JPS5988450A - Preparation of bisazide-type photo-crosslinking agent - Google Patents

Abstract

PURPOSE:To prepare a bisazide-type photo-crosslinking agent, easily, with a simple process, at a low cost, by oxidizing 1,4-cyclohexanediol with deficient amount of oxidizing agent, and subjecting the resultant aldehyde compound to dehydrative condensation reaction in the presence of an alkali catalyst. CONSTITUTION:1,4-Cyclohexanediol is oxidized wth a deficient amount of an oxidizing agent such as chromic acid (the amount oxidizing 2-40% of the OH group of the diol to ketone group) to obtain a mixture of 1,4-cyclohexanediol and 4-hydroxycyclohexanone. The objective 2,6-di(p-azidobenzal)-4-hydroxycyclohexanone and 2,6-di(p-azidocinnamylidene)-4-hydroxycyclohexanone can be prepared by the dehydrative condensation of the above mixture with p-azidobenzaldehyde or p-azidocinnamaldehyde in a solvent inert to alkali (e.g. methanol), in the presence of an alkaline catalyst such as NaOH, KOH, etc. at 0-100 deg.C.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to 2,6-di(paraazidobenzal)-4-hydroxycyclohexanone (.
lI) or 2,6-di(paraazidocinnamylidene)-4-hydroxycyclohexanone (also
The present invention relates to a method for producing a bisazide photocrosslinking agent selected from the group consisting of

This photocrosslinking agent has high solubility in polar solvents and high photoreactivity, so it is used as an effective crosslinking agent.

[Prior art]

Conventionally, the above bisazide photocrosslinking agent (II or 4-
It was synthesized using an alkali-catalyzed condensation reaction of hydroxycyclohexanone and para-azidobenzaldehyde or para-azido cinnamaldehyde (Japanese Patent Publication No. 55
-49295), I.However, in the case of the prior art, there is no way to economically obtain the raw material 4-hydroxycyclohexanone, so it is also an expensive substance, and in the end, its industrial use is limited. It was restricted. Raw material 4
-Hydroxycyclohexanone can be obtained by synthesis using 1,4-cyclohexanediol as a starting material by esterification, selective deesterification, oxidation, and deesterification [D, E.

Emrnert, D., Lednicgr., Org.
, Prep, and Procedures.

127 (1969)), but the synthesis steps are long (4 steps) and include selective deesterification, which is difficult in the synthesis method, resulting in low yield (16.5%) and production cost. On the other hand, when 1,4-cyclohexanediol is oxidized using a silver carbonate-celite reagent,
Method for selectively oxidizing only hydroxyl groups CM, Fgti
zon, M., Golfigr, J-M., Lovi.
s.

Chem, Commtbn, 1102 (1969)
, l are also known, but this method requires only one synthesis step.
However, the process of making the oxidizing reagent is difficult and the silver compound is expensive, making manufacturing costs high.

In order to obtain the photocrosslinking agent (lIl) or (ii) at a low cost, it is necessary to obtain its precursor, 4-hydroxycyclohexanone, by a simple production method. However, in this case, when 1,4-cyclohexanediol is used as a starting material, it is necessary to prevent the by-formation of 1,4-cyclohexanedione in which two hydroxyl groups of the starting material compound are oxidized during the synthesis process. . This is because the by-product compound with also has a methylene group at the α-position of the carbonyl group that is active in alkali condensation, so it will undergo a condensation reaction with the aldehyde compound that is the reaction partner under the conditions of alkali condensation.
This is because it becomes a by-product.

This by-product is difficult to separate because it has similar crystallinity to the target compound (Illll or (2)) or (2)) or (2).
When the product) contains this by-product, it does not adversely affect the photosensitivity of the photosensitive composition using the product.

Under these circumstances, the conventional method for producing 4-hydroxycyclohexanone described above uses a selective deesterification method and an expensive special silver compound in order to prevent the by-formation of 1°4-cyclohexanedione. be.

[Purpose of the invention]

The purpose of the present invention is to provide 2,6-di(paraazidobenzal)-4-hydroxycyclohexanone (2,6-di(paraazidobenzal)-4-hydroxycyclohexanone (
I[lJ or 2,6-di(paraazidocinnamylidene)
It is an object of the present invention to provide a manufacturing method capable of obtaining -4-hydroxycyclohexanone (Incorporated) easily and inexpensively through a simple process.

[Summary of the invention]

In order to achieve the above object, the inventors of the present invention made extensive studies and found that 1,4-cyclohexanediol (I) was oxidized with an insufficient amount of oxidizing agent. l) If a mixture of CI) and 4-hydroxycyclohexanone (■) is prepared, and this mixture is reacted with a raw material aldehyde under condensation reaction conditions,
Desired compound (III) can be obtained easily and inexpensively through an easy process.
Or, we have reached the point where we can obtain control.

The present invention is based on the following findings.

