of the 3°11-dimethylnonacosene stereoisomer obtained by oxymer clarification-demer clarification with mercury acetate (n) and sodium borohydride gave the alcohol. This alcohol is
It was oxidized with chromium oxide to give the desired pheromone component having formula (1).

In the case of both heptagonal lomone components [formulas (I) and (to)], the compounds with the (3S, 11S) configuration proved to be identical to the natural sex of the poisonous insect.

The authors did not find any significant differences between the biological activities of the various stereoisomers.

A known method for producing a pheromone component having formula (1) is:
Due to the large number of cumbersome reaction steps and expensive reactants,
It is inconvenient and uneconomical.

The object of the present invention is to provide a more economical process for the production of a pheromone component having formula (1), which can be easily carried out on an industrial scale.

Means for Solving the Problems According to the present invention, 3,11-tmethyl-2-nonacosanone having the formula (I) has the general formula (n)n3CH3 (wherein R is a C1-5 alkyl group). a.) 2,1o-dimethyloctacosanoic acid ester having the general formula (10) is reacted with trialkylsilylmethyllithium in an ether type solvent, preferably under cooling; The thus obtained general formula (to) (wherein R1, R1 and R3 may be the same,
Alternatively, they may be different and represent a C1-5 alkyl group. ) is reacted, preferably without isolation, with an aliphatic alcohol; - reacting the dimethyl octacosanoic acid ester with a solution of methylsulfinyl methide in dimethylsulfoxide in an ether type solvent and the compound thus obtained preferably without isolation;
It is produced by reacting with a reducing agent, preferably aluminum amalgam; and separating the solute from the reaction mixture.

According to step n,) of the method according to the invention, the general formula (JT
) is reacted with trialkylsilylmethyllithium in an ethereal solvent, preferably under cooling. It is not necessary to isolate the intermediate having the general formula (-) thus obtained and it can be reacted with an aliphatic alcohol, preferably methanol, in the reaction mixture produced. According to the method steps according to ), the general formula (ID
The compound is reacted with a solution of methylsulfinyl methide in dimethylsulfoxide.

Methylsulfinyl methide can be prepared from dimethylsulfoxide with a strong base, preferably sodium hydride, at temperatures below 70°C.

The intermediates obtained in the reaction of compounds with formula (1) with methylsulfinylmethide do not need to be isolated; their reduction can be accomplished in the reaction mixture formed. The reduction is carried out in a conventional manner, preferably with an aluminum amalgam derived from aluminum and mercuric chloride.

The compound having formula (1) obtained in the reaction is treated by known methods (e.g. distillation, chromatography).
It can be separated from the reaction mixture.

The esters with the general formula (If) used as starting materials have not previously been described in the literature. To manufacture them, we have painstakingly developed two methods.

According to the first one, the formula % formula % (
) 10-Undecenoic acid having the general formula (to) CH3-
It is converted into an ester having C-(CH2)8-C0OR(V)1 (wherein R is a C1-5 alkyl group). This reaction can be carried out in two ways. 10-Undecenoic acid is oxidized with hydrogen peroxide in the presence of a catalytic amount of a palladium salt, preferably palladium acetate, and the acid thus obtained is converted to an ester of general formula (V), or 10-undecenoic acid is Either undecenoic acid is first converted to the corresponding ester, which is then oxidized to a compound having the general formula (-). This latter is then combined with a strong base, preferably methylsulfinylmethide, to give the general formula 0Φ (C6H5) 3P+CH2-(CJ(2) 16-C
It is reacted with a phosphorane derived from a compound having H3X-(t) (wherein X represents a halogen). The general formula (b) thus obtained: CH3-(CH2)16-C)l=c-(CH2)8-
The ester having COOR(■)H6, where R is as defined above, is catalytically hydrogenated over palladium on a charcoal catalyst. The general formula (■) thus obtained: CH3-(CH2)16-CH2-C)i-(CH2)
The saturated ester having 8-COQR(■)CH3, where R is as defined above, is hydrolyzed and the acid thus obtained is converted to the corresponding dianion with a strong base, preferably an alkyl lithium. is converted to The dianion reacts with methyl iosite and the acid thus obtained is converted into an ester having the general formula (It).

