JPS5946233A - Diphenyldiacetylene having trifluoromethyl group - Google Patents

Abstract

NEW MATERIAL:The diphenyldiacetylene of formula [R is 2-trifluoromethylphenyl, or 2,4-, 2,5-, or 3,5-bis(trifluoromethyl)phenyl]. EXAMPLE:2,2',5,5'-Tetrakis(trifluoromethyl)diphenyldiacetylene. USE:A photosensitive material and a monomer for preparation of crystalline polymer semiconductor. PROCESS:The objective compound of formula can be prepared e.g. by the oxidative coupling reaction of a phenylacetylene having trifluoromethyl group in the presence of a copper salt (preferably cupric salt) as a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to diphenyl diacetylenes having a trifluoromethyl group that are useful as monomers for photosensitive materials and crystalline polymer semiconductors.

In recent years, it has become clear that some compounds among diacetylenes represented by the general formula % have solid phase polymerizability and are useful as monomers for photosensitive phase contrast and crystalline polymer semiconductors. Became. -1
Although there are an extremely large number of known diacetylenes represented by the following general formula, the number of diacetylenes having solid phase polymerizability is unknown. Moreover, those with such gender a are −R
Only No. 13 belongs to the Nida-type, especially those in which methylene is partially bonded to acetylene atom, and most of them are those in which R is CH or R' type. However, in this type of compound, R is not conjugated with the acetylene bond, and even in the polymer, R is conjugated to the unsaturated system in the main chain, so the electrical influence of R on the same system is There is one small unit, and the properties tend to be similar to IJ.

When a diacetylene-substituted compound represented by the general formula 1-1, in which R is an aromatic W conjugated with the triple bond in the formula, undergoes solid phase polymerization, the crystalline polymer to be produced as a result Excellent properties are expected. However, such diacetylenes generally do not have solid +1 polymerizability. For example, diphenyl diacetylene has no solid (:11) polymerizable property, and the polymerizable one in this persimmon family is the acetylate at each of the two phenyl/L/J- ortho and meta positions of diphenyl diacetylene. Those with amino groups/low number of 4H2.

The present invention aims to develop a compound substituted with diacetylenes represented by the above general formula (where R is an aromatic group conjugated with the triple bond in the formula and has solid 4.11 polymerizability).
O゛As a result of research, it was found that by light, n'J
t': Output 41 indicating that there is a shiyazui compound.

This invention was based on this knowledge.

This invention is represented by the general formula %, where R is a 2-1-lifluoromethylphenyl group and R is 2, 4-, 2, 5-, and 6°5-
It presents four compounds that are bis(trifluoromethyl)phenyl groups.

The compounds of this invention are all new compounds that have not been published in any literature, and can be obtained by oxidative coupling reaction of phenylacetylene having I-IJ fluoromethyl/L/ groups.
nt can be constructed.

This oxidative coupling reaction can be carried out under various reaction conditions, but in all cases the catalytic action of the copper salt is
- The method can be divided into two depending on the proportion of copper salt added to phenylacetylene having a 1-lifluoromethyl group. In the first method, since the copper "72+ also acts as an oxidizing agent, chemical
Theoretical 111th -:', it is necessary to use a copper salt.

As a solvent, use pyridine at a temperature of about 50°C. 1. Objective reaction conditions. In method 2 to h', usually ace1-
Using a resistant medium such as
, N' , N' -Oxidative coupling is carried out by passing oxygen in the presence of N' -tetramethylethylenecyamine.

In order to isolate the target compound from the reaction mixture thus obtained, in the method of No. 71, the crystalline precipitate formed by pouring into water may be collected by filtration and dried. When the second method is used, the reaction mixture is treated with -1: or after the solvent used in the reaction is removed using an evaporator, an organic solvent such as ether and an aqueous hydrochloric acid solution are added to remove the organic layer. After washing and drying, the target compound is obtained as crystals by removing the solvent.

The resulting trifluoromethyl, phenyl diacetylene can be purified by recrystallization from an organic solvent such as ethanol. Since it is easy to polymerize and color when exposed to light, it is necessary to prevent light from hitting it during the above-mentioned isolation and preparation operations and during storage. (When it is in solution (There is no need to shield the compound from light.) The compound of this invention exhibits characteristic absorption due to vibratory vibration of the acetylene bond at a distance of 2150 cm, so it can be identified based on this. The compounds of this invention have also been confirmed by hydrogen and fluorine nuclear magnetic resonance spectroscopy as well as elemental analysis.

