JPS6051143A - Manufacture of 29-hydroxy-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 Industrial Application The present invention relates to 29-hydroxy-3,11-dimethyl-2
-Regarding a novel method for producing nonacosanone.

Problems to be Solved by the Prior Art and the Invention It is known that 3,11-dimethyl-2-nonacosanone having the formula (1) exhibits an extremely strong irritant response to male German cockroaches. It's a place.

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 becomes widespread and appears in new residential areas.

In addition to the aesthetic reasons for eradicating 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, poisonous insects that have survived despite eradication by chemical poisons can be trapped, thus preventing pest outbreaks.

Nishida et al. [R, N1ahida, H, Fukam
i & S, l5hii:Experientia
30, 978 (1974); Appl, En.
t.

Zool-10, 10 (1975); R, N15h
jda, T., 5ato, Y., Kuwahara,
H, Fukami & S, l5hll: J.
Chem.

Ecol, 2, 449 (L976): Agr.
, Bias, Chem, 40.

1407 (1976)) reported on the extraction of German cockroach pheromones. Sexually mature I! ! 1t
from the epidermal wax of 29-hydroxy-3,11-dimethyl-2-nonacosanone with formula (1) and
Two components identified as 3,11-dimethyl-2-nonacosanone with Xl) 1 were separated. Both compounds elicit wing flotation and reorientation responses from adult males. It has been demonstrated that the compound having formula (1) is highly active.

Later, Sora (K, Marl, T, Suguro
& S, Mashuda: Tetrahedron-
G., 1329 (1981)) synthesized all possible stereoisomers of both pheromone components. It has been shown that natural pheromones are of the (3S, 115) configuration.

The compound having formula (1) was first developed by Nishida et al. (R,N15
hjda.

T., 5ato, Y., Kuwahara, H.
, Fukami & S, l5hii: Agr, B
iol, Chem, 40 (7), 1407 (
(1976)). They reacted the anion obtained in the reaction with ethyl methyl acetoacetate shari-butyrate with 1,6-diprosohexane.

The thus obtained ethyl A・(8-bromo-2-acetyl-
2-methyl-ocucnoate) was hydrolyzed and then decarboxylated to give 9-bromo-3-methyl-2-
gave nonanon. The ketone was converted to its ethylene ketal, which was reacted with the anion obtained from ethyl acetoacetate. Ethyl (2-acetyl-9-methyl-10-oxoundecanoate) thus obtained
of ethylene acetal was subjected to alkaline hydrolysis and then decarboxylation. The thus obtained 3-methyl-
2. To 11-dodecanedione-2-ethylene acecool was added is-tetrahydropyranyloxyoctadecylmagnesium bromide obtained from 1,18-dihydroxydioctadecane in four reaction steps. The ethylene acetal of 3,11-tmethyl-11-hydroxy-29-tetrahydropyranyloxy-2-nonacosanone thus obtained is dehydrated to obtain 3,11-tmethyl-29-hydroxy-11-nonacomon-2. -ol was subjected to catalytic hydrogenation to give a pheromone component having formula (1).

The method of Burgstahler et al. (A.W. Bu
rgstahler.

L.O. Weigel SM. E. Thunder
s, C. G. Shaefer.

W. J. Bell & S. B. Vuturo
: J. Org. Chem-± et al. 566 (197
According to 7)), the benzyl ether of 4-bromo-1-buknol was reacted with lithium acetyl P in the presence of ethylenediamine. The lithium salt of the acetylene derivative thus obtained was alkylated with 1,12-nopromododecane. 1-Bromo18-benzyloxy-13-
Octadesine was obtained which was converted to the corresponding phosphorane.

In the next step, the Quitschich reaction is carried out with phosphorane and 9-
bromo-2-nonanone. The bromo compound thus obtained was used together with sodium hydride for the alkylation of the anion obtained from 2-methylacetoacetate. The subsequent catalytic hydrogenation was performed using 3.11-tmethyl-3-
gives ethoxycarbonyl-29-hydroxy-2-nonacosanone, which is hydrolyzed and decalcified. When xylated, it gave the desired compound of formula (1).