According to a second, painstaking process for the preparation of esters having the general formula (It), 1o-undecenoic acid having the formula (T) is reacted with an alkyl lithium, and the dianion thus obtained is methyl iosito The 2-methyl-10-undecenoic acid thus obtained is converted to the corresponding ester, which is reacted with hydrogen peroxide over a palladium salt catalyst - preferably acetic acid/('radium) in the presence of radium. It is oxidized to a compound having the formula cH3, where R is as defined above. This latter is reacted with a phosphorane derived from a phosphonium salt having the general formula (-). Formula (to) CH3'' CJ15-CCH2)16-CII=C(CH2)7-
An ester having the formula CHC0OR00CH3 is obtained, in which R is as defined above, which is subjected to catalytic reduction to obtain an ester having the general formula (n).

According to another step of the process, a compound of formula (IX) is prepared from 2-methyl-10-undecenoic acid. That is, it is first oxidized to the corresponding oxocarboxylic acid, which is converted into an ester with the general formula (DO).

The trialkylsilylmethyllithium used for step a,) of our synthesis is prepared from trialkyrnlylmethylhalide together with lithium metal.

EXAMPLE 1.0 g of radium chloride and 1.0 g of crystalline cupric chloride are dissolved in a mixture of 5 Q of purified dimethylformamide and 7.5 d of water. Heat to 100° C. in a stream of oxygen. 9 in 10 ml of purified dimethylformamide, maintaining a flow of oxygen.
．． 0 g (0,004'9 mol) of 10-undecenoic acid (
iv; the solution of R=l is added dropwise thereto at the same temperature and the mixture is stirred for a further 3 hours. Then it is cooled and poured into water. The mixture is extracted four times with a total amount of 2001R1 ether, the ether solutions are combined, washed with water, dried and the solvent is distilled off. The remaining yellow crystals are recrystallized from hexane.

Yield: 4.4.1 il (45%) of yellow crystalline product.

M, P,: 57-59°C (58-60°C in the literature, R
,E.

Bowman: J, Ch@m, Soc, 1950+
322).

IR(KBr): 1720.1705. (CO) $1
460°144, O, 1420t1360.1280°124 0. 1205 + 1 14 0 cnIo
lH-listening (cDcz, ): δ1.35 (12”) (
9m +6 CH2), 2.14(3H,5-CH3
), 2.35 (4H, Brq, 2CH2), 9.5
(IH.

br+s+C00FI) Ms:M+200 (1)+m/zl '82 (2)
, 125 (8).

97 (8), 71 (13), 57 (53,),
54(36).

44 (・100).

(1) Into an ether solution containing 3 g (0.07 mol) of diazomethane, 10.0 g (0.05 mol) of 10-oxoundecanoic acid is added at 0° C. under stirring,
The mixture is stirred at the same temperature for half an hour.

The solvent is distilled off and the residue is distilled off in vacuo.

Yield: 9.3. Colorless liquid with p (87).

B-p-: 158-160°C (10+nm) (Reference: 1
33~b&E, Vismara: 5ynthesis 1
980p751) IR (Film): 1730, 1715, (
Co).

1460.1430,1360,1230°1150
cm-'” 'H-NMR (CC).),: δ1.3 (12H+
m, 6 CH2) + 205 (3H, s, CH
3), 2.25 (4H.

br q , 2 CH2), 3.58' (3H, s,
OCH3) Ms: M214 (11), m/z
183 (28), 157 (47).

125 (85), 97 (38), 87 (29
).

83 (26), 74 (29), 58 (73),
55 (100), 41 (91).

(2) 13.5g of 1 in looml of anhydrous methanol
In a solution of 0-oxyundecanoic acid, ' O,, 51 nl
of sulfuric acid is added and the solution is boiled for 4 hours. The solvent is distilled off in vacuo, the residue is dissolved in 100 ml of ether,
The ethereal solution is washed with water and dried over magnesium sulfate. Distill the solvent and distill the residue in vacuo.

Yield: 12.0 fI (83%), product is identical to the compound prepared by step (1).

