JP2562987B2 - Manufacturing method of photosensitive compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a process for producing a photosensitive compound comprising a formylstyrylpyridinium salt or a formylstyrylquinolinium salt.

[Conventional technology]

Formylstyrylpyridinium salt and formylstyrylquinolinium salt are useful compounds as raw material compounds for water-soluble photosensitive resins.

As a method for producing the salt, as disclosed in JP-A-55-24126, a methylpyridinium salt or a methylquinolinium salt and phthalaldehyde are condensed in a reaction solvent at a reflux temperature in the presence of a basic catalyst. The method of making it known is conventionally known. In this production method, a polar solvent such as methanol or ethanol is used as a reaction solvent, but there is a drawback that the yield of the main product (target product) is low (50% or less) because there are many by-products. When such a polar solvent is used alone,
In addition to the diolefin-type compound as a by-product, the production rate of the adhesive coloring compound is high, and it is difficult to separate this from the main product.

As another manufacturing method from the same starting material, JP-A-59-1996
As disclosed in JP-A-72, a method of reacting in a mixed solvent system of a polar solvent and a non-polar solvent, and JP-A-59-193872.
As disclosed in the publication, a method of dropping a quaternary salt is known. In these production methods, the diolefin-type compound as a by-product is reduced as compared with the case where the polar solvent is used alone, but since it is a reaction in a mixed solvent system, it is difficult to recover and reuse the solvent. However, it is hard to say that the manufacturing method is industrially advantageous.

[Problems to be Solved by the Invention]

An object of the present invention is to provide a process for producing a photosensitive compound that can be industrially obtained in high yield.

[Technical Means and Actions for Solving Problems]

As a result of repeated studies to solve the above-mentioned problems, the inventors of the present invention improved the reaction solvent and reaction temperature by suppressing side reactions in the condensation step and promoting the main reaction. Was completed.

That is, the process for producing the photosensitive compound according to the present invention is carried out according to the general formula [I] or [II] (In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aralkyl group, and these may include a hydroxyl group, a carbamoyl group, an ether bond, or an unsaturated bond, and R ² represents a hydrogen atom or a lower alkyl group, X ^- is condensed in the presence of a basic catalyst in a reaction solvent and a compound with phthalic aldehyde represented by represents an anion), the general formula [III] (In the formula, A is a general formula [IV] or [V] R ¹ in the general formula [IV] or [V],
R ² and X ⁻ each have the same meaning as described above), and in producing the photosensitive compound represented by the above, the reaction solvent is at least selected from the group consisting of lower alcohols, polyhydric alcohol derivatives, dimethylformamide and dimethylsulfoxide. It is a kind of polar solvent and has a reaction temperature of 25 to 70 ° C.

The photosensitive compound represented by the general formula [III] is represented by the general formula [I] or [I
[I], that is, a methylpyridinium salt or methylquinolinium salt and phthalaldehyde can be obtained by condensation in the presence of a basic catalyst in a reaction solvent, and in the condensation reaction, as a by-product, Generally, the general formula [VI] (In the formula, A has the same meaning as described above), and a diolefin type compound represented by the formula or an adhesive coloring compound which is difficult to specify in the general formula is produced.

Although the mechanism of formation of the adhesive coloring compound is not clear,
When condensation is carried out in a polar solvent such as methanol or ethanol at a high temperature such as under reflux conditions, the general formula [II
[1] The photosensitive compound (main product) of [I] is further reacted with phthalaldehyde at a methyl group in which the nitrogen atom in the compound is quaternized, or the by-produced diolefin-type compound of the general formula [VI] is phthalate. It is presumed that the adhesive coloring compound is produced by a reaction route such as further reaction with aldehyde. It should be noted that the increase in the amount of the tacky coloring compound reduces the main product and makes it difficult to purify the main product.

Since the tacky coloring compound is abruptly generated by increasing the reaction temperature and interferes with the main reaction, a reaction temperature of 25 to 70 ° C. lower than the reflux temperature is selected in the present invention. When the reaction temperature is lower than 25 ° C, the main reaction is difficult to proceed, and when the reaction temperature is higher than 70 ° C, the side reaction which forms the adhesive colored compound is easily promoted, which lowers the yield of the main product and the main product. Purification becomes difficult.

The reaction solvent used in the present invention is preferably a solvent having high polarity, and at least one selected from lower alcohols, polyhydric alcohol derivatives, dimethylformamide and dimethylsulfoxide can be selected.

Examples of the lower alcohols include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, pentyl alcohol, ethylene glycol and propylene glycol. Further, as a polyhydric alcohol derivative, a compound represented by the general formula [I]
Alternatively, a compound capable of dissolving the compound of [II] is preferable, and methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Examples thereof include tertiary butyl cellosolve.

Among the above polar solvents, an alcohol having 3 to 4 carbon atoms is particularly preferable, and these solvents are represented by the general formula [I] or [II].
However, the compound has low solubility in the photosensitive compound of the general formula [III] and precipitates at the reaction temperature.

If phthalaldehyde is dissolved in the reaction solvent, it will be dissolved sequentially as the condensation proceeds, even if it is not completely dissolved. Therefore, there is no problem with the reaction. The compound of the general formula [I] or [II] is preferably dissolved in a reaction solvent and gradually added dropwise.

