JPS61172836A - Production of halogenated unsaturated alkylbenzene - Google Patents

Abstract

PURPOSE:To obtain the titled substance useful as a monomer for high polymers, etc., containing a vinyl group with three halogen atoms, by reacting an alkylbenzene with a halogenated ethylene under irradiation of high-energy radiation. CONSTITUTION:An alkylbenzene shown by the formula I (R1 is phenyl, or alkylphenyl; R2-R4 are H, or alkyl) is reacted with a halogenated ethylene shown by the formula II (X1-X4 are halogen) in a molar ratio of 2-5:1 under high-energy radiation, to give the titled substance containing a vinyl group with three halogen atmos shown by the formula III at the alpha-position or beta-position of benzene ring or alkyl group. A radioactive isotope such as Co 60, Ce 124, etc., as a radiation source is used as the high-energy radiation, and the irradiation temperature is effectively 10-200 deg.C. EFFECT:The aimed substance which has been hitherto extremely difficult to synthesize is easily produced.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for producing halogenated unsaturated alkylbenzenes. More specifically, the present invention can be used as a polymer monomer itself, and can also be easily used for other vinyl monomers and acetylene monomers useful as raw materials for polymer materials and organic semiconductors. The present invention relates to a method for efficiently and easily producing unsaturated alkylbenzene having a vinyl group having three halogen atoms, which can lead to the following.

Conventional technologyUnsaturated alkylbenzenes having ethylenically unsaturated bonds or acetylenically unsaturated bonds have been used as raw materials for polymer materials, and have recently attracted attention as raw materials for organic polymer semiconductors. .

These unsaturated alkylbenzenes have so far been obtained by dehydrohalogenation or dehalogenation of corresponding compounds having one or two halogen atoms (Bull, Soc, Chin.

Fr, J 1966, p. 1293, Journal of the Society for Organic Synthesis, Vol. 31, p. 777 (1973).

By the way, unsaturated alkylbenzene having a vinyl group having 3 halogen atoms can be made into a polymer by replacing the halogen atom with an atom or group such as a hydrogen atom or another halogen atom, or by dehalogenation. It can be easily led to other vinyl monomers and acetylene monomers that are useful as materials and raw materials for organic semiconductors, etc.
Moreover, it is itself useful as a polymeric monomer.

However, such an unsaturated alkylbenzene having a sulfinyl group with three halogen atoms.

Conventionally, synthesis has been extremely difficult, so there are almost no examples of practical use of this product for the above-mentioned purposes.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to solve a problem that is difficult to synthesize in the past, and which has three halogen atoms and is useful as a raw material for polymeric materials and organic semiconductors. An object of the present invention is to provide a method for efficiently and easily producing unsaturated alkylbenzene having a vinyl group.

Means for Solving the Problems As a result of extensive research, the present inventors have discovered that the above object can be achieved by irradiating high-energy radiation to cause the alkylbenzene and perhalogenoethylene to react. Based on this finding, we have completed the present invention.

That is, the present invention is based on the general formula % formula % (1) (wherein R1 is a phenyl group or an alkylphenyl group, R
2, R3 and R4 are each a hydrogen atom or an alkyl group, and they may be the same or different. By irradiating high-energy radiation and reacting halogenated ethylene represented by atoms A9, which may be the same or different, the general formula (Xl, X2 and x3 has the same meaning as above) is introduced into the α-position or β-position of the benzene ring or alkyl group of the alkylbenzene. It is something to do.

The alkylbenzene represented by the general formula (1) used in the method of the present invention is preferably one in which the number of carbon atoms in the alkyl group is in the range of 1 to 10.
For example, toluene, ethylbenzene, flobylbenzenes, phthylbenzenes, amylbenzenes, cumene, cymenes, methylethylbenzenes, diethylbenzenes, and the like are preferably used.

Further, the halogenated ethylene represented by the general formula (El) preferably contains fluorine, chlorine, or bromine as a halogen atom, and the four halogen atoms may be the same or different. Good 0 Something like this:
For example, tetrafluoroethylene, tetrachlorethylene, tetrabromoethylene, trifluoromonochloroethylene, trifluoromonobromoethylene, trichloromonobromoethylene, etc. are preferably used.