Later, Burgatahler et al. painstakingly developed an improved method for producing compounds having formula (1) (
A. W.

Burgstahler, M. E. Thunder
s SC. G. Shaefer &L. 0. Waig
el: Synthesis, 405 (1977)
). They employed phase transfer methylation of pennolacetoacetate using tetra-n-butylammonium hydrogen sulfate catalyst to give pennol 2-methyl-3-oxtubuctuate, and then 26-benzyloxy-8- Further alkylation with methyl-8-hexacomon-21-ynylbromide gave benzyl (2-acetyl-2,10-dimethyl-28-benzyloxy-10-oftacocene-
23-inoate) was produced. This compound was then subjected to catalytic reduction to give 2-acetyl-2,10
-Dimethyl-28-hydroxyoctacozanic acid is decarboxylated to produce a pheromone component having formula (I).

Mori et al. (K. Mori SS. Mosuda,
T. Sugar: Tetrahedron Le
tters, 3 4 4 4 (1 9 7 8
) ; Tetrahedron.

, No. 7, 1329 (1981)) discloses 29-hydroxy-3,11-tmethyl-2-nonacosanone having the formula (1) and 3,11-tmethyl-2-nonacosanone having the formula (XI).
A method for the stereocontrolled synthesis of all possible stereoisomers of nonacosanone was presented. The basic step of their synthesis is the presence of dilithium sawtetrachloride, each with 4
Chiral Grignard reagents and chiral tosylates derived from R- and 4S-methyl-5-hexenyl bromide (in the case of the pheromone component with formula (1), 5 R- and 58-methyl-23, respectively) -benzyloxy-
8-tricosinyl tosylate). To produce 4R-methyl-5-hexenyl bromide, one of the binding components, 3R-7-methyl-6,7-epoxy-1-heptene was oxidized with periodic acid to form the corresponding aldehyde. which was then reduced with lithium aluminum hydride. 4R-methyl-5 thus obtained
-Hexanol was converted to the corresponding tosylate, which was treated with lithium bromide in A7T. In order to prepare the counterpart of the compound thus obtained, 7-phenyl-4R-methylbexanoic acid ester was mixed with chromium oxide (Vt
) to form a half ester. The silver salt was subjected to Hunssieker reaction to give methyl (4S-methyl-6-bromohexanoate). This is reacted with o-nitroselenophenol, the selenyl group of the compound thus obtained is removed by oxidative elimination, and the olefin thus obtained is reduced with lithium aluminum hydride.
The corresponding alcohol was provided and the tosylate was converted to 4S-)'fk-5-hexenylzolomide in the usual manner.

In comparison to the 4R- and 4S-methyl-5-hexenyl bromides thus obtained, S- and R-23-benzyloxy-5-methyltricos-8-ynyl tosylate, respectively, were used as linking components. To prepare R-) sylate, tetradecane-1,14-diol was converted to the corresponding monobenzyl ether. The tosylate was treated with lithium bromide to give 14-benzyloxytetradecanyl bromide. Halodane conversion with sodium iodide gave the corresponding iosito. R-←)
-Used for alkylation of R-citronellyl acetylene converted to X4 from citronellyl iodide. The alkylated product was epoxidized with m-chloroperbenzoic acid. Oxidation of the epoxide thus obtained with periodic acid is
4R-methyl-21-benzyloxy-7-heneicosinal was obtained. Elongation of the i t;+ carbon of this aldehyde, followed by reduction with lithium aluminum hydride,
This gave 5R-methyl-23-pennoloki 7-8-tricosinol, which was tosylated in the usual manner.

S-23-benzyloxy-5-methyltricos-8-
To produce inyl tosylate, 7-formyl-5
8-Methylheptyl acetate was converted to olefin by Wittig reaction.

Addition and subsequent elimination of bromine produces (7-hydroxy-3
8-methylheptyl)acetylene, which is converted into 14-
Alkylated with benzyloxytetradecanyl bromide. Acid treatment of this latter compound gave S-23-pennoloxy-5-methyltricos-8-ynol, which was converted to the desired tosylate.