If 1,4-cyclohexanediol (1) is oxidized with too little oxidizing agent, the 4-hydroxychlorohexanone produced will be further oxidized to produce cyclohexanedione, but the concentration will be overwhelmingly high. Due to the high probability of oxidizing cyclohexadiol to 4-hydroxycyclohexanone, the resulting product is a mixture of 1,4-diol (I) and 4-hydroxycyclohexanone. If this mixture is subjected to a condensation reaction with an aldehyde compound under alkaline synthesis conditions, 1,4-diol (11 does not undergo a condensation reaction because it does not have an active methylene group and remains dissolved in the reaction solvent. , 4-hydroxycyclohexanone undergoes a condensation reaction with an aldehyde, and the product (IIl) or (Nl) crystallizes and precipitates from the reaction solution. Therefore, it can be isolated by a conventional oral filtration method.

Therefore, according to the present invention, special reagents may be used.
Moreover, the desired compound can be obtained in two short reaction steps without the generation of non-separable by-products, and therefore the photocrosslinking agent can be easily produced through simple steps and at low cost.

The invention may be practiced in a number of ways.

Examples of the oxidizing agent used in the oxidation reaction include methods using chromic acid, dichromate, permanganate, manganese diaate, etc., but any reaction that oxidizes a hydroxyl group to a carbonyl group is sufficient; Very limited.

As for the amount of oxidizing agent used, it is desirable to use the amount calculated to oxidize 2 to 40% of the hydroxyl groups of diol (I) into ketone groups. If more than this amount is used, the by-formation of cyclohexanedione is unavoidable.

During the reaction, it is desirable to add the oxidizing agent little by little stepwise to the entire diol (1) in order to maintain the selectivity of the oxidation reaction and prevent the by-formation of cyclohexanedione.

Acetone is used as a solvent in the oxidation reaction.

Methyl ethyl and other ketones, methylene dichloride,
A typical example is a halogenated solvent such as chloroform, but the solvent is not limited to these as long as it is stable against oxidizing agents.

The reaction temperature is preferably in the range of -50 to 50°C, and if it deviates from this range, the yield will decrease.

The reaction mixture obtained by the above reaction is concentrated and isolated as a mixture of 1,4-cyclohexanediol and 4-hydroxycyclohexanone by vacuum distillation.

If the liquid is acidic, neutralize it before concentration.

For the condensation reaction, dissolve this mixture and paraazidobenzaldehyde or paraazidocinnamaldehyde,
The blending ratio is 1 to 5 moles, preferably 2 to 3-[nyl] per mole of 4-hydroxycinolohexanone. Outside this range, the yield of the product decreases.

Examples of the solvent for the synthesis reaction include alcoholic solvents such as methanol and ethanol, but the solvent is not limited to these as long as it is stable under alkaline conditions and does not inhibit the synthesis reaction.

Representative examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, sodium alcoholade, potassium alcoholade, etc., but the catalyst is not limited to these as long as it can activate the condensation reaction.

The amount of the alkali catalyst is 0.01 to 2 mol, preferably 0.1 to 0.5 mol, based on 4-hydroxycyclohexanone.
It is preferable to use it in a molar range; deviations from this range may activate the condensation reaction, cause side reactions, and reduce the yield.

The alkaline catalyst is usually added to the reaction mixture after being made into an aqueous solution, but if a solvent that dissolves the alkaline compound is used, it may be added directly to the solution.

The reaction temperature is preferably within the range of 0 to 100°C, and if it deviates from this range, the yield will decrease.

The reaction time varies depending on the reaction temperature.

The preferred time is from 1 hour to several days, and if it deviates from this, the yield will decrease.

The product (III or head) obtained by the above reaction precipitates as crystals, and is isolated by the oral filtration method and purified by recrystallization.

Examples of the recrystallization solvent include acetonitrile, methyl cellosolve, and ethyl cellosolve.

[Embodiments of the invention]

Some examples of the present invention are shown below.

Example 1: 100# (0.86 mol) of 1.4-cyclohexanediol was dissolved in 3 L of acetone, and this solution was treated with anhydrous water while controlling the reaction temperature at 0 to 10°C using a cold bath. 2Of chromic acid (0.2 mol, calculated amount to oxidize 1z hydroxyl group of the above diol to ketone group), concentrated sulfuric acid 17t, water 55? A solution consisting of was added dropwise under stirring. After the addition, the solution was further stirred for 10 minutes, and then a portion of the solution was separated using a tilted filtration method.
The product 74f gold was obtained.

This fraction is the result of gas chromatography analysis.

It was a 7:2 mixture of 1.4-cyclohexanediol and 4-hydroxycyclohexanone (the yield of 4-hydroxycyclohexanone based on the oxidizing agent was 73%).
). From this result, assuming that the content of 4-hydroxycyclohexanone is 25P (0.22 mol), this mixed solution and para-azidobenzaldehyde 73.5y (0.s mol)
was dissolved in 500yxt of methanol, and to this was added a solution of 1f (0,025 mol) of sodium hydroxide in 1rnt of water.

After reacting for 2 days at room temperature, the formed crystals were separated by suction filtration, recrystallized from acetonitrile, and converted to 31S.
# (Yield: 41!1%) of 2,6-di()chlorazidobenzal)-4-hydroxycyclohexanone was obtained (thermal decomposition point: 148°C).

Example 2: A mixture 10f of 1,4-cyclohexanediol and 4-hydroxycyclohexanone obtained in Example 1 (4-
Hydroxycyclohexanone content 3t, 0.026 mol) and paraazide cinnamaldehyde ID# (0,0
58 mol) was added to 100 mt of methanol, and a solution of 0.29 (0,0036 mol) potassium hydroxide dissolved in 1 mL of water was added and reacted for 2 days. The formed crystals were separated by suction filtration and recrystallized from ethyl cellosolve to obtain 2.6-di(paraazidocinnamylidene)-4-hydroxycyclohexanone of 2.85F ([ratio 25%)]. (Thermal decomposition point: 165°C).

Example 3: 1,4-cyclohexanediol 10p (0,086
mol) in 30 omt methylene dichloride and stirred. Next, pyridinium chlorochromate <Q-CrO
, -HCL) 4.5ft (0.02 mol, calculated amount to oxidize the 116th hydroxyl group of the above diol to a ketone group)
was divided into 043i portions and added at 5 minute intervals under room temperature conditions.

After adding the entire amount, stir for another 60 minutes, take a portion of the solution, concentrate and distill under reduced pressure to bp 115-125℃.
8.2 t of product was obtained. As a result of gas chromatography analysis, this fraction was found to contain 1,4-cyclohexanediol and 4-cyclohexanediol.
- 8:2 mixture of hydroxycyclohexanone (48% yield of 4-hydroxycyclohexanone)
. This mixture and paraazidobenzaldehyde 2.05#
(0.03 mol) was dissolved in 50 mt of methanol, and 0.5+5# (0.01 mol) of potassium hydroxide was added thereto to dissolve and react for 2 days. The formed crystals were separated by suction filtration and recrystallized from methyl cellosolve to obtain 2.1# (yield 40%) of 2,6-di()(laazidobenzal)-4-hydroxycyclohexanone.

〔Effect of the invention〕

As detailed above, p2.6-
The steps for synthesizing di(paraazidobenzal)-4-hydroxycyclohexanone or 2,6-cy(nocraazidocinnamylidene)-4-hydroxycyclohexanone could be reduced from the conventional five steps to two steps. Furthermore, there is no generation of non-separable by-products, and the target compound can be obtained without using special reagents or difficult reactions.

Therefore, according to the present invention, a useful gabisazide crosslinking agent can be produced simply and inexpensively through easy steps.

Representative Patent Attorney Susuki 1) O024,4',i,'ゝ.

Nitan 211

Claims (1)

[Scope of Claims] t By oxidizing 1,4-cyclohexanediol (IJ) using an insufficient amount of an oxidizing agent in a solvent inert to the oxidizing agent, 1,4-cyclohexanediol ( I
) A mixture of 4-hydroxycyclohexanone (n) is formed, and then this mixture is subjected to a dehydration condensation reaction with baraazidobenzaldehyde or baraazidocinnamaldehyde in an alkali-inert solvent using an alkali catalyst. selected from the group consisting of 2,6-di(baraazidobenzal)-4-hydroxycyclohexanone (lIl) or 2,6-di(baraazidocinnamylidene)-4-hydroxycyclohexanone (Foundation). A method for producing a bisazide photocrosslinking agent. 2. For the amount of oxidizing agent, use the amount calculated to oxidize 2 to 40% of the hydroxyl groups in 1,4-cyclohexanediol (11) to ketone groups, and add this oxidizing agent to the entire 1,4-cyclohexanediol (1). A method for producing a bisazide photocrosslinking agent according to claim 1, characterized in that the bisazide photocrosslinking agent is added stepwise to 1 mole of 3.4-hydroxycyclohexanone, baraazidobenzaldehyde or baraazidocinnamaldehyde. A method for producing a bisazide photocrosslinking agent according to claim 1, characterized in that chromic acid is blended in an amount of 1 to 5 moles, preferably 2 to 3 moles.4. Chromic acid as an oxidizing agent; A method for producing a bisazide photocrosslinking agent according to claim 1, which uses military chromate, permanganate, or manganese dioxide. 5. Sodium hydroxide or potassium hydroxide as an alkali catalyst. , sodium alcoholade, or potassium alcoholatra, the amount of which is 0.01 to 2 mol, preferably 0.1 per mol of 4-hydroxycyclohexanone.
2. The method for producing a bisazide photocrosslinking agent according to claim 1, wherein the amount is used within the range of 0.5 mol.