C1) Octadecyl triphenyl phosphonium pro-10
, 09 (0,03 mop-) of stearyl bromide and 8. OF (0.03 mol) of triphenylphosphine is dissolved in 20 ml of anhydrous benzene and the solution is refluxed for 48 hours. The solvent is distilled off, the residue is dissolved in anhydrous ether Group 20, and the crystalline product is filtered off and washed with anhydrous ether.

Yield: 14.06.9 (79%) of white crystalline product I
H-NMR (CDC73): δ0.85 (3H
, t, J=6Hz.

CH3) 11.28 (32H, m, 16 CH2
).

3.6 (2H + m + CH2), 7.75 (9H
2m, aromatic pr-)+ s, o (6H+m, aromatic pr.)0 0.8. @(0,033 mol) of sodium hydride,
20- of anhydrous dimethyl sulfoxide and the mixture is stirred at 70° C. for 1 hour under argon.

The solution was then cooled to room temperature and 16.0.9 (0,027 mol) in gQm of anhydrous dimethyl sulfoxide was added.
of octadecyltriphenylphosphonium bromide (■
;X=Br ) is added thereto under vigorous stirring. The reaction mixture was stirred for half an hour at a temperature between -40°C and 50°C, cooled to room temperature, and 4.6 g (0,021 mol) of methyl 10-oxyundecanoate in 10 ml of anhydrous dimethyl sulfoxide ( v*R=C
A solution of H3) is added dropwise thereto under vigorous stirring.

The reaction mixture is stirred for 8 hours at room temperature, 301 nl of distilled water is added to it and the mixture is extracted three times with a total volume of 301 nl of bexane.

The hexane solution is washed successively with water and saturated sodium chloride solution and dried over magnesium sulfate. The solvent was distilled off, the residual product was dissolved in 20% hexane,
The separated precipitate was filtered, the solvent was distilled off, and the residue was subjected to column chromatography (Kieselgel 60 r
Purify by benzene-methanol lo: 0.2).

Yield: 4.44 g (47%) cell free (according to liquid chromatography it is a 3-2 mixture of E and 2 isomers) IR (film): 1740 (Co), 1460.

1440.1380,1360,1220゜1180t
1160+1090, 1020c, t+'1H-NMR
(CC14): δ0.9 (3H, t t J=6Hz
, CH3).

1.26 (42 genera 1m, 21CH2), 1.55 (3H
2m.

CH5) + 1.8~2.4 (6H+ m + 3
CH2) + 3.05(31(+S tOCH5
), 5.0 (I Ht br t + J=6 h
z r C=CH).

Ms: M+450 (31), m/z419 (3),
418(8).

300 (3), 295 (10), 294 (40), 27
9(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 (3
4).

69 (83), 68 (25), 58 (80), 57 (5
1).

56 (100), 43 (66).

4.0 g of methyl (10-methyl-10-octacosenoate) in 200 methanol (Vll; R=
A solution of CI-I,) is hydrogenated in the presence of 1.0 g /e radium on a charcoal catalyst. A theoretical amount of hydrogen (approximately 21
When dissolved (0 ml, 4 hours), the melting medium is filtered, washed with methanol, the organic solutions are combined and the solvent is distilled off. The remaining oily product solidifies on standing.

Yield: 3.85 g (96.3%) IR (KBr) 91740. (Co), 1460, 1
440, 1380.

1360.1240.115Or, n-1゜”H-NM
R (CDCA3): δ0.88 (3H, t + J
=7Hz +C)I3)11.3 (52H1rn12
4 CH2, CH3, CH).

2, 2 (2H, t, J=7Hz, CH2),
3. ．． 68 (3H, a + OCH3).

Ms: M+452(100), rrV'z421(
3), 409(5).

199(8), 172(5), 167(6), 143(
19:>.

129(82), 111(6), 87(41), 83(
20), 75 (33), 74 (55), 71 (23).