In the present invention, the optimum ratio of the above-mentioned 7-logogenated ethylene and alkylbenzene varies depending on the type of raw materials, but is usually in a molar ratio of i:o, oi to 1:10.
, preferably in the range of 1:2 to 15.

In addition, as high-energy radiation for irradiation, 60CO
A radiation source using a radioactive isotope such as 1124Ce or one from an accelerator is used, and the effective irradiation temperature is in the range of 10 to 200°C. ) by reacting an alkylbenzene represented by the general formula (■) with a halogenated ethylene represented by the general formula (■) by irradiating it with high-energy radiation, three halogen atoms represented by the general formula @) are produced. A vinyl group that reacts with tV is introduced into the benzene ring of the alkylbenzene or the α-position or β-position of the alkyl group.

The reaction-completed liquid is treated according to a conventional method to recover unreacted substances, and then subjected to vacuum distillation or the like to obtain the desired halogenated unsaturated alkylbenzene. The recovered unreacted materials can be reused for the reaction.

Effects of the Invention The method of the present invention irradiates high-energy radiation to cause a total reaction between alkylbenzene and par-710 genoethylene, thereby producing an unsaturated alkylbenzene having a vinyl group having three nitrogen atoms, which has been extremely difficult to synthesize in the past. The obtained halogenated unsaturated alkylbenzene is itself useful as a polymeric monomer (1), and is also useful as a raw material for polymeric materials, organic semiconductors, etc. It can be easily converted into vinyl monomers and acetylene monomers.

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

Example 1 After sealing a mixed solution of 92.20 r (1.0 mol) of toluene and 41.48 y (0.25 mol) of tetrachlorethylene under reduced pressure, γ-rays of 60Co were applied at a dose rate of 2 x 105 R/hr. Irradiated for 200.17 hours at room temperature. After irradiation, unreacted raw materials were collected to obtain 6.06 f of crude oil. This crude oil was distilled under reduced pressure to a bp of 99.5 to 108.4℃.
A fraction 2.36f of /7uHg was obtained.

When the obtained fraction was analyzed by gas chromatography, it was found that the reaction product was 0.90 f [0,0040 mol] of methylated side chain substituted product of toluene, yield 21.4.
%, bp 82.0-82.3℃/3mal HP
, d41.3324, n, ) 1.5627. Ct4
8.10ii (amount % (calculated value 48.01 weight %)), 1.26F (0,0057 mol, yield 29.8
0.08F (0,0006 mol, yield 2.4%, b
p104.0~105.3'C/81mHg%a4
1.2859, nDl, 5656) was obtained.

Note that the yield is a value per tetrachlorethylene actually consumed in the reaction, as shown in the following formula.

For comparison, when toluene and tetrachloroethylene were reacted using a catalyst, a side chain substituted product and a dimerized product were obtained. In the NMR spectrum of this side chain substituted product, the methylene group in the benzyl group showed a signal at 3.82 ppm, and the phenyl group showed a signal at 7.16 ppm, which coincided with the side chain substituted product determined by the γ-ray method. However, in the gamma ray method, there was also a signal from the methyl group at 2.33 ppm of the original toluene, indicating that the methyl group of toluene remained. This was also confirmed in the engineering R spectrum, proving that the nitrichlorovinyl group in the toluenobenzene nucleus was substituted. It was confirmed by mass spectrometry that the side chain substituted product and the nuclear substituted product had the same molecular weight.

Example 2 A mixed solution of 120°09 t (1.13 mol) of ethylbenzene and 41.45 t (0.25 mol) of ethylbenzene was sealed under reduced pressure, and then the gamma rays of 60 CO were applied at a dose rate. Irradiation was performed at 2×105 R/hr for 297.88 hours at room temperature. After irradiation, unreacted raw materials are recovered and crude oil 4.7
Obtained 1t. This crude oil was distilled under reduced pressure to a bp of 93.5°C/
80Hg~119.0℃/7fiHg fraction 2.24
I got f.

