JPS6350344B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a photosensitive compound. More specifically, the present invention relates to a method for producing a photosensitive compound having a pyridinium group or a quinolinium group in high yield in an organic solvent. Background of the Technology Conventionally, a polar solvent such as methanol or ethanol has been used alone as a reaction solvent for formylstyrylpyridinium salts and formylstyrylquinolinium salts. Such a polar solvent can dissolve both the intermediate product, methylpyridinium salt or methylquinolinium salt, and the final product, formylstyrylpyridinium salt or formylstyrylquinolinium salt. When the synthesis reaction is carried out in this polar solvent, brown sticky side reaction products are produced which have very similar solubility in various solvents to the main products, formylstyrylpyridinium salt and formylstyrylquinolinium salt. rate becomes higher. The reaction system is then contaminated, resulting in the following drawbacks. (1) It is difficult to wash and separate the main product, formylstyrylpyridinium salt or formylstyrylquinolinium salt, from the brown sticky side reaction product. (2) When terephthalaldehyde added in large excess to methylpyridine or methylquinoline is recovered, brown sticky side reaction products are mixed in, making purification and recovery of terephthalaldehyde difficult. (3) The synthesis yield of the main product, formylstyrylpyridinium salt or formylstyrylquinolinium salt, is low. (4) Even though terephthalaldehyde is added in large excess to methylpyridine or methylquinoline, the following formula The yield of the side reaction product indicated by is increased. Purpose of the Invention The purpose of the present invention is to develop a photosensitive material that can precipitate the final product as a solid and reduce various side reactions by carrying out the reaction in a mixed solvent system of a polar solvent and a nonpolar solvent. An object of the present invention is to provide a method for producing a compound. Structure of the Invention The present invention is directed to improving the method for producing the compound represented by the general formula (). That is, the present invention provides the following general formula () or (): [However, in the above formula, R ₁ represents a member selected from the group consisting of a hydrogen atom, an alkyl group, and an aralkyl group, and the alkyl group and aralkyl group each represent a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond. R ₂ represents a hydrogen atom and a lower alkyl group, and X ^- represents an anion. ] Methylpyridinium salt or methylquinolinium salt represented by phthalaldehyde is condensed in an organic solvent in the presence of a basic catalyst to form the following general formula (): [However, in the above formula, Y is the following general formula () and (): R ₁ , R ₂ and X ⁻ in the above formulas () and () are each as defined above. ] In the method for producing the photosensitive compound shown in the following, highly polar lower alcohols, polyhydric alcohol derivatives, dimethyl formamide, or dimethyl sulfoxide and low polar aromatic hydrocarbon compounds, aliphatic hydrocarbons, alicyclic carbonization A mixed solvent consisting of hydrogen, halogenated hydrocarbon, higher alcohol, ketones, esters or ethers, which dissolves the compound of the general formulas () and () and the phthalaldehyde, It is characterized by having the property of not dissolving the product compound of the general formula (). Detailed Description of the Invention The compound represented by the above general formula () is represented by the following general formula () or (). (In the formula, R ₁ ^and You can get it. In this reaction, the general formula () (In the formula, Y is as defined above.) A by-product mixture (2) is produced which has a brownish viscosity and is thought to contain the diolefin type compound represented by the following formula and various compounds other than this compound (2). Here, usually the general formula () or the general formula ()
In order to reduce the yield of the side reaction compound () and improve the yield of the compound () relative to the amount of the compound used, in the reaction of terephthalaldehyde with the general formula () or the compound of the general formula (), , a method has been adopted to increase the proportion of terephthalaldehyde used. The molar ratio of the two is usually 2.5:1 to 5:1, that is, terephthalaldehyde is used in large excess. When a highly polar lower alcohol such as methanol or ethanol is used as a reaction solvent as used in conventional synthesis methods, the compound () precipitates out, and the compound (), the by-product mixture (), and , unreacted terephthalaldehyde is dissolved in the solvent. The reaction system is a dark brown opaque solution. This reaction system is separated during heating to remove the precipitate of compound (), and the liquid is mixed with a mixed solvent of ethanol and acetone, which is a precipitant for compound (), and cooled. At this time, even if the crystallized compound () is separated and washed and dried, the by-product mixture () cannot be completely removed by washing. It is difficult to recover terephthalaldehyde from the liquid in which terephthalaldehyde and the by-product mixture () are dissolved. This is a mixture of terephthalaldehyde and by-products ()
This is because it is difficult to separate. In the conventional method, the production rate of the by-product mixture () is high;
The concentration of the by-product mixture () in the liquid is higher than that of terephthalaldehyde, and therefore,
It is thought that it will be difficult to recover terephthalaldehyde from the liquid. However, according to the method of the present invention, a mixed solvent of a highly polar solvent and a less polar solvent is used as a reaction solvent, whereby compound () and compound () precipitate out.