In order to obtain all possible stereoisomers of the pheromone component with formula (1), R- and S-23-pennoloxy-5-methyltricos-8-ynyl tosylate, respectively, are converted into R- and S-(→-methyl Coupling was carried out with a Grignard reagent derived from Roux-en-5-enyl bromide.

In the case of both heptadromone components [formulas (]) and (X)], the compound with the (:3S, 115) configuration proves to be identical to the natural sex of the poisonous insect. did. The authors found important 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 method for the production of pheromone components having formula (1), which can be easily carried out on an industrial scale.

Means for solving the problems According to the invention, 29-hydroxy-
3,11-tmethyl-2-nonacosanone has the general formula (n
) (In the formula, R represents a C1-5 alkyl group, and Y represents a detrahydrobilanyl or 2-ethoxyethyl group.) A novel alkyl (2,10-dimethyl-28-
a) alkyl (2,10-dimethyl-28-octacosanoate) having general formula (n) in an ethereal solvent, preferably under cooling, from trialkylsilylmethyl Reacting with lithium, the intermediate thus obtained having the general formula @) (wherein R, , R2 and R3 each represent a 01-4 alkyl group), preferably without isolation, or b) reacting with an aliphatic alcohol and treating the compound thus obtained having the general formula ( ) (in which Y is as defined above) with an acid; or b) the general formula (■) (formula Medium, R
and Y are as specified above. ) is reacted with a solution of methylnurfinyl methide in dimethylnurphoxide in an ethereal solvent and the compound thus obtained is treatment with a reducing agent, preferably aluminum amalgam, and the thus obtained compound having the general formula (IV), in which Y is as defined above, with an acid; (compound having general formula (1)) from the reaction mixture.

According to step a) of the process according to the present invention, a compound of general formula (II) is reacted with trialkylsilylmethyllithium in an ethereal solvent, preferably under cooling. The general formula thus obtained @)
It is not necessary to isolate the intermediate having , and it can be reacted with an aliphatic alcohol, preferably methanol, in the reaction mixture produced. The protecting group of the general formula (I) thus obtained can be removed by treatment with an acid (for example, p-toluenesulfonic acid).

According to step b) of the process according to the invention, general formula (II)
The compound having 1 is reacted with a solution of methylsulfinylmethide in dimethylsulfoxide. Methylsulfinyl methide can be prepared from dimethyl nulphoxide with a strong base, preferably sodium hydride, at temperatures below 70°C.

The intermediates obtained in the reaction of compounds of formula (1) with methylnurfinyl methide 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 protecting group of the thus obtained compound having the general formula ([V)] can be removed by treatment with an acid.

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

The compounds with general formula (n) used as starting materials for the synthesis have hitherto not been described in the literature. To manufacture them, we have painstakingly developed two methods. According to one of the first developments, 10-undecenoic acid, an inexpensive commercial product, is reacted with an alkyl lithium and the dianion thus obtained is alkylated with methyl iosite, thus obtaining a product having the formula (V) 2-Methyl-10-undecenoic acid is converted to the corresponding ether. It is then converted with hydrogen peroxide in the presence of a catalytic amount of a palladium salt into a compound having the general formula (b) in which R is an alkyl group. This latter compound is then combined with a strong base, preferably butyllithium, to a compound of the general formula (6) % (wherein X represents halodane and Y represents a tetrahydrobicinyl or 2-ethoxyethyl group). The thus obtained compound having the general formula (4) (wherein R and Y have the meanings defined above) is subjected to catalytic reduction to give the general formula (4). A compound having formula (If) is obtained.

According to our second method, which we have worked out for the preparation of compounds with the general formula (It), the entel of 10-oxycundecanoic acid is reacted with a phosphorane derived from a phosphonium salt with the general formula 〇D. The thus obtained compound having the general formula (IX) (wherein Y and R are as defined above) was subjected to catalytic reduction to give the general formula (IX) (wherein Y and R are as defined above).
3) A compound having the formula (wherein Y and R are as defined above) is hydrolyzed to the corresponding carboxylic acid. This latter compound is converted to the dianion with a strong base, preferably methyllithium. Its subsequent reaction with methyl iosito gives the desired compound having general formula (U).

