JPS5811439B2 - N-(P-vinylphenyl) carbazole - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel compound N-(,p-vinylphenyl)carbazole.

N-(p-vinylphenyl)carbazole obtained by the method of the present invention is a novel compound that can be effectively used as a monomer for providing image-forming materials and photoconductive polymers.

Polymers and copolymers of vinyl derivatives having a conjugated π atom system exhibit photoconductivity, can be sensitized, and can be easily formed into films, so they can be applied to general semiconductor materials and photoconductive materials for electrophotography. is progressing.

In particular, when photosensitivity is required for practical purposes, it is necessary to improve the sensitivity of the photosemiconductor material and to add a sensitizer.

The synthesis of vinyl polymers having aromatic side groups with high photoconductivity has attracted interest and demand as an important compound.

The present inventors used an organic optical semiconductor to develop a new material, which is a raw material for poly-N-(p-vinylphenyl)carbazole, which is expected to have the above-mentioned properties and uses, especially for the purpose of obtaining highly sensitive photographic materials. Monomer N-(p-vinylphenyl)
Completed the manufacturing method of Carbasol.

The manufacturing method of the present invention consists of three steps.

That is, the first step: General formula (R: IA such as hydrogen, lithium, sodium, potassium, etc.
This is the synthesis of N-(p-(β-hydroxyethyl)phenyl)carbazole obtained by a coupling reaction between a group atom) and p-halogenated phenethyl alcohol.

The p-halogenated phenethyl alcohol used here as a starting material is
Société Simique de France' (S, 5ab
etay.

”Bulletin de la 5ociete C
France” (j), 45.
842 pages, (1929), “Periodique Bupure-Abecle Concours du Saint-Cyr National de la Richierche Cientifique” (P.
eradique Pablie avec leC
oncourses du Center Nation
al de 1aRecherche 5cint
Issue one ifique; 11. ``Journal of the Chemical Society'' (G, Baddel)
ey,”'Journal of the Chemical
al 5ociety”) 1819 pages, (1935>,
The Chemical Society London” (The Ch
chemical 5ociety (London))
It is produced from phenethyl alcohol by a known method as described in the publication.

Second step: N-(p-(β-hydroxyethyl)phenyl)carbazole is converted into thionyl chloride, phosphorus oxytrichloride (POC
12), etc., and the product is extracted with n-hexane to obtain N-(p-(β-ethylhalide)phenyl)calhasolka.

Third step: The dehydrohalogenation reaction of N-(p-(β-ethyl halide) phenyl dirubazole is performed using a deoxidizing agent, such as an alcoholic alkali metal hydroxide (alkali metals include sodium, potassium, lithium, etc.). ), and the crude crystals are purified by a recrystallization method to obtain N-(p
-vinylphenyl)carbazole can be obtained.

The alcohol used here is most preferably isopropyl alcohol, and methanol and ethanol are not preferred because they lower the yield.

The reflux conditions in the second and third steps described above vary depending on the boiling point of the solvent used, but are preferably about 5 to 10 hours in the second step and about 1 to 5 hours in the third step.

These conditions can be easily determined by those skilled in the art by selecting the solvent to be used.

In order to clarify the contents of the present invention, the following examples will be described.

However, it goes without saying that the content of the present invention is not limited to the scope of the embodiments.

Example (i) N-(p-(β-hydroxyethyl)phenyl)
Synthesis of carbazole: 87.2 g of carbazole, 124.5 g of p-iodophenethyl alcohol, 78.0 g of anhydrous potassium carbonate, 3.7 g of copper powder. 500 ml of nitrobenzene was charged, and the mixture was kept at 215° C. and refluxed for 6 hours while stirring vigorously.

After nitrobenzene was distilled off from the reaction mixture by steam distillation, it was cooled.

The filtered residue was washed with water and dissolved in 500ml of benzene.
After filtration, water was completely removed from the filtrate by distillation.

After cooling, dry hydrogen chloride was passed through, the resulting carbazole hydrochloride was filtered off, and benzene was distilled off to obtain a tar-like substance.

This was extracted with n-hexane, and 130 g of pale yellow flocculent crystals (
Yield: 80.1%).

mp 113.1-114.0°C N (element) analysis Calculated value 4.87% Actual value 4.50% MS (mass spectrum) measurement Calculated value 287.1310 Actual value 287.1271 NMR (CDC13) r=1 .7~2.9 (m), 6
．． 1(t), 7.1(t), 8.4(s) IR (KBr
) 3300,1360°13301030cfrL
-1 shows absorption.

It was confirmed to be the substance by N analysis, MS measurement, NMR, IR, etc.

(!1) Synthesis of N-(p-(β-chloroethyl)phenyl]carbazole: The aforementioned N-(p-(β-hydroxyethyl)phenyl)
18.1g of carbazole to 110.0rIll of benzene
12.0 rfll of thionyl chloride was added dropwise.

After stirring and refluxing for 7 hours, benzene and thionyl chloride were distilled off, and the residue was extracted with n-hexane and treated with activated carbon to obtain 16.2 g of colorless plate-like crystals (yield: 84.1%).

mp 140.0-140.9°C C1 (element) analysis Calculated value 11.59% Actual value 11
．． 45% NMR (Acetone-D5) T=1.6-3.
0 (m), 6.1 (t), 6.8 (t) IR (KBr) 1360, 1330°710 69
It shows absorption at 5CrrL-1.

It was confirmed to be the substance by C6 analysis, NMRlIR, etc.

(iii) Synthesis of N-(p-vinylphenyl)carbazole: 10.8 g of the above N-(p-(β-chloroethyl)phenyl)carbazole was mixed with 295 g of isoprobil alcohol.
．． After heating and dissolving with 0 ml, potassium hydroxide 32.5
g was added and refluxed for 1 hour.

The reaction solution was pressurized to 1.75% water, cooled, filtered, and the white powder crystals were washed with water until the pH reached 7.

The crystals were dried, dissolved in heated acetone, treated with activated carbon, separated, and the filtrate yielded 8.49 white crystals (yield 88.1
%).

mp 121.5-122.1°C Elemental analysis Calculated value Actual value C89,19% 89.21% H5,61% 5.62% N 5.20% 5.01% NMR (CDCJ!3) r=1 .7-3.0(m)3.
2(q), 4.2(d), 4.7(d) IR (KBr
)1650,1360°1330.985,910Cr/l-'.

It was confirmed to be the substance by elemental analysis, NMRl IR, etc.

Claims (1)

[Claims] 1 N- obtained by the reaction of carbazole or its alkali metal salt with p-halogenated phenethyl alcohol
N-(p-vinylphenyl) is produced by halogenating the hydroxyl group of (p-(β-benzene)phenyl)carbazole after refluxing, and then carrying out a vinylation reaction under the action of an alcoholic alkali metal hydroxide. ) Method for producing carbazole.