JPS6247166B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing cis-olefins, more specifically, the general formula [In the formula, R ¹ is a lower alkyl group, R ² is a hydrogen atom or an organic residue that can serve as a protecting group for a hydroxyl group, and n is 8-8.
Each represents 10 integers. ] Cis-
The present invention relates to a method for synthesizing olefins with high purity and high yield. In the above general formula (1), specific examples of the lower alkyl group represented by R ¹ include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, etc., and the protecting group for the hydroxyl group represented by R ² Examples of organic residues that can be used include an alkyl group that may have an aralkyloxy group, an alkoxy group, or an alkylthio group as a substituent, an alkenyl group, an alkynyl group, an aralkyl group that may have a halogen atom as a substituent, Examples include an alkylsilyl group, a heterocyclic group, a heterocyclic alkyl group, an acyl group, and a nitro group. Examples of the alkyl group that may have an aralkyloxy group, alkoxy group, or alkylthio group as a substituent include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, benzyloxymethyl, α-phenethyloxymethyl, Examples include methoxyethyl, methoxymethyl, and methylthiomethyl groups. Alkenyl groups that may have a halogen atom as a substituent include vinyl,
Examples include allyl, 2-butenyl, 2-heptenyl, and 3-chloroallyl groups. Examples of the alkynyl group include ethynyl group, 1-propynyl group, and 2-propynyl group.
Examples of the aralkyl group include benzyl, α-phenethyl, β-phenethyl, α-naphthylmethyl, triphenylmethyl, and anthramethyl groups. Examples of the alkylsilyl group include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, and pentamethyldisilyl. Examples of the heterocyclic group include 2-tetrahydropyranyl group. Examples of the heterocyclic alkyl group include furfuryl and pyridylmethyl groups. Examples of acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl,
Alkanoyl groups that may have halogen atoms as substituents such as pentanoyl, hexanoyl, trifluoroacetyl, trichloroacetyl, tribromoacetyl groups, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, tert
- Substitution of alkoxycarbonyl groups such as butoxycarbonyl groups, arylcarbonyl groups such as benzoyl and p-nitrobenzoyl groups, alkyl groups such as carbamoyl, methylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl, and benzylcarbamoyl groups, aryl groups, or aralkyl groups Carbamoyl group, methylthiocarbonyl, ethylthiocarbonyl, propylthiocarbonyl, isopropylthiocarbonyl, butylthiocarbonyl, alkylthiocarbonyl group such as tert-butylthiocarbonyl group, cis-2-methyl-△ ² -butenoyl, which may have as a group Examples include groups. The cis-olefins represented by the above general formula (1) are compounds useful as intermediates for synthesizing the sex pheromone of the C. chinensis species. Conventionally, as a method for producing cis-olefins represented by the above general formula (1), for example, as shown in the following formula, 9-9-
A method of hydrogenating tetradecyn-1-ol is known [Minoru Uchida, Kenji, Mori
and Masanao Matsui, Agric.Biol.Chem., 42
(5), 1067-1070 (1978)]. However, in the above method, cis isomer accounts for 90-93%
and trans isomer mixed at a ratio of 10 to 7% 9
-tetradecen-1-ol is obtained. It is also known that only the cis-form is effective as a sex pheromone for the cockroaches, and if more than 2% of the trans-form is mixed in, the attraction effect for the cockroaches decreases [Takeda Research Institute Bulletin, Vol. 36 , No. 3/4, pp. 288-294 (1977)], therefore, the 9-tetradecene-1 obtained by the above method has a cis isomer content of 90 to 93%.
