JP2562983B2 - Method for producing photosensitive compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a photosensitive compound comprising a formylstyrin pyridinium salt or a formylstyryl quinolinium 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 methylquinolinium salt and phthalaldehyde are condensed in a reaction solvent in the presence of a basic working medium. 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 are many by-products and the yield of the main product (target product) is low (50% or less).

As another manufacturing method from the same starting material, Japanese Patent Laid-Open No.
-Method of reacting in a mixed solvent system of a polar solvent and a non-polar solvent, as disclosed in JP-A-199672, and JP-A-59-
As disclosed in Japanese Patent No. 193872, a method of dropping a quaternary salt is known. In these production methods, the amount of the by-product diolefin type compound is reduced as compared with the case where the polar solvent is used alone, but it is still difficult to say that it is an industrially advantageous production method.

Further, regarding the treatment of the reaction product after completion of the condensation in the above-mentioned known production method, it is very difficult to take out the reaction solution from the reaction vessel due to the formation of precipitated solid, When washing the precipitated solid of the product with a solvent, the washing result varies depending on the state of precipitation, and complete washing is difficult,
There are many problems such as the operation of hot filtration is required to take out the desired product, and the final step is to evaporate the filtrate to dryness to produce the desired product.

[Problems to be Solved by the Invention]

An object of the present invention is to provide a method for producing a photosensitive compound that can be industrially obtained in high yield. Another object of the present invention is to provide a method for producing a photosensitive compound in which the reaction product after the condensation is easily treated.

[Technical Means and Actions for Solving Problems]

As a result of repeated studies to solve the above problems, the present inventors have completed the present invention by improving the condensation step and the purification step after completion of the condensation.

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 ^- it 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 [II
I] (In the formula, A is a general formula [IV] or [V] R ¹ in the general formula [IV] or [V],
R ² and X ⁻ have the same meanings as defined above, respectively. In producing the photosensitive compound represented by the above formula, the compound represented by the general formula [I] or [II] and phthalaldehyde are dissolved as a reaction solvent. In the method using a compound which does not dissolve the photosensitive compound represented by [III], water to be purified by condensation is successively removed to the outside of the system.

In addition, another method for producing a photosensitive compound according to the present invention is a method of condensing a compound represented by the general formula [I] or [II] and phthalaldehyde in the presence of a basic compound, In producing the photosensitive compound represented by the formula [III], the compound represented by the general formula [I] or [II] and phthalaldehyde are dissolved as a reaction solvent. A method using a compound which does not dissolve the compound is characterized in that the photosensitive compound represented by the general formula [III] is dissolved in water and separated and purified after completion of the condensation.

The photosensitive compound represented by the general formula [III] is obtained by condensing a compound represented by the general formula [I] or [II], that is, a methylpyridinium salt or methylquinolinium salt and phthalaldehyde in a reaction solvent in the presence of a basic catalyst. The compound of the general formula [IV] is usually used as a by-product in the condensation reaction. (In the formula, A has the same meaning as above), and a diolefin type compound represented by the formula is produced.

The condensation reaction and side reaction are represented by the formulas as follows.

[I] or [II] + phthalaldehyde → [III] + H ₂ O [III] + [I] or [II] → [VI] + H ₂ O In the conventional production method described above, the reaction solvent is represented by the general formula [I] ]
Alternatively, the compound of [II] and phthalaldehyde are dissolved, and the photosensitive compound of general formula [III] and the compound of general formula [VI] are not dissolved but precipitated as a precipitate. However, in practice, water generated by condensation is added to the solvent, so that the photosensitive compound of the general formula [III] is slightly dissolved in the solvent, and further the following side reaction proceeds to further advance the compound of the general formula [VI]. Are considered to be by-products.