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

Example The invention will be illustrated in detail by the following non-limiting example.

Dissolve 3.0 (001 mol) of 18-chlorooctadecanol in 20 ml of anhydrous benzene and add 1.
OF (0.0j2 mol, 1.1 ml) ty)
Schich Pr:tpyran and 0.05p p-toluenesulfonic acid were added to the solution and the reaction mixture was heated at room temperature for 4 hours.
Stir for an hour. It is then diluted with ether, washed successively with 5% sodium bicarbonate solution, water and sodium chloride solution, dried over magnesium sulfate, the solvent is removed directly and the residue is distilled.

Yield: 3.5 no (90%) 13, p, : i 24-126°C 10.15 mmI
R()-1lum): 1025.720cm-'H-NM
R(CD(Jρ: δ1.15-2.0(38H9mlC
H2): 3.25-4.0 (4) i9m, CH2-0)
:3.52(2H,t, J=7Hz, CJ(2-
C#): 4.57 (IH, m, -0-CI-0).

Analysis: C23I (4502C7 (389,067) Calculated value: C%=71.0OH911+=11.66C
ff1%=9.11 Experimental value: C%=71.21 H%
=11.5I C7%=9.02ax)1.95F(0
,005 mol) of 18-chlorooctadecanyltetrahydro-2-pyranyl ether was dissolved in 15 ml of methyl ethyl ketone and 1.12 F (0,0075 mol) of porous sodium iodide was added to the solution. , boil the mixture for 20 hours. Then it is cooled, the separated salt is filtered and the P liquid is evaporated in vacuo.

Dissolve the residue in ether and mix the ether solution with water,
Wash successively with 5 g of sodium bisulfite solution and sodium chloride solution, dry over magnesium sulfate and evaporate in vacuo. The crude 18-iodooctadecanyltetrahydro-2-hyranyl ether is purified by chromatography (penzene-acetone 10:1).

Yield: 1.9P (90%) TLC: Rf=0.55 (benzene-acetone 10
:1) IR (film): 1025cm-'”H-
N)/JR, (CDC), ): δ1.15-2.0 (
38H1m, CH2): 3.05~4.0(6T(,
m, -CH20, -CH2-I); 3.09. (2H1
t+J=6I(z+-CH5I):4,.
44 (IH, m, 0-CH-0).

Analysis: C23H450□I (480,518) Calculated value:
C←57.49 H←9.44 I←26.41 experimental value; C←57.63 H furnace 9.52 I←26.12a3
) 2.4 (0,005 mol) of 18-iodoocucudecanyltetrahydro-2-pyranyl ether and 1.3
1P (0,005 mol) of triphenylphosphine,
50. d in anhydrous acetonitrile, 50 to 70
Boil for an hour. The solvent is then evaporated in vacuo. The remaining honey-like product is decanted several times with ether, the solvent is removed in vacuo and it is dried.

Yield: 2.2P (60 pieces) of hydrogenated oil IR (film): 1590.1110,730,6
90cy++-''H-NMR (CDC)5): δ1.
1-2.0 (38H9m, CH2).

3.1-4.1 (6H, m, ~CH2-0, -C
)I2-P).

4.56 (IH, rn, 0-CIIO2°7.5-8.
2 (15H, m, aromatic) analysis: C41H6oO2
PI (742,614) calculated value: CfP66.29
H%=8.14 P←417■←17.08 Experimental value:
C%=66.41) 1%=8.25 PI3.06
Production of H%=16.91 7.4. ? (10 mmol) of 18-(2-tetrahydropyranyloxy)-octadecanyltriphenylphosphonium iosite was dissolved in 60 ml of anhydrous tetrahydrofuran, the solution was cooled to 10°C, and 10 mmol of butyllithium ( 6.3 ml of 15% hexane solution) are added thereto under inert gas with cooling. Sakura-red solution was stirred at the same temperature for 30 minutes,
lQmA of 2.2F (10
A solution of methyl (2-methyl-10-oxoundecate) (Vi; n=cn3) in 3 mmol)
Add to it within 0 minutes. The reaction mixture is stirred for a further 5 hours at room temperature. It is then quenched with 10 polyammonium chloride solution, extracted with petroleum ether and the organic phase is washed successively with 5 parts sodium bicarbonate solution, water and sodium chloride solution, dried over magnesium sulfate and evaporated. let Approximately 3.57 g of crude product is obtained.

