JPH0729984B2 - 1,1-bis (trifluoroacetoxy) cyclohexane and process for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel compound, 1,1-bis (trifluoroacetoxy) cyclohexane, and a method for producing the same.

[Prior Art and Problems Thereof] 1,1-bis (acyloxy) cyclohexane and its manufacturing method have not been known.

[Means and Actions for Solving Problems] As a result of intensive studies by the present inventors,
1-bis (trifluoroacetoxy) cyclohexane was found. That is, the present invention provides 1,1-bis (trifluoroacetoxy) cyclohexane and a method for producing the same.

As cyclohexanes having an acylal structure, 1,
1-Bis (trichloroacetoxy) cyclohexane is the only known one, but the yield is very low at 13%. [Tetrahedron, Vol. 25, p. 1679 (1969)] The 1,1-bis (trifluoroacetoxy) cyclohexane of the present invention may be produced by any method, but is preferable. One of the production methods is a method of reacting cyclohexanone [formula (II)] represented by the following reaction formula with trifluoroacetic anhydride [formula (III)].

By this method 1,1-bis (trifluoroacetoxy)
Cyclohexane can be obtained with high yield and high selectivity.

This reaction can be carried out without a solvent, but a solvent which does not adversely influence the reaction can also be used. For example, ethers such as diethyl ether, tetrahydrofuran, biphenyl ether; carbon disulfide; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane; chlorobenzene, dichlorobenzene, bromobenzene, chloro. Halogenated aromatic hydrocarbons such as naphthalene; Nitro compounds such as nitrobenzene, nitrotoluene, and nitromethane; Aliphatic hydrocarbons such as hexane;
Alicyclic hydrocarbons such as cyclohexane are used.

The cyclohexanone and trifluoroacetic anhydride used as raw materials in this reaction may be produced by any method.

The amount ratio of cyclohexanone and trifluoroacetic anhydride used as a raw material in this reaction is not particularly limited, but when expressed by the molar ratio of trifluoroacetic anhydride to cyclohexanone, usually 0.01 to 100, preferably
0.1 to 50 is used.

It is also possible to add a catalyst. Examples of the catalyst include carboxylic acids such as trifluoroacetic acid and trichloroacetic acid, Lewis acids such as boron trifluoride, organic sulfonic acids such as paratoluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, and mineral acids such as sulfuric acid. Can be used.

The reaction temperature and reaction time when carrying out this reaction differ depending on the amount ratio of the raw materials and the presence or absence of a solvent, but are usually -40 to 250.
C., 5 minutes to 500 hours, preferably 0 to 150.degree. C., 10 minutes to 200 hours.

[Effect of the Invention] The 1,1-bis (trifluoroacetoxy) cyclohexane of the present invention can be used as a synthetic intermediate for industrial chemicals and the like. That is, a trifluoroacetoxy group, which is a strong electron-withdrawing group and which is inactive in itself, is 2
Since the structure has three substituted carbon atoms, the carbon atom has high activity for nucleophilic reaction. As an example, by reacting with a halogenating agent, it is possible to produce halogenated cyclohexanes substituted with fluorine, which has been difficult to produce conventionally.

[Examples] The present invention will be specifically described below with reference to Examples.

Example 1 44.2 g (0.45 mol) of cyclohexanone and 283.5 g (1.35 mol) of trifluoroacetic anhydride were placed in a reactor whose system was previously replaced with nitrogen and stirred at 25 ° C. for 3 hours, then at 70 ° C. at 70 ° C.
Let stand for hours. The reaction solution was purified by distilling off unreacted trifluoroacetic anhydride under reduced pressure at room temperature, and then further performing vacuum distillation. Boiling point as main fraction 84 ~
A colorless liquid at 86 ° C. (19 mmHg) was obtained. Yield 115 g (83% yield based on cyclohexanone).

This colorless liquid was identified as 1,1-bis (trifluoroacetoxy) cyclohexane by the analytical method shown below.

Infrared absorption spectrum: (thin film, KBr) 2960cm ^-1 , 1795cm ^-1 ,
1230 cm ^-1 , 1,170 cm ^-1 , 1,115 cm ^-1 Mass spectrum: m / e = 195 (M ⁺ -CF ₃ CO ₂ ), 194 (M ⁺ -CF ₃
CO ₂ H), 81,80 Proton NMR (δ value): 1.2 to 2.0 ppm (6 H, m), 2.0 to 2.7 pp
m (4H, m) Example 2 9.8 g (0.10 mol) of cyclohexanone and 21.0 g (0.10 mol) of trifluoroacetic anhydride were used as raw materials, and the reaction temperature and reaction time were after stirring at 25 ° C. for 3 hours. The same method as in Example 1 was carried out except that it was allowed to stand for 40 hours. 21.6 g (yield 70%) of 1,1-bis (trifluoroacetoxy) cyclohexane was obtained as the main fraction by distillation under reduced pressure.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of 1,1-bis (trifluoroacetoxy) cyclohexane of the present invention, FIG. 2 is a proton NMR spectrum of 1,1-bis (trifluoroacetoxy) cyclohexane of the present invention, FIG. Is 1,1 of the present invention
2 shows a mass spectrum of bis (trifluoroacetoxy) cyclohexane.

Claims (2)

[Claims] 1. A 1,1-bis (trifluoroacetoxy) cyclohexane represented by the formula (I). 2. A method for producing 1,1-bis (trifluoroacetoxy) cyclohexane, which comprises reacting cyclohexane with trifluoroacetic anhydride.