In the present invention, since water generated by condensation is sequentially removed from the system, the solvent composition does not change, and the solvent of the photosensitive compound of the general formula [III] is suppressed in the solvent as compared with the conventional method. By-product of the general formula [VI] is reduced,
It is considered that the yield of the photosensitive compound of the general formula [III], which is the main product, was improved.

Further, in the conventional method, the excess amount of phthalaldehyde, that is, the unreacted residual phthalaldehyde is dissolved in the solvent under the reaction conditions, but it is partially precipitated when the reaction system is cooled and then separated by filtration. It will be contained as an impurity in the precipitate composed of the photosensitive compound of the formula [III] and the compound of the general formula [VI].

However, in the present invention, after cooling the reaction system, water is added to dissolve the photosensitive compound of the general formula [III] and the compound of the general formula [VI] in the aqueous layer, contrary to the conventional method. At this time, the reaction liquid is separated into two layers, the residual phthalaldehyde is dissolved in the oil layer, and the coloring component produced as a by-product is also dissolved in the oil layer. By separating this and further washing the aqueous layer with a non-polar solvent such as benzene, it is possible to completely remove phthalaldehyde and coloring components contained in a trace amount. It is difficult to take out the reaction product from the reaction vessel by the conventional method, but in the present invention, the reaction product can be easily taken out as a solution. The compound of the general formula [VI] can be filtered out from the aqueous layer after the washing due to the difference in solubility, and the photosensitive compound of the general formula [III] can be obtained by crystallization.

The reaction solvent used in the present invention is preferably a mixed solvent of a solvent having a high polarity and a solvent having a low polarity, and examples of the former include at least one selected from lower alcohols, polyhydric alcohol derivatives, dimethylformamide, dimethylsulfoxide and the like. As an example of the latter, an aromatic hydrocarbon,
At least one kind can be selected from aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, higher alcohols, ketones, ethers, esters and the like.

Examples of the lower alcohol include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, ethylene glycol, propylene glycol and the like. As the polyhydric alcohol derivative, those capable of dissolving the compound of the general formula [I] or [II] are preferable, and methyl cellosolve, ethyl cellosolve, butyl cellosolve, tertiary butyl cellosolve and the like can be mentioned. Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene and the like. Examples of the aliphatic hydrocarbon include hexane, heptane, octane and the like. Examples of the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, cycloheptane and the like. Examples of the halogenated hydrocarbon include carbon tetrachloride, dichloroethane, trichloroethane and the like. Examples of higher alcohols include octanol and cyclohexanol. Examples of ketones include methyl ethyl ketone and methyl propyl ketone. Examples of ethers include dipropyl ether and dibutyl ether. Examples of the esters include ethyl acetate, isopropyl acetate, isobutyl acetate, isopentyl acetate, butyl propionate and the like.

As a method for removing the water generated by the condensation out of the system, for example, a solvent having an azeotropic composition in a ternary system containing water is condensed under reflux conditions, and liquid is separated in the collected reflux fraction. The water tank part or the part containing water is removed to the outside of the system, or a fraction containing water, that is, a fraction in a state where water is more concentrated than the composition of the reaction solution is removed to the outside of the system. be able to. The compound of the general formula [I] or [II] is preferably gradually added dropwise under reflux of a solution containing phthalaldehyde and a basic catalyst.

In the present invention, the amount of phthalaldehyde used is 1.0 to 1.5 times the mole of the compound of the general formula [I] or [II].

〔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 a mixed melt of 80 g of isopropyl alcohol and 60 g of benzene, and 63 g (0.50 mol) of dimethylsulfate was added dropwise to this solution under stirring for 1 hour. The reaction solution was further stirred at room temperature for 1 hour, and this was designated as solution A.

Next, 100.6 g (0.75 g) of terephthalaldehyde was placed in a flask equipped with a reflux condenser and a device capable of distilling any of the reflux liquid having a liquid separating part and a distilling cock at the bottom thereof.
Mol) and 8.5 g (0.1 mol) of piperidine were dissolved in a mixed solvent of 80 g of isopropyl alcohol and 110 g of benzene. This solution is heated and stirred, and the solution A is mixed under reflux conditions.
Dropped over time.