The crude product was also prepared by diluting the reaction mixture with 1001 nl of hexane and pouring the solution onto a short Kieselgel gel.
It can be isolated by flash chromatography using a TM column. The solution thus obtained is evaporated in vacuo to give approximately 2-2.5 mm of crude product. It can be purified by column chromatography (benzene-acetone 10:0.5).

Yield: 1.2F (21 lines) colorless oil TLC: Rf=0.6 IR (film): 1735 (Co), 1460,1
375,1160°1030crn-1''H-NMR (CDC)5): δ1.0~], l3
(54B,,m,CH2-,2-C)]3).

1.8-2.1 (4111m, Cf (to 2)).

2.3 (IH, m, CII-Coo).

3.25-4.1 (4H, rn, cl(20).

3.68 (3H, s, CH300C).

4.5-4.65 (IH, m, 0-CH-0).

5.1 (IH, m, -CH=).

Analysis; He6H6604 (564,94) Calculated value: C%
=76.54 H←12.13 Experimental value: C←76.67
H←1195o, 56p (1 mmol) of methyl (2
,10-trimethyl-28-(2-tetrahydropyranyloxy)=10-octacosenoate] at 20 r
rri of anhydrous methanol and the solution is added to 0.32 palladium on bone char catalyst mixed in 10 ml of anhydrous methanol under an inert glass.

The reaction mixture is stirred at room temperature under hydrogen. Strain the catalyst and evaporate the furnace liquid.

Yield: 0.53F (96%) colorless oil IR()(/l/mu) = 1735(Co), 1460c
m-1'1i-N dish (CDC7ρ: δ0.82 (3H
1d+J=6Hz, 10 CHs).

1.0-1.8 (58H,m, -CH2-,2-C
13).

2.3 (IH, m, CM-COO).

3.2-4.1 (4iI, m, cl(2o).

3.65 (JH9s, CH300C).

4.5-4.65 (IH, m, 0-CH-0).

Analysis: C, H7oO4566,958) Calculated value: C
%-76, 26H furnace 1244 experimental value: C←76.05
0.12y, (20 mmol.

Add 0.47) of lithium dispersion. 0.30F (
0.34 rnl, 2.5 mmol) of trimethylsilylmethyl chloride is added thereto under inert gas,
Boil the mixture for 2.5 hours. It is then cooled and precipitated. Residual lithium is separated from the trimethylsilylmethyllithium solution by pressurizing it with inert gas into another flask. Then 5 m,! 0.5F (1 mmol) of methyl [2,10-trimethyl-28-('2'-
A solution of octacosanoate (tetrahydropyranyloxy) is added to the solution at 0°C. The reaction mixture is stirred at 0° C. for 2 hours, 21 nl of anhydrous methanol are added to it under cooling and the mixture is stirred at room temperature for 15 hours. It is quenched with water, extracted with ether, the ethereal solution is washed with ammonium chloride solution, water and sodium chloride solution, dried over magnesium sulphate and evaporated in vacuo. A crude product of 0.5% was obtained, which was chromatographed (benzene-acetone 10:0.2
).

Yield: 0.26 F (45 inches) colorless oil 1, R (7 inches): 1705 (Co), 1460,4080.103
0i'.

'H-NMR (CDC) 3): δ0.82 (3H, d,
J==6Hz, 11C horse).

1.05 (3H+d+, J=7Hz*3C
Hs) +1.1~1.9 (55H2m, CH2)
.

2.05 (3H+ se CHs r Co )
+2.4 (LH, m, CHCO), 3.2~4
．． 1 (4H.

m, -CH20), 4.5-4,65(IHlo-CH
−0, m).

Analysis: C66H7oO2 (550,95) Calculated value: c
hys, 4s H%=12.80 Experimental value: C←78.2
9 H←12.610.0551 p-toluenesulfone i is dissolved in a mixture of 5 m methanol and 0.5 m water.

