JPS584738A - Preparation of 2-halogenated vinylcyclohexanol - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful for synthesizing a raw material for a flame retardant of nylon, etc. easily, by irradiating a mixture of cyclohexanol with a halogenated ethylene with a high energy radiation, and introducing a halogenated vinyl group directly into the 2-position of the cyclohexanol. CONSTITUTION:A mixture containing cyclohexanol with a halogenated ethylene of formulaI(X1, X2, X3 and X4 are halogen atoms), preferably at a molar ratio between the cyclohexanol and the halogenated ethylene of 1:(0.01-100), is irradiated with a high energy radiation and reacted to give a compound of formula III having a halogenated vinyl group of formula II at the 2-position. Tetrachloroethylene, etc. may be cited as the halogenated ethylene. Gamma rays using cobalt 60 or cesium 137 as the radiation source is used, and the exposed dose thereof is selected in the range of 0.1-10<3>MR.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides -J-
, 6 cyclohegi 4J nor's iJΦθ, and its characteristics are the link l-J /\ key linol and the general formula
, E, 1: By reacting a mixture of halogenated ethylenes (X4 represents a halogen atom) with high-energy radiation q by observing the line 2X3 1, the general formula X, -C is added to the 3- position. =-C-(
X, +, X2 and χ (have the same meaning as above)
An object of the present invention is to produce cyclohegizanol having a vinyl halide l:': t in a good yield.

Ω-Vinyl halide cyclohegizanol is dehydrated to form 4'rl or 3-ha1' vinylcyclohegicene, and then further oxidized to form 2-halogenated vinyl adipic acid. can get. , 2-halogenated vinyladipinoic acid is an important raw material that can impart flame retardancy to liiron, borie ether, synthetic rubber, alkyd resin, etc. produced using it as a raw material.

This method of synthesizing 2-vinyl halide cyclohegizanol (Vk) from cyclohexanol does not require derivatization such as an acetylated product to protect the human hydroxyl group of cyclohexanol, and directly converts cyclohexanol into
A halogenated vinyl group can be introduced at the - position. In addition, in this case, a compound containing a vinyl halide group at the /- position (in the formula, x1, X2, X3 and x4 have the same meanings as above). Depends on conditions.

In this way, this reaction can produce the desired cyclohexano/V having a halogenated vinyl)V group at the 2-position in one step.

The feature of the present invention is that after mixing cyclohexanol with halogenated ethylene k at a surface light molar ratio (0.0/~100 mol per 1 mol of cyclohexanol), the mixture is sealed in an ampoule under reduced pressure, and high-energy radiation is emitted. Predetermined reaction temperature (0 to 200 °C) and irradiation time (70 to 70 °C)
The target compound can be easily obtained by irradiation (for 3 hours).

Examples of halogenated ethylene include tetrachlorethylene,
Tetrachlorethylene, tetrabromoethylene, etc. are used. As the high-energy radiation, gamma rays using cobalt Otsu0 and cesium/37 as a radiation source are used, and the irradiation dose is selected within the range of 07 to 103 MH. If the irradiation dose rate is low, the irradiation time will be long, and vice versa, the irradiation time will be short.

Next, the present invention will be explained in more detail with reference to Examples.

Example/ Cyclohexanol 200f! (,2O-E=L) and tetrachloroethylene g23P (03;Mo)v)
The mixture was kept in an ampoule under total vacuum, γ-ray f23'C from 60C○, dose rate 0337X / 05R/h
1g MR irradiation was performed at r. After irradiation, the unreacted raw materials are collected and the distillate in the range of bp//S~/Otsu5'C/g*mHg is extracted! ; got 7. This is further fractionated to bp/3
2g9 of a distillate of Hg S°C/Riho Hg was obtained (yield 5.5
%, d': /3q/s, n, /533r>. Cononomono C1-analysis (i[=g/3%) agreed with the calculated value of 2-trichlorovinylcyclohexanol (g/33).

Also, XB spectrum Hg (7) /~trichlorovinylcyclohexanol/Otsu. 2oy<yield/g/%) was obtained as a by-product.

Example Ω A mixture of cyclohegisanor/I/; 200IC (20 mol) and tetrachloroethylene was sealed in an ampoule under reduced pressure, and γ-rays from 60 C□ were emitted. 2J-C, dose rate 0/
33×/O” R/hr and .2/MR verification. After collecting unreacted raw material after irradiation, bp / / 3~/Otsu S
A fraction in the range 'C/πmI-'Jg. 2 3. 7
I got an F. All of the fractions were distilled to obtain 2-trichlorovinylcycloheki'J-/-tv3299 (yield: %) and by-products. l! 220 g of chlorovinyl cyclohexanol (10%) was obtained.

Example 3 A mixture of cyclohexanol (20 mol) and tetrachloroethylene g239 (0.!; mol) was sealed in an ampoule under reduced pressure, and γ-ray f from 6°Co: 23″C, dose rate 0 0g L7X/05F 27MR irradiation was carried out at /bγ°. After collecting unreacted raw materials, the temperature was bp/./3 to /1.
A fraction of 3"C/rihoHg//3y was obtained. The fraction was fractionally distilled to yield 2-2g9 of chlorovinylcyclohegisanol (yield 2θ%) and a by-product of /3y. 54 (ltVMJ g/%) was obtained for -1-licrovinylcyclohegisanol l/!7.

Example cyclohexanol, 2009 (,20 mol) and tetrachloroethylene g23? <03 mol) was sealed in an ampoule under reduced pressure, and the r-rays from 60CO were heated to 0°C.
At a dose rate of 032 x / 0'' R/h, 23 MR was set at 1. After collecting unreacted raw materials, 111 p/h was applied.
/)~/Otsu J'C/Rito T- (G of fraction も07 was obtained.The fraction was fractionated to obtain 2-trichlorovinylcyclohexa/-)v27.5flc yield-21I%) by-product/
-Trichlorovinylcyclohegisanol 37g9 (yield 4t5%) was obtained.

Example j Cyclohexanol/,! ; Oy (/, 3 mo/I/) and tetrachlorethylene, 2. ! ;F! After sealing the mixture of (03 mol) in an ampoule in the same manner as in Example/,
r-rays from CO (z, 25'CX dose rate 0330×
70"R/hr was checked by /S MR. After recovering the unreacted raw materials, 1) p / / , ! ~ / Otsu J'C / Guho Hg fraction / Otsu 2 was obtained. The fraction was fractionated to give 2-trichlorovinylcyclohexanol 372IC14'f1
332%) /-1.lichlorovinylcyclohexanol/vg/P (ILV rate 75%) was obtained as a by-product.

Patent applicant: Makoto Ishizaka, director of Kogyo Wave 1111 - Designated agent: Akira Inukai, director of Institute of Industrial Science and Technology, Nagoya 2

Claims (1)

[Claims] Cyclohegizanolt is a mixture with halogenated ethylene represented by the general formula (1 x, -c = c -x4 (in the formula, X1, X2, X3 and χ4 are halogen atoms) General χ2X at the 3- position characterized by irradiation with high-energy radiation to cause a reaction.1 Formula Xl-C=C- (χ1, χ2 and X3 are the same as above (in the formula, ) has the same meaning).