As the basic catalyst, for example, a secondary amine or a tertiary amine can be used alone or in combination of two or more kinds.

As the secondary amine, piperidine, pyrrolidine,
Examples thereof include diethylamine and dicyclohexylamine. Further, as tertiary amines, lower aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine, N-methyl, N-
Examples thereof include N-C ₁ -C ₄ lower alkylpiperidine or pyrrolidine such as ethyl, tetramethylethylenediamine, tetramethyldiaminopropane and the like.

In the present invention, phthalaldehyde is equimolar or more to the compound of the general formula [I] or [II], preferably 1.0
It may be used in an amount up to 1.5 times.

〔Example〕

Hereinafter, examples of the present invention will be described in comparison with comparative examples, but the present invention is not limited to these examples.

<Example 1> 46.6 g (0.50 mol) of γ-picoline was added to 100 parts of isobutanol.
In addition to g, 63 g of dimethyl sulfate (0.
(50 mol) was added dropwise over 1 hour, and the reaction solution was further stirred at room temperature for 1 hour to obtain a solution A.

Next, in a reaction flask, 100.6 g of terephthalaldehyde
(0.75 mol), piperidine 8.5 g (0.1 mol) and isobutanol 200 g were charged, and this solution was heated and stirred at 60 ° C.,
When the solution A was added dropwise over 5 hours, yellow crystals gradually precipitated.

After completion of the dropping, heating and stirring were continued at 60 ° C. for another 2 hours. After cooling the reaction solution, the precipitated solid substance obtained by filtration was washed with acetone and dried to obtain N-methyl-4 as a main product.
A yellow mixed crystal of-(p-formylstyryl) pyridinium methosulfate and a by-product diolefin type compound was obtained (yield 153 g).

When 153 g of the mixture was added to a mixed solvent of 300 ml of methanol and 40 ml of water and heated to 70 ° C., the main product was dissolved and the diolefin type compound as a by-product was not dissolved but remained as a solid. there were. This solution was filtered while hot to separate yellow crystals of the diolefin-type compound from the filtrate (yield
13 g, yield 9.7%).

The filtrate was evaporated to dryness to obtain yellow crystals of the main product, N-methyl-4- (p-formylstyryl) pyridinium methosulfate (140 g, 83.6% yield).

<Example 2> Example 1 except that methyl p-toluenesulfonate was used instead of dimethyl sulfate, isopropanol was used instead of isobutanol, and the reaction temperature was 50 ° C instead of 60 ° C.
The same process was carried out.

Main product N-methyl-4- (p-formylstyryl)
The yield of pyridinium p-toluenesulfonate is 74.2%,
The yield of the by-product was 9.0%.

<Example 3> 4-methylquinoline was used in place of γ-picoline, and ethyl cellosolve was used in place of isobutanol, and the same steps as in Example 1 were carried out.

Main product N-methyl-4- (p-formylstyryl)
The yield of quinolinium methosulfate was 78.3% and the yield of by-products was 10.1%.

<Example 4> [alpha] -picoline was used in place of [gamma] -picoline, isopropanol was used in place of isobutanol, and the reaction temperature was 60.
The same process as in Example 1 was carried out except that the temperature was changed to 65 ° C instead of 65 ° C.

Main product N-methyl-2- (p-formylstyryl)
The yield of pyridinium methosulfate was 82.8% and the yield of by-products was 9.8%.

<Comparative Example 1> The same steps as in Example 1 were carried out except that the reaction temperature was changed from 60 ° C to 90 ° C.

The reaction liquid was strongly colored by-products, became opaque dark reddish brown, and the crystals separated by filtration were brown yellow, and the main product was also obtained as brown yellow crystals.

Main product N-methyl-4- (p-formylstyryl)
The yield of pyridinium methosulfate was 49.5% and the yield of by-products was 14.8%.

〔The invention's effect〕

As described above, according to the method for producing a photosensitive compound of the present invention, a side reaction is effectively suppressed, and a photosensitive compound composed of a formylstyrylpyridinium salt or a formylstyrylquinolinium salt is easily produced in high yield. It can be manufactured.

Further, since only a polar solvent needs to be used as the reaction solvent, the solvent can be easily recovered and reused.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 59-193872 (JP, A) JP 59-199672 (JP, A) JP 4-49278 (JP, A)

Claims (2)

(57) [Claims] 1. A general formula [I] or [II] (In the formula, R ¹ represents a hydrogen atom, an alkyl group or an aralkyl group, and these may include a hydroxyl group, a carbamoyl group, an ether bond, or an unsaturated bond, and R ² represents a hydrogen atom or a lower alkyl group, X ^- is condensed in the presence of a basic catalyst in a reaction solvent and a compound with phthalic aldehyde represented by represents an anion), the general formula [III] (In the formula, A is a general formula [IV] or [V] R ¹ in the general formula [IV] or [V],
R ² and X ⁻ each have the same meaning as described above), and in producing the photosensitive compound represented by the above, the reaction solvent is at least selected from the group consisting of lower alcohols, polyhydric alcohol derivatives, dimethylformamide and dimethylsulfoxide. A process for producing a photosensitive compound represented by the general formula [III], which is a polar solvent and has a reaction temperature of 25 to 70 ° C. 2. The method for producing a photosensitive compound represented by the general formula [III] according to claim 1, wherein the reaction solvent is an alcohol having 3 to 4 carbon atoms.