-ol is difficult to use as it is as an intermediate for synthesizing the sex pheromone of the Physcomitrella sp. Therefore, a separation method using a silver nitrate column has been applied to separate the cis isomer and the trans isomer, but the separation operation is complicated and, moreover, only a small amount of the target 9-tetradecen-1-ol, which has a high content of the cis isomer, is produced. In addition, there are many problems in the post-treatment of the silver nitrate column used. Therefore, there is a need for the development of a new synthetic method that can industrially advantageously produce cis-olefins represented by the above general formula (1) with high purity and high yield through simple operations. is the current situation. In order to meet the above-mentioned needs, the present inventors have conducted intensive research on a method for producing cis-olefins represented by general formula (1). As a result, it was found that the desired objective could be achieved when alkynes represented by the following general formula (2) were hydrogenated in the coexistence of Lindlar's catalyst and amines. The present invention was completed based on this knowledge. That is, the present invention provides R ¹ C≡C(CH ₂ ) _o OR ² (2) [wherein R 1 is a lower alkyl group and R ² is a hydrogen atom or a hydroxyl group-protecting group ^] in the coexistence of a Lindlar catalyst and an amine. The organic residues that can be
Each represents 10 integers. ] General formula characterized by stereoselective hydrogenation of alkynes represented by [In the formula, R ¹ , R ² and n are the same as above. ] It concerns the manufacturing method of cis-olefin represented by these. In the present invention, the hydrogenation of alkynes represented by general formula (2) is carried out in the presence of Lindlar catalyst and amines. As the Lindlar catalyst, a wide variety of conventionally known catalysts can be used, and a typical example is one composed of three components: palladium, calcium carbonate, and lead. This 3
The composition ratio of the components is not particularly limited and can be appropriately selected within a wide range, but it usually contains palladium in an amount of about 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the calcium carbonate carrier. It is preferable to use a catalyst containing lead, usually about 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the carrier. The amount of Lindlar catalyst to be used is not particularly limited and can be appropriately selected from a wide range, but usually the Lindlar catalyst is used in an amount of about 0.1 to 30% by weight, preferably 1 to 30% by weight, based on the alkynes represented by general formula (2). It is best to use proportions. In addition, a wide variety of known amines can be used, specifically methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, n-
Butylamine, di-n-butylamine, isobutylamine, hexylamine, dihexylamine,
Monoamines such as heptylamine, octylamine, dioctylamine, nonylamine, n-amylamine, isoamylamine, decylamine, dodecylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-
Diaminopentane, 1,8-diaminooctane,
Polyamines such as N-methyl-diaminoethylene, N·N-dimethyl-diaminoethylene, N·N-dimethyl-diaminoethylene, N·N-diethyl-diaminoethylene, tetramethylenetriamine, hexamethylenetetramine, cyclohexylamine, dicyclohexylamine Examples include alicyclic amines such as morpholine, piperazine and piperazine, and aromatic amines such as dimethylaniline, pyridine and quinoline. Among these, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, n-butylamine, di-n-butylamine, isobutylamine,
Ethylenediamine, 1,3-diaminopropane,
Monoamines or polyamines such as 1,4-diaminobutane and 1,5-diaminopentane are preferred.
The amount of amines to be used is not particularly limited and can be appropriately selected from a wide range, but usually the amount of amines is 0.005 to 1 mole of the alkyne represented by general formula (2).
It is preferably used in a proportion of about 1 mol, preferably 0.01 to 0.25 mol. Hydrogenation of alkynes represented by general formula (2) is carried out without a solvent or in a suitable solvent. Any solvent that does not adversely affect the reaction can be used, specifically methanol, ethanol,
Examples include lower alcohols such as isopropanol, hydrocarbon solvents such as hexane and cyclohexane, ethers such as dioxane and tetrahydrofuran, acid esters such as ethyl acetate, and mixed solvents thereof. Among these solvents, lower alcohols are particularly preferred. The hydrogenation reaction is carried out under cooling,
Although the reaction can be carried out either at room temperature or under heating, the reaction normally proceeds suitably at about -30 to 50°C, preferably about 0 to 10°C. The reaction can be carried out either under increased pressure or normal pressure, and is usually carried out under normal pressure to 300 atmospheres, preferably normal pressure to 10 atmospheres. The above reaction is generally completed in about 1 to 10 hours. The olefins represented by the general formula (1) thus produced can be easily isolated and purified from the reaction mixture by conventional purification means such as distillation and solvent extraction. When alkynes represented by general formula (2) are hydrogenated by the method of the present invention, the cis isomer is stereoselectively produced. Therefore, according to the method of the present invention, the target cis-olefins represented by the general formula (1) can be produced with a high purity of 98% or more and at least