The compounds of this invention have several uses that take advantage of their solid phase polymerizability. For example, if a crystal is irradiated with gamma rays, a crystalline polymer compound with semiconducting properties can be obtained. In addition, if you dissolve it in an organic solvent and apply it to a piece of paper, etc., and then evaporate the solvent, countless microcrystals will precipitate out, and if you shine light on it, the areas that are most likely to hit will develop a color (reddish), so it will be photosensitive. 4g E+
It can also be used as

Next, the present invention will be explained in further detail with reference to Examples and Reference Examples.

Example 1 20 g (0,0084 mol) of 2.5-his(trifluoromethyl)phenylacetylene was dissolved in 30I11e pyridine, put into a 1i[th] flask, and stirred with a magnetic stirrer. - Rough 1-medium), heat in a hot water bath set to 50%. Crystals of cupric acetate hydrate 4
．． 0. 1:1' at this bath temperature after adding g! '11 Pa
With continued stirring, one reaction mixture is poured into approximately 500 m6 of water with stirring, forming a white crystalline precipitate.

This was filtered and dried with calcium chloride in a vacuum stage.
I゛Lifluoromethyldiphenyldiacetylene 1.95
g (yield 98%, melted gas 101=102°C) was obtained.

The yield after recrystallization from ethanol was 89%, and the midpoint was 101.5-1025°C.

Example 2 2.2' in the same manner as in Example 1 from 2,4-bis(+-lifluoromethyl)phenylacetylene.

4.4'-Tetrakis(trifluoromethyl)diphenyldiacetylene was obtained. The yield after recrystallization using ethanol was 84%, and the melting point was 144-1445°C.

Real JrBi Example: Similarly, from 5-bis(trifluoromethyl)phenylacetylene, 3.3',5.5'-tetrakis()
・Lifluoromethylacetylene was obtained. The yield after recrystallization from benzene is 77
%, and the melting point was 1545-1555°C.

N, N, N' in a 100IrIe Erlenmeyer flask
, N'-te1'-methylethylenediami70. 2 4
g(7) 7 setone (30 ni) solution (It was stirred in a Maknethysox cooler, and cuprous chloride 0.2
Add 0 g.

Oxygen is introduced from the tip of a glass tube inserted into the liquid. 3
．． After adding a solution of 2.0 g of 5-bis(trifluoromethyl)phenylacetylene in acetone (10me). Two doses of oxygen and stirring were continued for 1 hour.

The resulting reaction mixture was poured into a mixture of ether and aqueous hydrochloric acid, the whole was stirred, and the ether layer was washed with an aqueous solution of hydrochloric acid, water, and then an aqueous solution of 1.
It was dried with anhydrous sulfuric acid (l-IJ). 3.3', 5.5'-Te1-
Lagis(trifluoromethyl)silophenyldi7 7f
L' 71. 9 2 g (IIM '4A 9
6%, Wl, +jWPI; 1°C) was obtained.

Example 4 20 g of 2-1-lifluoromethylphenylacetylene (
0.0118 mol) and 40 g of cupric acetate hydrate in 30 m
2.2'-
Bis(1'trifluoromethyl)diphenyldiacetylene1. 69 g (yield 98.5%, melted, 067-68
°) was obtained. This compound can be recrystallized from ethanol to form crystals with solid phase affinity. polymerization and
In some cases, crystals that do not have a strong polymerization tendency may be obtained.

Polymerizability was generally observed in transparent, elongated purinum-like crystals that were precipitated and grown over a relatively long period of time from ethanolic acid.

On the other hand, d-polymerizability was not observed in the crystals that precipitated relatively quickly from the ethanol solution. However, the %l1 points of these two 3-1 crystals were the same at 675-685°C.

Reference number S11 Each sample of the invention compound consisting of 1 crystalline 1"f (size differs from one compound to another) was sealed in a glass tube to eliminate depletion. Kobal l--6 The dose rate for gamma rays was 7.3 X, and the product was irradiated for 10 hours at the 10 hour position. After opening,
The polymerization rate of the acetone-insoluble matter was determined. The results are shown in the table below.

Compound Polymerization rate (substituents on each benzene ring) (%) 2-trifluoromethyl 272, 4-bis(trifluoromethyl/1z) 352, 5-bis(trifluoromethyl) 9
65,5-bis(+-refluoromethyl/l/) 33 It is clear that both compounds have considerable solid 4'[1 polymerizability. Incidentally, it is known that diphenyl diacetylene does not polymerize at all under these conditions.

Designated fee J] 11 people

Claims (1)

[Claims] It is represented by the general formula %, where R is a 2-trifluoromethylphenyl group and R is 2.4-. 2.5-t and 6゜5-bis(trifluoromethyl)phenyl thearcyphenyl diacetylenes