The fraction was analyzed by gas chromatography, and the product was 1.061F (0,0046 mol, yield 19.4%, bp 76. 6-77.3℃/21
01Hg%d4 1.2555, nDl, 5580.
C145.56% by weight (subtraction value 45.15% by weight)]
, a nuclear substituted product with a trichlorovinyl group introduced into the benzene ring 0.99 F [0,0043 mol, yield 18.1%
, bpl, 5575 ], and dimer 0.11 ?
(0,0005 mol, yield 2.1%) was obtained.

Example 3 120.09 t (1.0 mol) of n-propylbenzene and 41.45 F (0.25 mol) of tetrachloroethylene
After sealing the mixture under reduced pressure, the mixture was irradiated with 60 cO gamma rays at a dose rate of 2 x 105 R/hr for 205.49 hours at room temperature. After irradiation, unreacted raw materials are recovered and crude oil 7.9
Obtained 0t. Distill the crude oil under reduced pressure to bpH 4.0 to 1.
A fraction of 2.17 f at 35.0° C./8 u Hg was obtained.

This fraction was analyzed by gas chromatography, and the product was 0.52 y (0,0020 mol, yield 9.9%) of a nuclear substituted product in which a trichlorovinyl group was introduced into the benzene ring.
, bp125; 3-129.0°C/70) (g, d41
．． 1871, nDl, 5508), a side chain substituted product in which a trichlorovinyl group is introduced at the α- or β-position of the propyl group of n-propylbenzene 0.54 f [0,00
22 mol, recognition rate 10.39, bp88.1-89
．． 2℃/1.5111Hg, d41.2281, nD
l, 5475, Ct43.60% by weight, (tl calculated value 4
2.62 f (0
,0025%, yield 12.0%).

Example 4 Kume7120.20? After sealing a mixture of (1.0 mol) and 41.47 t (0.25 mol) of tetrachlorethylene under reduced pressure, it was irradiated with gamma rays of 60CO at a dose rate of 2XIOR/hr for 200.17 hours at room temperature. .

After the irradiation, unreacted raw materials were recovered to obtain 5.31 f of crude oil.

Distill the crude oil under reduced pressure to bp116.2-120.2℃
2.14 t of Hg/7% fraction was obtained.

The fraction was analyzed by gas chromatography and the product was 1.47 F (0,0058 mol, yield 23.4), a nuclear substituted product in which a trichlorovinyl group was introduced into the benzene ring.
%%bpH3.0-116.0℃/7mHg, d4
1.2377, nDl, 5596) and dimer 0.28? (0,0014 mol, yield 5.6%) was obtained.

Example 5 1)-? Imen 134.23 f(1,0-E:k)j
- After sealing a mixed solution of 41.48 f (0.25 mol) of trachloroethylene under reduced pressure, 60 co of gamma rays were applied at a dose rate of 2 x 105 R/hr te 200,
It was irradiated at room temperature for 17 hours.

After irradiation, unreacted raw materials were collected to obtain crude oil 8.16F.

This crude oil was distilled under reduced pressure to a bp of 119.5 to 136.2℃.
A fraction of 4.29 F with /8 nHg was obtained.

The fraction was analyzed by gas chromatography, and a nuclear substitution product in which a trichlorovinyl group was introduced into the benzene ring was found to be 1.85
f (0,0070%l, yield 20.5%bp 12
3.0-123.4℃ 790I (g%d4 1.178
01nDl, 5444) and dimer 0.84f
(0,0031% l, yield 9.3%) was obtained.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_1 in the formula is a phenyl group or an alkylphenyl group,
R_2, R_3 and R_4 are each a hydrogen atom or an alkyl group, and they may be the same or different. , X_2, X_3 and X_4 are each halogen atoms, and they may be the same or different. , chemical formulas, tables, etc. ▼ (X_1, X_2, and X_3 in the formula have the same meanings as above) A method for producing halogenated unsaturated alkylbenzene, which is characterized by introducing halogenated unsaturated alkylbenzene.