JPH0710792B2 - Novel formate ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel formate ester, 8-acetoxy-2,
The present invention relates to 6-dimethyl-1-formyloxy-2,6-octadiene (hereinafter, this compound may be simply referred to as formic acid ester).

[Conventional technology]

The formic acid ester of the present invention is a novel compound, and, of course, the nature and synthetic method of this compound are not known.

[Problems to be solved by the invention]

An object of the present invention is to provide a new formate ester.

[Means for solving problems]

The present inventors 8-acetoxy-2,6-dimethyl-1 having the structure
-Formyloxy-2,6-octadiene was successfully synthesized.

This formate ester has a green note-like odor and can be used as a fragrance. This compound can also be used with weakly basic substances such as aqueous ammonia, sodium bicarbonate, sodium carbonate, sulfuric acid,
The formyl group is easily selectively hydrolyzed under the condition of using an acidic substance such as hydrochloric acid or p-toluenesulfonic acid as a catalyst,
8-acetoxy-2,6-dimethyl-1-hydroxy-2,6
-Can lead to octadiene. This 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene is used for preparing various terpene compounds having a polyprenyl unit in the molecule such as vitamin A or fragrances and pheromones. It is a widely used compound. A synthesis example of vitamin A and a terpene compound from 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene is shown below.

1) Synthesis of vitamin A (J.Drg.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) Synthesis of C ₁₇ juvenile hormone (JCSChem.Comm., 486
(1972)) 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6
As a method for synthesizing octadiene, 8-acetoxy-2,6-dimethyl-3-chloro-1,6-octadiene obtained by reacting geranylacetate with hypochlorous acid or the like is added to dimethylamine, acetic anhydride, peracetic acid. , Zinc, etc. are known to act sequentially (lit, Inoue et al. Chem. Lett., 2
035 (1986)), this method has problems such as a long reaction step and the use of a peroxide with danger of explosion.

The 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene (I) of the present invention is 8-acetoxy-2,6-dimethyl-3-chloro-1,6-octadiene (II).
A high yield can be obtained by reacting I) with sodium formate and a catalytic amount of a tetraalkylammonium iodide salt while heating under reflux with toluene. Further, as shown in the reference example described later, this product was treated with a catalytic amount of sodium carbonate in a methanol solution at room temperature to give a good yield of 8-acetoxy-2,6-dimethyl-1-hydroxy-.
It can be induced to 2,6-octadiene (II). That is, the formic acid ester (I) of the present invention is not only useful as a perfume per se, but also 8-acetoxy-2,6 which is important as a synthetic intermediate for vitamin A, juvenile phorphone and the like.
-Dimethyl-1-hydroxy-2,6-octadiene (I
It provides a very effective manufacturing method of I).

The starting compound 8-acetoxy-2,6-dimethyl-3-chrome-1,6-octadiene (III) is a known method, for example, a method in which hypochlorous acid or bleaching powder is allowed to act on geranyl acetate (Tetrahedron Lett., 21,441). (1980)), and also geranyl acetate can be easily synthesized by a method of reacting chlorinated isocyanuric acid (JP-A-58-52231).

The amount of sodium formate used is the amount of allyl chloride (II
It may be equimolar or more with respect to I), but it is preferably used in an amount of about twice the molar amount for efficient reaction. The halogenated tetraalkylammonium salt as a catalyst preferably has a total carbon number of four alkyl groups within the range of 8 to 20, and as a typical example, iodinated tetra-n-
Butyl ammonium can be exemplified. The amount used is usually 0.1 to 20 mol% and particularly preferably 1 to 5 mol% based on allyl chloride.

For this reaction an inert solvent such as hexane, benzene,
Aliphatic and aromatic hydrocarbons such as toluene, chlorinated hydrocarbons such as chloroform, ethers such as dioxane and isopropyl ether, and esters such as ethyl acetate can be used. 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 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. Further, the organic phase was washed with 50 ml of 5% aqueous sodium thiosulfate solution, 50 ml of 5% sodium bicarbonate 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. Gas chromatographic analysis revealed that the target 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene had a purity of 76.5% and a yield of 2
The yield was 4.82 g (10.34 mmol), 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 mm Hg).

8-acetoxy-2,6-dimethyl-1-formyoxy-
The results of instrumental analysis of 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),
84 (100), 43 (100) Reference Example As a reference example, 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene to 8-acetoxy-2,6-dimethyl-1-hydroxy-2 An example of synthesis into 6,6-octadiene is shown.

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
After stopping the reaction by adding a solution and 0.1 g of pyridine,
The solvent was distilled off under reduced pressure to obtain 113 g of an oily substance. Gas chromatographic analysis showed that the target 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene had a purity of 72.7% and a yield of 82.
The yield was 19 g (387.7 mmol), 96.9%. The cis-to-trans ratio of the double bond at the 2-position was 54.7: 45.3. 8
-Acetoxy-2,6-dimethyl-1-hydroxy-2,6-
The results of the octadiene analysis by the equipment 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), 4.00
(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) [Effect of the Invention] According to the present invention, a novel formic acid ester, 8-acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene, is provided. This compound is expected to be used as a fragrance, and vitamin A and various terpene compounds can be synthesized from 8-acetoxy-2,6-dimethyl-1-hydroxy-2,6-octadiene derived from this compound. You can

Claims (1)

[Claims] 1. 8-Acetoxy-2,6-dimethyl-1-formyloxy-2,6-octadiene