Immediately after the dropping, yellow crystals were deposited, and an aqueous layer was separated as a lower layer in the refluxed portion as the reaction progressed. Therefore, the aqueous layer was gradually removed from the system with a distillation cock. After the dropwise addition was completed, the reflux was continued for another 5 hours, and the aqueous layer separated during that period was gradually removed in the same manner as above.

After cooling, add 200 g of water to separate into two layers, an upper layer (oil layer) containing excess terephthalaldehyde and coloring components, and a lower layer (water layer) containing diolefin type compounds, which are main products and by-products. Then, this lower layer was washed several times with benzene.

The solution of the lower layer was separated by filtration to separate the crystals of the by-product diolefin type compound (yield 5 g, 3.7% yield) to obtain a filtrate in which a styrylpyridinium salt was dissolved. Acetone was added to the filtrate to precipitate crystals, and yellow crystals of the main product N-methyl-4- (p-formylstyryl) pyridinium methosulfate were obtained (amount 148 g, yield 88.3%).

<Example 2> The same process as in Example 1 was carried out except that methyl p-toluenesulfonate was used in place of dimethyl sulfate and ethanol was used in place of isopropanol.

Main product N-methyl-4- (p-formylstyryl)
The yield of pyridinium p-toluenesulfonate is 86.0%,
The yield of by-products was 5.0%.

<Example 3> Example 1 except that 4-methylquinoline was used in place of γ-picoline, and cyclohexane was used in place of benzene.
The same process was carried out.

Main product N-methyl-4- (p-formylstyryl)
The yield of quinolinium methosulfate was 87.5% and the yield of by-products was 4.6%.

<Example 4> A process similar to that of Example 1 was carried out except that α-picoline was used in place of γ-picoline, and n-propanol and cyclohexane were used in place of isopropanol and benzene, respectively.

Main product N-methyl-2- (p-formylstyryl)
The yield of pyridinium methosulfate was 85.1% and the yield of by-products was 5.8%.

<Comparative Example 1> A treatment was performed in the same manner as in Example 1 except that a flask equipped with a reflux condenser was used and condensation was performed under the simple reflux condition without removing the produced water.

Main product N-methyl-4- (p-formylstyryl)
The yield of pyridinium methosulfate was 70.5% and the yield of by-products was 14.9%.

〔The invention's effect〕

As described above, according to the method for producing a photosensitive compound of the present invention, a photosensitive compound comprising a formylstyrylpyridinium salt or a formylstyrylquinolinium salt can be easily produced in high yield.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-193892 (JP, A) JP-A-59-199672 (JP, A) JP-A-4-112871 (JP, A)

Claims (3)

(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 ^- it 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 [II
I] (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.) In producing the photosensitive compound represented by the formula (I), the compound represented by the general formula [I] or [II] and phthalaldehyde are generally dissolved as a reaction solvent. In a method using a compound which does not dissolve the photosensitive compound represented by the formula [III], the water generated by condensation is sequentially removed out of the system to obtain a photosensitive compound represented by the general formula [III] Production method. 2. A compound represented by the general formula [I] or [II] of claim 1 and phthalaldehyde are condensed in the presence of a basic catalyst to give a compound of the general formula [III] of claim 1. In producing the photosensitive compound represented by, the compound represented by the general formula [I] or [II] and phthalaldehyde are dissolved as a reaction solvent, but the photosensitive compound represented by the general formula [III] is not dissolved. In the method using the compound of the general formula [II], the photosensitive compound represented by the general formula [III] is dissolved in water and separated and purified after completion of the condensation.
I] A method for producing a photosensitive compound represented by the formula [I]. 3. The method for producing a photosensitive compound according to claim 2, wherein water produced by condensation is successively removed from the system.