It can be obtained with a high yield of 95% or more, usually 98% or more. The cis- of the general formula (1) obtained in this way
Olefins can be used as intermediates for sex pheromone synthesis without further separation. According to the method of the invention, therefore, the general formula
The production of cis-olefins represented by (1) can be carried out on an industrial scale. In the present invention, as alkynes represented by general formula (2), R ² is a benzyl group, an alkyl group with an aryl group bonded to the α-position such as α-naphthylmethyl, and a heterocyclic group bonded to the α-position. When using a compound having an alkyl group, the above hydrogenation reaction may produce cis-olefins of the general formula (1) in which R ² is a hydrogen atom. Furthermore, among the cis-olefins of general formula (1) obtained in the present invention, R ²
is an alkyl group that may have an aralkyloxy group, an alkoxy group, or an alkylthio group as a substituent, an alkenyl group, an alkynyl group, an alkylaryl group, a heterocyclic group, or an acyl group that may have a substituent and a halogen atom. In this case, it can be converted into a compound in which R ² represents a hydrogen atom by conventional hydrolysis, for example by heating using hydrobromic acid. Further, among the cis-olefins of general formula (1), a compound in which R ² is a hydrogen atom can be converted into a compound into which an acetyl group is introduced by reacting with acetic anhydride in pyridine as shown in the reaction formula below. [In the above formula, R ¹ and n are the same as above. ] Examples are given below. Example 1 10 g of 9-tetradecin-1-ol, Lindlar catalyst (containing palladium at a ratio of 5% by weight relative to calcium carbonate, and containing lead at a ratio of 2.7% by weight relative to the total amount of calcium carbonate and palladium) 0.25 g, ethylenediamine 0.29 g, and methanol 100 ml were charged into an autoclave with an internal volume of 500 ml. After replacing the air in the system with hydrogen, hydrogen 5Kg/cm ²
was press-fitted and cooled to 5°C while stirring. Thereafter, the mixture was stirred at the same temperature for 2 hours, then the Lindlar catalyst was removed, and the liquid was concentrated under reduced pressure. The resulting residue is dissolved in chloroform, washed with 10% hydrochloric acid and then with saturated aqueous sodium chloride, and then dried over magnesium sulfate. The chloroform layer is concentrated to obtain 9-tetradecen-1-ol with a yield of 99.4%. The resulting 9-tetradecen-1-ol was transferred to Shimadzu
Gas chromatographic analysis using GC-4CM manufactured by Co., Ltd. revealed that the ratio of cis and trans isomers was
99.2: It was 0.8. Also, in the infrared absorption spectrum, almost no trans characteristic absorption at 970 cm ^-1 was observed. Example 2 10 g of 9-tetradecine-1-acetate, Lindlar catalyst (containing palladium at a ratio of 5% by weight to calcium carbonate, and lead at a ratio of 4.05% to the total amount of calcium carbonate and palladium) 0.5 9-tetradecene-1-acetate was prepared in the same manner as in Example 1 except that 0.26 g of isopropylamine and 100 ml of methanol were used.
Obtained with a yield of 98.6%. The ratio of cis isomer to trans isomer is 98.5:1.5. Example 3 10 g of 1-(2-tetrahydropyranyl)-11-hexadecine, Lindlar catalyst (containing 5% by weight of palladium relative to calcium carbonate, 2.7% lead relative to the total amount of calcium carbonate and palladium)
1-(2-tetrahydropyranyl)-11-tetradecene was obtained in a yield of 99.2% in the same manner as in Example 1, except that 0.5 g (wt%), 0.05 g diethylamine, and 100 ml of isopropanol were used. . The ratio of cis and trans isomers is
98.3:1.7. Example 4 10 g of 11-hexadecyn-1-ol, Lindlar catalyst (containing 5% by weight of palladium relative to calcium carbonate and 4.05% by weight of lead relative to the total amount of calcium carbonate and palladium) 11-tetradecen-1-ol at 98.9% in the same manner as in Example 1 except that 0.5 g, cyclohexylamine 1.09 g and methanol 100 ml were used.
obtained in a yield of . The ratio of cis and trans isomers is
98.4:1.6. Examples 5-8 General formula C ₄ H ₉ C≡C(CH ₂ ) _o OR ³ as starting material
A compound corresponding to the general formula C ₄ H ₉ CH=CH(CH ₂ ) _o OR ⁴ is obtained in the same manner as in Example 1 using a compound corresponding to . The yield of the obtained compound and the ratio of the cis isomer to the trans isomer are shown in Table 1 below. [Table] [Table] Comparative Example 1 9-tetradecen-1-ol was obtained in a yield of 98.9% in exactly the same manner as in Example 1 except that ethylenediamine was not used. The ratio of cis isomer to trans isomer is 93:7.

Claims (1)

[Claims] 1 In the coexistence of Lindlar catalyst and amines, the general formula R ¹ C≡C(CH ₂ ) _o OR ² [In the formula, R ¹ is a lower alkyl group, and R ² is a hydrogen atom or a protected hydroxyl group] The organic residue that can be used as a base, n is 8 to
Each represents 10 integers. ] General formula characterized by stereoselective hydrogenation of alkynes represented by [In the formula, R ¹ , R ² and n are the same as above. ] A method for producing cis-olefins represented by: