JPS60239473A - 2-trihalomethyl-5-penyl-1,3,4-oxadiazole compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is H, Cl, Br, 1-4C alkoxyl or 1-4C alkyl; X is Cl or Br). EXAMPLE:2-Trichloromethyl-5-(p-styrylphenyl)-1,3,4-oxadiazole. USE:A photochemical reaction initiator used in a photosensitive composition and element, which is a substance having high sensitivity to light and liberating and producing ability, and incorporable with photopolymerizable compositions useful for producing printing plates, e.g. lithography, letterpress printing and intaglio printing plates, IC circuits, photoresists, photographic elements and baking compositions and photosensitive resist forming compositions capable of giving visible images only by exposure to light. PREPARATION:A carboxylic acid hydrazide derivative of formula II is reacted with a compound of formula III (R' is CF3, CBr3, Cl, Br, O-CO-CCl3 or O-CO- CBr3) in a solvent to form a compound of formula IV, which is then heated with POCl2 or acetic anhydride, etc. in a molar amount of 2 times or more, etc. to afford the aimed compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to λ-trichloromethyl! -phenyl-i, 3
．． This invention relates to a new substance belonging to t-oxadiazole compounds.

“Conventional technology” Compounds that decompose and generate free radicals when exposed to light (
Free radical generator) Fi is well known in the field of graphite isoarts. They are widely used as photoinitiators in photopolymerizable compositions, photoactivators in free radical photographic compositions, and photoinitiators for reactions catalyzed by photogenerated acids. Such free radical generators are used to make a variety of photosensitive materials useful in printing, duplication, copying and other imaging systems.

Organic halogen compounds are useful as photoinitiators because they generate halogen free radicals when exposed to light. Conventionally, carbon tetrabromide, iodoform, tribromoacetophenone, and the like are representative compounds that generate halogen free radicals by the action of light, and have been widely used. However, these free radical generators have the disadvantage that they are only decomposed by light in a very limited wavelength range. In other words, it was sensitive to the ultraviolet region, which is shorter than the dominant wavelength of commonly used light sources. Therefore, these compounds lack the ability to effectively utilize light in the near-ultraviolet to visible range emitted by a light source, and therefore have poor free radical-generating ability.

The following general formula (1) is a substance that can improve these drawbacks and has the ability to generate free radicals with high sensitivity to light.
It has been found that the novel compound shown is useful.

"Structure of the Invention" That is, the present invention has the following general formula CI).
A trihalomethyl-j-phenyl-7,3゜p-oxadiazole compound is provided.

In the formula, 几 is a hydrogen atom, a chlorine atom, a bromine atom, the number of carbon atoms/
represents an alkoxy group having 1 to 3 carbon atoms, and X represents a chlorine atom or a bromine atom.

Novel coat trihalomethyl-j-phenyl-/ of the present invention
, 3. II-oxadiazole compounds can be advantageously synthesized by a series of reactions shown in the following reaction formula.

+ α3cmC0-R'-> (III) The synthesis of the carboxylic acid hydrazide derivative of general formula (II) used for the production of the compound of the present invention is carried out using W, 0° Godt
Acta by fredsen & S., Vangedal
Chem, 5cand, ta /4Crir(/rijj
) and S. Harada & H. Konao,
Bull, Chem, Soc, J'ap, II / (
/0) It can be carried out according to the method described in 2j. That is, a mixed acid anhydride synthesized from an alkali metal salt of a carboxylic acid and ethyl chlorocarbonate is added to an ice-cooled dispersion of hydrazine hydrate in chloroform.
After dissolving or dispersing an activated ester such as Kayaponic acid D cyanomethyl ester or p-nitrophenyl ester in methanol, chloroform, etc., add foamy hydrazine and heat from room temperature to reflux temperature. This method involves stirring within a range. The resulting crude carbo/acid hydrazide can be purified by recrystallization in ethanol or methanol or water.

The compound of general formula (2) can be derived from the compound of general formula (1) and general formula I by a known method.

For example, a method in which carboxylic acid hydrazides are stirred in a slight excess of hexaclodiacetone and a solvent such as acetonitrile at room temperature at reflux temperature, a method in which carboxylic acid hydrazides are stirred with an equimolar amount of trichloroacetic anhydride at room temperature, There is a method in which 2 moles of carboxylic acid hydrazide and 1 mole of trichloroacetic acid chloride are stirred at room temperature using a solvent such as dioxane or tetrahydrofuran. The crude product can be purified by recrystallization with acetonitrile, ethanol, methanol, etc.

-mIy from the corresponding l,3. M, P, Hutt lead to ≠-oxadiazole.

Elslager, E.F., Werbel, L.M.
Author J, Heterocylic Chem, 7 (J
) s/i (performed according to the method described in 7(17)).

That is, it can be synthesized by heating and refluxing N-acryloyl-N/-haloacetyl hydrazide with phosphorus oxychloride or acetic anhydride in an amount of 2 times the mole or more. Toluene, benzene, etc. can be used as a reaction solvent. The crude product is ffffffed by recrystallization from ethanol-containing ethanol or the like.

Specific examples of compounds of the present invention are as follows.

"Effects of the Invention" (a) When irradiated with active light having a wavelength of about 300 to about 500 nm, the /,J,44-oxadiazole compound of the present invention generates free radicals. For this reason, the compounds are useful as photoinitiators for use in photosensitive compositions and elements. Thus, these are lithography, letterpress, intaglio, etc.
The photopolymerizable compositions and bakes used to make any printing plate, photoresist, and photographic element can be formulated into a photosensitive resist-forming composition that provides a visible image upon exposure to light alone.

The free radical generating agent of the present invention can be used in photosensitive resist-forming compositions for producing lithographic printing plates, IC circuits, and photomasks.
It is particularly useful in providing the ability to provide a visible image upon exposure without development.

Since such a photosensitive resist composition can obtain a visible image only by exposure under a yellow safety light during the exposure process, it can be used, for example, in the process of exposing many printing plates at the same time, for example, when the work is interrupted, etc. This makes it possible for a person to know whether a given plate has been exposed or not.

Similarly, for example, when making a lithographic printing plate, when a large plate is exposed to light many times, as is the case with the so-called plate printing process, the operator immediately checks which areas have been exposed. be able to.

The free radical generator of the present invention can be advantageously used in a photosensitive resist-forming composition that provides a visible image immediately upon exposure, which contains as essential ingredients a photosensitive resist-forming compound, a free radical generator, a color change agent and an optional It usually consists of one or more plasticizers, binders, non-color-changing dyes, pigments, antifogging agents, sensitizers for photosensitive resist-forming compounds, etc.

Example 1 p-Aminebenzoic acid! 0.79 in concentrated hydrochloric acid io.

ml, add 100 ml of water, and add 23.ml of sodium nitrite while cooling on ice. A solution of jtf dissolved in 30 parts water and 1 part water was added dropwise. Furthermore, cinnamic acid 5
μ2g2 and acetone 2. After dropping the solution dissolved in Owrl, add sodium acetate 709. A solution of cupric chloride/j, jt in water IIJt@l was added. The mixture was stirred for 2 hours under water cooling and further stirred for 2 hours at room temperature to react, and then left in the apparatus overnight to complete the reaction. After acetone was distilled off under reduced pressure, the mixture was cooled with water and the resulting precipitate was collected. Recrystallization from acetic acid and further from ethanol gave stilbe/-≠-carboxylic acid.

Stilbene-triple-carboxylic acid co≠, o? , p-nitrophenol/l, 7? , thionyl chloride 3/.

oy and toluene were heated under reflux for 2 hours.

After distilling off excess thionyl chloride, the reaction solution was cooled,
The precipitated stilbene-Hiro-carboxylic acid p-nitrophenyl ester was collected.

Stilbene=≠-carboxylic acid p-nitrophenyl ester/2. Of and go% hydrazine hydrate were added to 30 ml of methanol and heated to reflux for 30 minutes.

After cooling, hydroxide the reaction solution) IJum≠7 and water 30@
1 was added to obtain stilbene-≠-carboxylic acid hydrazide.

Stilbene-≠-carphonic acid hydrazide lj.

Hirof was added to a solution of 21.29 kg of hexachloroacetone and 1 so7 acetonitrile, and the mixture was heated under reflux for 30 minutes. The reaction solution was cooled, and the precipitate was collected to obtain N-(p-styrylbenzoyl)-N'-)lichloroacetylhydrazide.

N-(p-styrylbenzoyl)-N'-trichloroacetylhydrazide/? , 09 and phosphorus oxychloride! 0@
After heating under reflux for 2 hours, the reaction solution was poured into 5 oz of ice water, and the resulting precipitate was recrystallized from acetonitrile to give trichloromethyl-S-(p-styrylphenyl)-/
, J, Hiro-oxadiazole r, sy was obtained. The melting point of the obtained compound and the ultraviolet absorption spectrum of the solution dissolved in CH3CN were measured, and the maximum absorption wavelength (λmax) and molecular extinction coefficient (ε) were determined. The results are shown in Table 7.

Example 2 p-aminebenzoic acid 3≠, 70.1 of concentrated hydrochloric acid was added to 32, and after adding water loOgl, sodium nitrite/7. A solution of the tag dissolved in 30@l of water was added dropwise. In this reaction solution, p-chlorocinnamic acid≠5.62
After dropping a solution prepared by dissolving 7 ml of tetrahydrochloride in 00 ml of tetrahydrochloride, add sodium acetate while cooling on ice.
A solution of 73.6f of cupric chloride dissolved in 30@l of water was added.

The mixture was stirred for 2 hours under water cooling and further stirred for 2 hours at room temperature to react, and then left in the apparatus overnight to complete the reaction. Tetrahydrofuran was distilled off under reduced pressure, and the resulting precipitate was collected by cooling on ice. By recrystallizing from acetonitrile and further from ethanol, <2-(p-chlorostyryl)benzoic acid was obtained.

≠-(p-chlorostyryl)benzoic acid 3/, 01, p-
Nitrophenol/l, 7t, thionyl chloride 3/, 0
? and toluene were refluxed for 2 hours. After distilling off excess thionyl chloride, the reaction solution was cooled and the precipitated ≠-(p-chlorostyryl)benzoic acid p-nitrophenyl ester was collected.

≠-(p-chlorostyryl)benzoic acid p-nitrophenyl ester 2j, jW and IrO% hydrazine hydrate i
o, or were added to methanol/20@l and heated under reflux for 30 minutes. After cooling, sodium hydroxide Ir2 was added to the reaction solution.
A solution prepared by dissolving 10011 of water was added to obtain Hiro-(p-chlorostyryl)benzoic acid hydrazide.

'I-(p-chlorostyryl)benzoic acid hydrazide 7.
32 and hexachloroacetone (7.12) were added to 100@l of acetonitrile, and the mixture was heated under reflux for 1 hour. The reaction solution was cooled and the precipitate was collected to obtain N-(p-(p-chlorostyryl)benzoyl)-N-trichloroacetylhydrazide.

N-(p-(p-chlorostyryl)benzoyl)-N
'-) Lichloroacetyl hydrazide 10, JV and oxychloride lymph 0. After heating under reflux for 2 hours, add 5 oz of ice water.
The reaction solution was poured into y. The resulting precipitate was recrystallized from acetonitrile to give trichloromethyl-j-(p-(
p-chlorostyryl)phenyl)-i, 3. ≠-Oxadiazole was obtained.

The melting point, λmax and ε of the obtained compound were measured.
Shown in the table.

Example 3 After adding p-amine benzoic acid 3≠, JfiC@hydrochloric acid 70 liters and further adding water 100 tttl, sodium nitrite/7. 2 ml of water and 30 ml of water. A solution dissolved in 100 ml was added dropwise. In this reaction solution, p-methoxycinnamic acid≠≠
, &f in 5OO1 of tetrahydro7ran was added dropwise, followed by addition of 33 sodium acetate while cooling with water.
31. A solution of 13.62 cupric chloride dissolved in water JO@l was added.

The mixture was stirred for 2 hours under water cooling and further stirred for 2 hours at room temperature to react, and then left in the apparatus overnight to complete the reaction. After distilling off tetrahydrofuran under reduced pressure, the resulting precipitate was cooled with water.
I accomplished it. By recrystallizing from acetonitrile and further from ethanol, ≠-(p-methoxystyryl)benzoic acid was obtained.

Hiro-(p-methoxystyryl)benzoic acid 30°t2, p
-nitrophenol/l, 79, thionyl chloride 3/
, 09 and 260 @l of toluene were refluxed for 2 hours.

After removing excess thionyl chloride by distillation, the reaction solution is cooled to precipitate ≠-(p-methoxystyryl) benzoate e p-
Nitrophenyl ester-tF was collected.

'I-(p-methoxystyryl)benzoin [p-nitrophenyl ester 2! , 0? Oyo (jr O% hydrazine hydrate io, oy was added to methanol/20 ml and heated to reflux for 30 minutes. After cooling, a solution of sodium hydroxide solution dissolved in 100 g of water was added to the reaction solution, and ≠- (p-methkinstyryl)benzoic acid hydrazide was obtained.

Gu (p-methoxystyl A/)benzoic acid hydrazide 1
0.39 and 10.2 V of hexachloroacetone were added to 100 V of acetonitrile, and the mixture was heated under reflux for 1 hour. The reaction solution was cooled and the precipitate was removed to obtain N-(p-(p-methoxystyryl)benzoyl)-N/)lichloroacetyl V hydrazide.

N-(p-(p-methoxystyryl)benzoyl)
-N'-Trichloroacetyl hydrazide/3゜oy and oxychloride phosphorus 011 were heated under reflux for 2 hours, and then heated to 5゜ice of ice water.
The reaction solution was poured into the oy. The resulting precipitate was recrystallized from a7tonitrile to obtain two-trichloromethyl-5-(p-
(p-methoxystyryl)phenyl)-/,! , II-
Oxadiazole was obtained. The melting point of the obtained compound, λm
ax and ε were measured and shown in Table 1.

Reference Example: Apply the photosensitive liquid F using a rotary coater to a silicate-treated aluminum plate after sanding with a nylon brush.
It was dried for 13 minutes to form a photosensitive layer, thereby producing a photosensitive plate.

Pentaerythritol tetraacrylate IIQ Compound of general formula CI) (Exemplary compound A/) 2y Benzyl methacrylate-methacrylic acid (molar ratio 73/27) copolymer toy Methyl ethyl ketone ≠00Hl Methyl cellosolve acetate 300g1This photosensitive printing plate Jet printer (2kW ultra-high pressure mercury lamp,
After imagewise exposure with a (manufactured by Oak Manufacturing Co., Ltd.), the image was developed with a developer having the following composition, and the unexposed portion was removed and a clear image was obtained.

Anhydrous sodium carbonate 10f Butyl cellosolve jf Water 11 Also, even if an unexposed printing plate was subjected to a forced aging test (≠j0C7jchiR0H1j days) and then exposed and developed, a clear image was obtained that was exactly the same as the printing plate immediately after coating. .

Claims (1)

[Claims] Coatlyhalomethyl represented by the following general formula CI)! −
Phenyl-/, 3. II-Oxadiazole compound. In the formula, R is a hydrogen atom, a chlorine atom, a bromine atom, and a carbon number l
- represents an alkoxy group or an alkyl group having from l to g carbon atoms, and X represents a chlorine atom or a bromine atom.