69(27), 57(47).

f,) Preparation of 10-methyloctacosanoic acid (■; R=H) 3.0 g of methyl (10-methyloctacosanoate)
(■; R=CH3) was dissolved in a mixture of 30 ml (7) ml of water and 3 g of potassium hydroxide was added to the solution and the mixture was heated at 40° C. for 4 hours. Stir. It was then acidified with hydrogen chloride to a total volume of 150
Extract 3 times with mA' of ether.

The ether solution is washed with water, dried over magnesium sulphate and the solvent is distilled off. The residual product solidifies on standing.

Yield: 2.7 g (93%) M, p,: 31-32°C IR (KBr): 1710 (co), 1460114
401138011200.1140m-1゜'u-NMR (cDci5): δ0.87 (3H, t
, J=6Hz).

1 to 1.7 (5H, m, 24 CH2,0H3t C
f()12,1 (2H+ m v CH2).

Ma: M" 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-dimethyloftacosanoic acid (It;
R = H) in 2 oml anhydrous tetrahydrone run.
,0083 mol) of diisoprobylamine, 8
d 2M hexanezotelllithium solution (0,72,9,
0.011 mo/IJ butyllithium) is added at 0°C under argon and the mixture is stirred at 0°C for 20 minutes. Then 5 rnl of anhydrous tetrahydrofuran and 5 m
1.86 g in l of anhydrous hexamethylphosphoramide
(0,004 mol) of 10-methyloctacosanoic acid (■
; R=H) is added dropwise thereto and the solution is stirred at 5° C. for half an hour. Then 0.58.9 (0,255ml
, 0.004 mol) (D-methyl iodine is added to the mixture in one portion and the temperature rises to 20° C.) and the mixture is stirred at room temperature for 1 hour. Then, it was acidified with an aqueous hydrogen chloride solution, and the total amount of stone was 2001 rLl.

It is extracted four times with oil ether, the petroleum extract is washed successively with water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent is distilled off.

Yield: 1.311 (68 inches) IR (film): 1750 (Co), 1460,1
380°1230, 1140cm'.

'H-NMR (CD (J3): δ0.88 (3H,
t, J=7Hz).

1-1.7 (56H, m, 24 CH2p2CH3+
2CH).

Ms: M" 452. (69), m/z 438 (
7), 320(5).

199(10), 143(9), 130(11), 97
(17), 57 (32), 85 (15), 83 (24)
.

74 (100).

1.09 of 2,10-dimethyloctacosanoic acid (rt
; R=H) is treated with an ether diazomethane solution containing the diazomethane of No. 0.2. Distillation of the solvent gives a colorless oily product of 1.9.

IR (film): 1735 (CO), 1460,1
440°1385.1365+1240.1140t
yn-'.

'H-NMR (CDCJ!!3): δ0.89 (3H
, t, J=6 Hz.

CH3), 1.1~. 1.8 (56H+m+ 24
CH2+2CH3) *3.7 (3H, a e 0
CH5).

Ms: M” 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)
.

') Preparation of 3,11-dimethyl-2-nonacosanone (1) In 25 ml of anhydrous ether, 0.05.51 (8"
mmol) of lithium to a mixture of 2.0. @ (16 mmol) of trimethylsilylmethyl chloride is added under argon and the reaction mixture is boiled under stirring for 4 hours. It was then cooled to o'C and 1.5 g (3.2 mmol) of methyl (2
, 10-dimethyloctacosanoate) ([:R=CH
Pour the solution of 3) into it. The mixture is stirred at 0° C. for 4 hours, 5 mA' of methanol is added to it under cooling and it is stirred for a further 2 hours. It is then poured onto ice water and extracted with ether, the ethereal solution is washed successively with water and saturated sodium chloride solution and dried over magnesium sulfate. The solvent is distilled off and the residual product is purified by column chromatography.

Yield: O, 75 g (52 g) of colorless oil.

IR (film): 1715 (Co), 1460,1
450゜1380*1220,1170 twr-1゜1HNMR (CDCJ3): a O,84 (3H1
t, J=7Hz.

CH, )t 1.03 (3H, d, J=6 Hz, C
H3).

1.15-1.9 (49H, ml 24 C1■2.
CH), 2.02 (3H,s, CH3Co), 2.
3 (IH, m, cH).

