JPH0710793B2 - Method for producing primary allyl ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] (In the formula, R ¹ represents a hydrogen atom, a saturated or unsaturated alkyl group, an aryl group, a lower acyloxy group, a benzyloxy group, an arylsulfonyl group or a hydroxyl group, and R ² represents a hydrogen atom, a saturated or unsaturated alkyl group. Or an aryl group, and n represents a number of 0, 1, 2 or 3).

[Conventional technology]

No class of prior art is known so far regarding the synthesis of primary allyl esters of the general formula (I).

[Problems to be solved by the invention]

An object of the present invention is to provide a novel method for producing a primary allyl ester represented by the general formula (I).

[Means for solving problems]

According to the invention, the general formula (II) (In the formula, R ¹ represents a hydrogen atom, a saturated or unsaturated alkyl group, an aryl group, a lower acyloxy group, a benzyloxy group, an arylsulfonyl group or a hydroxyl group, and n represents a number of 0, 1, 2 or 3. ) A secondary allyl chloride represented by the general formula (III) in the presence of an iodinated tetraalkylammonium salt (Wherein R ² represents a hydrogen atom, a saturated or unsaturated alkyl group or an aryl group, and M represents a lithium atom, a sodium atom, or a potassium atom). It has been found that primary allyl esters of formula (I) can be produced in high yield.

The primary allyl ester represented by the general formula (I) is usually
The steric structure based on the carbon-carbon double bond at the 2-position is obtained as a mixture of a cis-regulated compound and a trans-regulated compound.

R ¹ and R ² in the general formula will be described in detail. R ¹
Represents a hydrogen atom, a saturated or unsaturated alkyl group, an aryl group, a lower acyloxy group, a benzyloxy group, an arylsulfonyl group or a hydroxyl group, and R ² represents a hydrogen atom, a saturated or unsaturated alkyl group or an aryl group. Here, as the saturated or unsaturated alkyl group,
Those having a straight or branched chain having 1 to about 20 carbon atoms are applicable, and are methyl group, ethyl group, n-propyl group, i-propyl group, n-pentyl group, n-nonyl group, 3-methylbutyl. Examples include groups. Examples of the aryl group include a phenyl group and a p-tolyl group. As the lower acyloxy group, a formyloxy group, an acetoxy group,
Examples thereof include a propionyloxy group and a butyryloxy group. Examples of the arylsulfonyl group include a phenylsulfonyl group and a p-tolylsulfonyl group.

In the method of the present invention, 8-acetoxy-2,6 in which R ¹ is an acetoxy group, R ² is a hydrogen atom, and n is 1 in the general formula (I).
-Synthesis of dimethyl-1-formyloxy-2,6-octadiene; R ¹ is benzyloxy group, R ² is hydrogen atom, n is 1
8-benzyloxy-2,6-dimethyl-1-formyloxy-2,6-octadiene; R ¹ is a phenylsulfonyl group, R ² is a hydrogen atom, and n is 1,6-dimethyl- 1-formyloxy-8-phenylsulfonyl-2,
Synthesis of 6-octadiene; ¹ -formyloxy-2-methyl-6- (p-tolyl) -2-wherein R ¹ is 2- (p-tolyl) -propyl group, R ² is hydrogen atom, and n is 0. Synthesis of heptene; Synthesis of 2,6-dimethyl-1-formyloxy-2,5-heptadiene in which R ¹ is 2-methyl-1-butenyl group, R ² is hydrogen atom, and n is 0; R ¹ is phenyl Group, 1-formyloxy-2-methyl-in which R ² is a hydrogen atom and n is 0
It is particularly useful for synthesizing 4-phenyl-2-butene and the like.

The primary allyl ester represented by the general formula (I) produced by the method of the present invention, particularly the formate ester in which R ² is a hydrogen atom, is easily hydrolyzed or transesterified under acidic or basic conditions. General formula (Wherein R ¹ and n are as defined above). For example, a catalytic amount of sodium carbonate can be used to obtain the corresponding allyl alcohol in a methanol solution under mild conditions such as room temperature (see Reference Example below). This allyl alcohol is widely used for producing various terpene compounds having a polyprenyl unit in the molecule such as vitamin A and the like or fragrances and pheromones. For example, in the general formula (IV), R ¹ is an acetoxy group, n
8-acetoxy-2,6-dimethyl-1 when is 1
-Hydroxy-2,6-octadiene is used in the production of the compounds shown below.

1) Vitamin A synthesis (J. Org. Chem., 51 , 3834 (198
6)) 2) Synthesis of (E) -3,7-dimethyl-2-octene-1,8-diol, which is a hairpencil secretion of African monarch butterfly (Tetrahedron Lett., 3485 (1971)) 3) It is a protective secretion of the whirligig water beetle.
Synthesis of Gyrindal (Tetrahedron Lett., 281 (1973)) Conventionally, as a method for synthesizing allyl alcohol of the type represented by the general formula (IV), for example, 1) a method of reacting a compound having an isopropylidene group at the tip with selenium dioxide and a peroxide such as t-butyl hydroperoxide ( J. Am. Chem. Soc. 99 , 5526 (197
7)) 2) Method of sequentially reacting allyl chloride with dimethylamine, peracetic acid, zinc, etc.
Page (1986)) Are known. However, these methods have problems that selenium dioxide, which is a toxic substance, is used, and that peroxide, which is a danger of explosion, is used. General formula (I)
When a primary allyl ester represented by the formula (3), particularly a formic acid ester in which R ² is a hydrogen atom, is used, as described above, the general formula (IV) is very easily achieved without causing such a problem.
Of allyl alcohol can be obtained.

The secondary allyl chloride represented by the general formula (II) is obtained by adding the following terpene compound to hypochlorous acid or bleaching powder (Tetrahed).
Ron Lett., 21 , 441 (1980)) or chlorinated isocyanuric acid (Japanese Patent Application Laid-Open No. 58-52231).

1. Terpene hydrocarbons such as myrcene, ocimene, farnesene 2. Terpenic alcohols such as geraniol, nerol, citronellol, linalool, farnesol 3. Esters of terpene alcohols such as geranyl acetate, neryl acetate, linalyl acetate, farnesyl acetate 4. Benzyl ethers of terpene alcohols such as geranyl benzyl ether and farnesyl benzyl ether 5. Terpene compounds having a phenyl group such as curcumene and ervirol 6. Terpene compounds having a chroman skeleton such as tocotrienol General used in the reaction according to the method of the present invention Formula (III)
As the metal salt of carboxylic acid represented by, for example, formic acid, acetic acid, aliphatic carboxylic acid such as propionic acid, benzoic acid, lithium, sodium, potassium salt of aromatic carboxylic acid such as p-trilic acid can be exemplified. . The metal salt of carboxylic acid is preferably used in an equimolar amount or more with respect to the secondary allyl chloride represented by the general formula (II), and is used in an amount of about 2 times the molar amount for the purpose of efficiently carrying out the reaction. . The iodinated tetraalkylammonium salt as a catalyst preferably has a total number of carbon atoms of four alkyl groups within a range of about 8 to 32, and specific examples include iodinated tetra-n-butylammonium and iodinated tetra- Examples thereof include n-pentyl ammonium, stearyl trimethyl ammonium iodide and the like. The amount of the iodinated tetraalkylammonium salt used should be the
It is usually 0.1 to 20 mol% relative to the grade allyl chloride,
Particularly preferably, it is 1 to 5 mol%.

In this reaction, an inert solvent, for example, an aliphatic or aromatic hydrocarbon such as hexane, benzene or toluene, a chlorinated hydrocarbon such as chloroform, an ether such as dioxane or isopropyl ether, and an ester such as ethyl acetate are used. be able to. A particularly suitable solvent is toluene. The reaction can be carried out at a temperature in the range of 30 ° C to 180 ° C, preferably at a temperature in the range of 70 to 140 ° C and under heating and reflux of the reaction solution.

Hereinafter, the method of the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 8-acetoxy-2,6-dimethyl-3-chloro-1,6-octadiene 30 g (90.9% purity, 118 mmol), sodium formate 16.32 g (240 mmol), iodinated tetra-n-butylammonium 0.9 g (2.4 mmol) A mixture of 100 ml of toluene was heated under reflux for 9 hours with vigorous stirring. After cooling, the solid was suctioned off and the liquid was washed with 50 ml of water. Furthermore, the organic layer was washed with 50 ml of 5% aqueous sodium thiosulfate solution, 50 ml of 5% aqueous sodium hydrogen carbonate solution and 50 ml of 5% saline solution, and the solvent was distilled off under reduced pressure to obtain 32.44 g of an oily substance. Analysis by gas chromatography revealed that the target 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene had a purity of 76.5% and a yield of 24.
The yield was 82 g (103.4 mmol) and 87.6%. The cis-to-trans ratio of the double bond at the 2-position was 58.2: 41.8. This crude formic acid ester can be distilled by a distiller equipped with a packed column (boiling point: 115-118 ° C / 0.2 mmHg).

The instrumental analysis results of 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene are shown below.

NMR (tetramethylsilane / carbon tetrachloride) δ: 1.71 (broad, 6H), 1.96 (s, 3H), 2.09 (broad, 4
H), 4.40 to 4.70 (m, 4H), 5.28 (t, J = 10Hz, 2H), 7.5
(S, 1H) IR (KBr plate) ν: 1720 cm ^-1 (C = O) MS m / e (relative intensity): 195 (10, M ⁺ -HCO ₂ ), 134 (62),
The reaction was carried out in the same manner as above except that the metal salts of 84 (100) and 43 (100) carboxylic acids were variously changed. The products and yields are shown in Table 1.

Reference Example As a reference example, a synthesis example from 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene to 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene Show.

To a solution of 100 g of 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene (96% purity, 400 mmol) in 500 ml of methanol was added 318 mg (3 mmol) of sodium carbonate,
Stirred at room temperature for 1 hour. Concentrated sulfuric acid 300 mg, methanol 30 ml
The solution and 0.1 g of pyridine were added to stop the reaction, and then the solvent was distilled off under reduced pressure to obtain 113 g of an oily substance. Analysis by gas chromatography revealed that the desired 8-acetoxy-2,6-dimethyl-1-hydroxy-
The purity of 2,6-octadiene is 72.7% and the yield is 82.19 g.
(387.7 mmol), the yield was 96.9%. The cis-to-trans ratio of the double bond at the 2-position was 54.7: 45.3. 8-
The instrumental analysis results of acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene are shown below.

NMR (tetramethylsilane / carbon tetrachloride) δ: 1.71 (broad, 6H), 1.96 (s, 3H), 2.05 (broad, 4
H), 3.20 (broad, 1H), 3.87,4.00 (s, 1H in total), 4.
40 (d, J = 6Hz, 2H), 5.15~5.60 (m, 2H) IR: 1720cm -1 (C = O), 3400cm -1 (OH) MS m / e ( relative intensity): 134 (21), 84 (90), 68 (10
0), 43 (100) Examples 2 to 6 Primary allyl esters and primary allyl alcohols were synthesized from allyl chloride shown in Table 2 using sodium formate in the same manner as in Example 1 and Reference Example. The product and its yield are shown in Table 2.

EFFECTS OF THE INVENTION According to the present invention, a secondary allyl chloride represented by the general formula (II) is reacted with a metal salt of a carboxylic acid represented by the general formula (III) in the presence of an iodinated tetraalkylammonium salt. By doing so, the primary allyl ester represented by the general formula (I) can be produced in high yield. The primary allyl ester represented by the general formula (I) is converted into various terpene compounds having a polyprenyl unit in the molecule such as vitamin A or a fragrance or pheromone through the corresponding allyl alcohol. Can be induced.

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Claims (1)

[Claims] 1. General formula (II) (In the formula, R ¹ represents a hydrogen atom, a saturated or unsaturated alkyl group, an aryl group, a lower acyloxy group, a benzyloxy group, an arylsulfonyl group or a hydroxyl group, and n represents a number of 0, 1, 2 or 3. ) A secondary allyl chloride represented by the general formula (III) in the presence of an iodinated tetraalkylammonium salt (Wherein R ² represents a hydrogen atom, a saturated or unsaturated alkyl group or an aryl group, and M represents a lithium atom, a sodium atom, or a potassium atom). General formula (I) (In the formula, R ¹ , R ² and n are as defined above).