0.277 (o, 5 mmol) of 3,11-tmethyl-
29-(2-Tetrahydropyranyloxy)-2-nonacosanone (Germany) is added to the solution and the reaction mixture is stirred at 60° C. for 4 hours. It is then cooled, the solvent is removed in vacuo, the residue is dissolved in ether, washed successively with 50% hydrogen carbonate solution, water and sodium chloride solution and dried over magnesium sulfate. ,
Remove the solvent in a vacuum. 0.229 of the crude product is obtained (m, p,: 34-38 °C). That (-20)~
It can be recrystallized from petroleum ether at (-30)°C.

Yield: 0.22 (80%) M, p,: 41-42°C (41-43°C in literature
.

A, W, Burgstahler et al., J, Org.
, Chem, 42.

566 (1977)).

IR (film): 3350 (OH), 1715 (Co
), 1040d'.

1H-NMR (CDC), ): δ0.82 (3H, d-
J=6Hz, 11 CH3).

1.04 (3H, d, J=7Hz, 3CHh)
.

1.1 to 1-6 (49H, m, CH2).

2.01 (3H, s, CH3Co), 2.34
(IH.

m, CH-Co), 3.52 (21(, t, J=6
Hz, CH20).

Analysis; C31H6□02 (466,84) Calculated value: C←
79.76 H←13.39 Experimental value: 79.62 to C
H%=13.61 Example 2 Preparation of 29-hydroxy-3,11-methyl-2-nonacosanone Preparation 7.44 (10 mmol) of 18-(2-tetrahydropyranyloxy)-oftadenylphonufonium iodine (Vll; X=l, Y=THP group), 60
Dissolve rLl in anhydrous tetrahydrofuran. The solution is cooled to 10° C. and 10 mmol of butyllithium (6.3 ml, 15% hexane solution) are added to it under argon with stirring. The mixture was stirred at room temperature for 30 minutes, and 2.0% was added to 10 ml of anhydrous sodium chloride run for 30 minutes. A solution of IP (10 mmol) in methyl-(10-oxoundecanoate) was added at 10 °C within 30 min.
Add to it. The reaction mixture is stirred at room temperature for 5 hours, poured into a 10 part ammonium chloride solution and extracted with hexane. The hexane solution is washed successively with 5 parts sodium bicarbonate solution, water and saturated sodium chloride solution, dried over magnesium sulfate and the solvent is distilled off. The residual product is purified by column chromatography.

Yield: 1.1 (20%) pale oil TLC: Rf=0.58 (benzene-acetone 1
0:05) In (film): 1735 (Co), 14
60. 1375゜1160.1030cn+0'H-NMR (CD(+3): δ1.1~1.8(5
1H,m, CfT2).

1.8-2.1 (4H, m, C112CF).

2.28 (2H9t, J=8Hv, CH2COO
) +3.25~4=1 (4H, m, CH20)
.

3.68 (3H1s, CHsooC).

4.5-4.65 (IJ-I, m, 0-CH-0).

5.1 (H(, m, -CJ(=).

Analysis: C35H6604 (550,91) Calculated value: C
←76.30 H Chi 12.07 Experimental value: C%=76
．． 18 H coefficient = 12.21 or less diwhite b) Methyl (io-methyl-28-(2-tetrahydro) 0.559 (1 mmol) of methyl [10-methyl-28-'(2- Tetrahydropyranyloxy)-10-octacosenoate]
The solution is hydrogenated through a 0.3 F Novum catalyst on bone charcoal. When the theoretical amount of hydrogen was converted to HF4 (3 hours, 24 ml), the catalyst was filtered and washed with methanol.
The entire methanol solution is combined and evaporated in open air.

Yield: 052 li (95 も) IR (film): 1735 (CO), 1460,13
80,1260°1075, 1030cy+0"H-NMR (CD(+3): δ0.82 (dH9
d, J=8Hz, 11 CHx).

1.0-1.9 (55H, n+, CH2-).

2.3 (2H1t + J-7Hz + CH2Co
o).

3.2~4.1 (4,111, CH20) *365
(3H18,C■■300C).