Example 2 Boll's 16.6. in anhydrous tetrahydrofuran. !
To a solution of ii' (23 ml, 0.16 mol) of diisoglobylamine are added l Q Q ml of a 15% hexanebutyllithium solution. Then 15-10. in anhydrous hexamethylphosphoramide. ! A solution of 9 (0,054 mol) of 10-undecenoic acid is added to the mixture at 0°C. The reaction mixture was stirred for 20 minutes at a temperature between 0°C and 5°C, then cooling was removed and 9.3g (4-
1 mJ + 0.065 mol) of methyl iosite are added at such a rate that the temperature rises to 36°C.

The reaction mixture is stirred for 2 hours, poured into 60 ml of 1:1 hydrogen chloride solution and extracted with ether.

The ether extract is washed successively with hydrogen chloride solution, water, 5 g of sodium bisulfite, again with water and saturated sodium chloride solution and dried over magnesium sulfate. The solvent is distilled off and the residue is distilled off in vacuo.

Yield: s, sg (sochi).

n, p,: 100-104°C 10.01 tone IR (film): 1710 (Co), 1630, 1440°1
370.1270*970,90'5,880 cm'
.

'H-NMR (CDCJ3): δ1. l 5 (3
H, d, J=7, Hz.

CH3), 1.1-1.85 (12H*m, CH2)-
1,4-2.15 (2H, m, CH2), 2.34 (I
H, t, J=7Hz, CH), 4.85-5.15
(2H, m, C=CH2).

5.6-6.0 (IH, m, -CH=C).

13C-NMR (CDCl3): 16.8 (
CH3), 27.2.29.0 *24.2, 29
．． 4, 29.6, 33.6 (CH2), 33.
9 (allyl CH2)w 39.5 (CH), 114.
2, 139.0 (CH2-CH) 1183.7
(Co).

Ms: M 198 (13), 'm/z180 (13),
153(16).

125 (85), 97 (20), 83 (40), 73 (
100), 69 (90) + 55 (85), 41 (45)
.

27 (65).

Analysis: C1 □ H220 □ (198, 31) Calculated value: C attack - = 72.68 H article - 11, 18 Experimental value: C attack = 72
．． 46 H%=11.32(1) 28.5,! i!
(0,025 mol) of 30% hydrogen peroxide, 0.085
．． 9 (0,0001 mol) Radium(II) acetate
) and 10.0 g (0.05 mol) of 2-methyl-1
0-Undecenoic acid is dissolved in 80 ml of acetic acid and the solution is stirred at 80° C. for 6 hours. then cool it down and
Add 40 ml of water to it. The mixture is extracted with ether, the ether solution is washed successively with water and saturated sodium chloride solution, dried over sodium sulfate and the solvent is distilled off in vacuo. 10 g of crude brown 2-
Methyl-10-oxoundecanoic acid is obtained.

IR (film): 1710 (Co), 1460,1
230. -1'H-NMR (CDCA'3): 1.12 (3H
, d*J=7 Hz, CH3) 91.1-1.
8 (12Hv m p 6 CH2) +2.1 (
3H,8tCH3) e 2-3 (3H+ m v
CH2v CH).

(2) Crude 2-methoxyproduced as described above; ;-10
- Dissolve the oxal/decanoic acid in 70M absolute methanol, add 0.2 ml of sulfuric acid and boil the solution for 8 hours. It is then cooled and neutralized with solid sodium bicarbonate, the solution is distilled in vacuo, the residue is dissolved in ether, and the ether solution is dissolved in 50% sodium bicarbonate solution, Wash successively with water and saturated sodium chloride solution and dry over magnesium sulfate.

The solvent is distilled off and the residue is distilled off in vacuo.

Yield: 6.0p (53%) yellowish oil.

B-p: 146°C 10.8 m.

IR (Film): 1740.1710 (Co), 1
460°1440t136 (L1185, 1155c
m-1゜'H-NMR (CDC/3): δ1.0-1
．． 9 (12H, m, 6CH2)e 1.1 (31(
+ d, J = 7 HztCH3) + 2.05 (3
H+ B + CH3C0) +2.3~2.45 (
3H+ m + CH2+CH), 3.65 (3H9s
+0CH3).

Analysis: C13H2403 (228,34) Calculated value 20% = 68.38 Hchi = 10.59 Experimental value 2C% = 68
．． l] H = 10.452.2 g of sodium hydride (80 g of oily suspension, 0.073 mol) was added to 50 ml of anhydrous dimethyl sulfoxide and the mixture was heated until the evolution of hydrogen gas ceased. Stir at 70° C. under argon until (approximately 40 minutes). The solution was cooled to room temperature and dissolved in 40 mL of anhydrous dimethyl sulfoxide.
．． A solution of 0 g (0,067 mol) of octadecyltriphenylphosphonium bromide (W p X = Br) is added thereto. The mixture was stirred at 40 °C for half an hour, cooled to 20 °C, and 12.0 g (0,056 mol) of methyl (2-methyl-10-oxo-undecanoate) 1 in 20 TLl of anhydrous dimethyl sulfoxide;
A solution of R=CH6) is added thereto. The reaction mixture was stirred at room temperature for 6 hours, poured onto ice, and the total volume was 60
Extract 3 times with 0 ml of pentane. The pentane solution is washed with water, dried over magnesium sulfate and the solvent is distilled off in vacuo. The remaining 4I4 ester is purified by column chromatography.

Yield: 6.7.147.9%), according to liquid chromatography it is a 3:2 mixture of E and Z isomers.

IR (film): 1735 (Co), 1460.1
640°1380.1360,1230+1180+1
060. .

990 cm 0 1H-NMR (CDC/3): δ0.9 (3H?t
lJ=7H2゜CI(3)? 1.15 (3H, d
, J=6 H2) 11.2~1,8 (42H, m
, 21 CH2) , 1.4-2.3(sa+rr++
2cn2t CH) 13.55 (3H1a +0CH3
)y5.0 (IH, m, cH=c).

-) ) Production of (II; R=CH3) 200111
4.0 g of methyl (2910-dimethyl-10-octacosenoate) in anhydrous methanol (X; R
A solution of = CH3) is hydrogenated through 0.5 g of palladium on bone char catalyst. When a theoretical amount of hydrogen is dissolved (
(approx. 200d, 6 hours), filter the catalyst, wash the solution several times with methanol, mix the methanol solution and distill the solvent. 3. Same as the product prepared according to example x/h.
8. ! +(95.0%) of methyl (2°10-dimethyloctacosanoate) is obtained. It can be converted into a pheromone component bearing formula (I) as described in Example 1/i.

Ri White J: Continuation of White Page 1 (2I Inventor András Dancho Banka+)
-Country.

0 shots Akuteira Kisuta Hungarian country.

Masa, 24 [Phase] Inventor: Jurak, Hungary.

Budapest 18. Tartsai Utsa.

Budapest 3. Sentendrei Urarabudapest
10. Rabinowicz Uzza.

Claims (1)

[Claims] 1. A method for producing 3,11-dimethyl-2-nonacosanone having the formula (1): a.) General formula (n) H3CH3 (wherein R is a C1-5 alkyl group) ) with 2
, 10-dimethyloctacosanoic acid ester, in an ether-type solvent, preferably under cooling, with trialkylsilylmethyllithium, thus obtained general formula (Ill) (wherein R1, R2 and R3 may be the same or different, and C1-5
Represents an alkyl group. ) is reacted, preferably without isolation, with an aliphatic alcohol, or ) 2 having the general formula (■) in which R has the meaning defined above; lO-dimethyloctacosanoic acid ester is reacted with a solution of methylsulfinyl methide in trimethylsulfoxide in an ethereal solvent and the compound thus obtained is treated with a reducing agent, preferably without isolation. is reacted with aluminum amalgam, and the compound having the formula (1) thus obtained is separated from the reaction mixture.Patent 2 characterized in that trimethylsilylmethyllithium is used as the trialkylsilylmethyllithium. The method according to claim 1. 3. The method according to claim 1, characterized in that methanol is used as the fatty 11tj group alcohol. 4. 2,10-dimethyloctacosanoic acid ester having the general formula (■) (wherein R is as defined above).