4.5-4.65 (IH, m, 0-CH-0).

Analysis” C35H6804 (552,93) Calculated value: C
←76.02 H←12.39 Experimental value: C←75.88
Preparation of 055 (1 mmol) of methyl [10-methyl-28
-(2-tetrahydropyranyloxy]-octacosanoate] and 10 ml of IN sodium hydroxide solution is quenched at room temperature for 6 hours. It is then dissolved in 12 TL of IN hydrogen chloride solution. Pour and extract with ethyl acetate, wash the organic phase successively with water and sodium chloride solution, dry over magnesium sulphate and evaporate in vacuo.

The remaining cured product can be used for the next reaction step without purification.

Yield: 0.45F (83%) IR (film): 1715(Co), 1460,1
380, 1200° 1080, 1030crn.

'H-NMR (CDC) 5): δ0.82 (3H9d
, J=8flz, 11 CH3).

1.0-1.9 (55H, m, cH2), 2.3
(2H9t, J=7Hz, CHs Coo”)
, 3.2-4-1 (4H, m, CH20), 4-5~
4.65 (IH-m, 0-CH-0).

A solution of 0.31.7 (3 mmol, 0.437 d) of diisoglobilamine and 1.9 ml (3 mmol) of 15-thihexanegutylithium was added to 10 m
Measure and add to J of anhydrous tetrahydrofuran. 3nr
A solution of 0.54 F (1 mmol) of 10-methyl-28-(2-tetrahydropyranyloxy)-oftacosenoic acid in 1 of hexamethylphosphoramide was added to the reaction mixture at 0°C and it 2 at a temperature between 0℃ and 5℃
Stir for 0 minutes. Warm the mixture to room temperature and add 0.1
7F (1.1 mmol, o, osy) of methyl iosodide is added thereto and the reaction mixture is stirred for 2 hours. It is then quenched by pouring it into a 10% ammonium chloride solution and extracted with ethyl acetate.

The organic phase is washed successively with ammonium chloride solution, water and brine, dried over magnesium sulphate and evaporated in vacuo. 0.4y of crude acid was obtained, which was esterified with diazomethane and the entel thus obtained was chromatographed (benzene-acetone 10:0
．． 5).

0.352 (65%) of a colorless oily product was obtained, which corresponds to Example 1. Identical to the product obtained by /e.

It can be converted into the pheromone component of formula (1) in the manner described in Example 1.

Below margin Continuation of page 1 0 shots clear András Dancho Hungary.

0 shots Attila Kisuta Hungarian country.

Square 7.24 ■Inventor: Felenc Yurak, Hungary.

Budapest I & Tartsai Uzza.

Budapest 3. Sentendrei Urarabudapest
10. Rabinowicz Uzza.

Claims (1)

[Claims] 1. 29-hydroxy-3,11-di)f-2- having the formula (1)
A method for producing nonacosanone, the alkyl (2,10 -dimethyl-28-octacosanoate) in an ethereal solvent, preferably under cooling, with trialkylsilylmethyllithium, thus obtained with the general formula ) (wherein R1, R2 and R3 are , each representing a 01-4 alkyl group) is reacted, preferably without isolation, with an aliphatic alcohol, and the intermediate thus obtained has the general formula (), where Y is as defined above. or treating a compound having the general formula (■) (wherein,
R and Y are as specified above. ) with alkyl (2,10-dimethyl-28-octacosanoate)
is reacted with a solution of methylsulfinyl methide in dimethyl nulphoxide in an ethereal solvent, and the compound thus obtained is treated with a reducing agent, preferably aluminum amalgam, so that the general formula ([V)(
In the formula, Y is as defined above. ) with an acid; and separating the compound thus obtained having the formula (1) from the reaction mixture. 2. Trimethylsilylmethyl as trialkylsilylmethyllithium The method according to claim 1, characterized in that lithium is used. 3. The method according to claim 1, characterized in that methanol is used as the aliphatic alcohol. 4. The method according to claim 1, characterized in that lithium is used. The method according to claim 1, characterized in that p-)luenesulfonic acid is used. 5. General formula (■) (in the formula, R and Y are υ as defined above)
It is. ).