The by-product mixture () and a large excess of terephthalaldehyde, which is the reaction residue, are dissolved in the solvent. This reaction system was a pale reddish-purple transparent solution, which indicates that the amount of by-product mixture () produced was small. After cooling the reaction system, compound () and compound () are taken out separately. In the acetalization reaction between polyvinyl alcohol and compound (), which contains almost no impurities such as by-product mixture (),
Usually, compound () is used which is easily isolated from a mixture of compound () and compound (), but it is also possible to use compound () as a mixture with compound () without isolating compound (). There are no particular problems. In addition, in order to recover terephthalaldehyde from the liquid, the liquid must be diluted with saturated saline, dilute alkaline aqueous solution, water,
After washing in the order of dilute acid aqueous solution and water, and drying the solution over anhydrous magnesium sulfate, magnesium sulfate is removed, and then the solvent is removed by evaporation. Thereby, clean terephthalaldehyde crystals can be easily recovered at a high rate. The mixed solvent used in the method of the present invention is a highly polar lower alcohol, preferably having 1 to 4 carbon atoms.
at least one selected from lower alcohols, polyhydric alcohol derivatives, dimethylformamide or dimethyl sulfoxide, and low polar aromatic hydrocarbon compounds, aliphatic hydrocarbons, alicyclic hydrocarbons,
At least one selected from halogenated hydrocarbons, higher alcohols, preferably higher alcohols having 5 to 10 carbon atoms, ketones, ethers, or esters.
It consists of seeds. Examples of the lower alcohol having 1 to 4 carbon atoms include methanol, ethanol, propyl alcohol, butyl alcohol, ethylene glycol, and propylene glycol. The polyhydric alcohol derivative is preferably one that can dissolve the above compound () or (), such as methyl cellosolve, ethyl cellosolve,
Methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve, butyl cellosolve, ethylene glycol isopropyl ether, diethylene glycol monoethyl ether,
Examples include butyl cellosolve acetate, diethylene glycol diethyl ether, and diethylene glycol dimethyl ether. As an aromatic hydrocarbon compound

[Formula] (In the formula, R ₃ and R ₄ represent a hydrogen atom or an alkyl group,
Z represents a hydrogen atom or a halogen atom, l is 1
Indicates an integer of ~4. ), and
For example, it is selected from benzene, toluene, xylene, chlorobenzene, dichlorobenzene, etc. Aliphatic hydrocarbons have the general formula C _o H _2o+2 (where n is 5
(representing an integer of ~10) is preferred, and is selected from hexane, heptane, octane, etc. Preferred alicyclic hydrocarbons are those represented by the general formula C _o H _2o (in the formula, n represents an integer of 5 to 10), such as cyclohexane and cycloheptane. The general formula for halogenated hydrocarbons is C _o A _n
Those represented by H _2(o+1)-n (in the formula, n represents an integer of 1 to 3, m represents an integer of 1 to 4, and A represents a halogen atom) are preferably chloroform, carbon tetrachloride, dichloroethane, trichloride. ethane, dichloropropane,
Examples include trichlorpropane. The higher alcohol is preferably a higher alcohol having 5 to 10 carbon atoms, and is selected from pentanol, hexanol, heptanol, octanol, cyclopentanol, cyclohexanol, cycloheptanol, and the like. Ketones that can be used in the method of the present invention are preferably those that are incompatible with water, and are selected from methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, diethyl ketone, ethyl butyl ketone, cyclohexanone, acetophenone, and the like. The ethers that can be used in the method of the present invention are preferably those that are incompatible with water, such as isopropyl ether, dioxane, tetrahydrofuran, anisole, and the like. Preferred esters that can be used in the method of the present invention include those that are incompatible with water, such as methyl acetate, ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, butyl propionate, butyl butyrate, and the like. In the mixed solvent used in the method of the present invention, the mixing ratio (high polarity solvent/low polarity solvent) is expressed as a volume ratio.
Preferably within the range of 0.1 to 10, 0.2 to 5
More preferably, it is within the range of . The present invention will be explained in more detail below with reference to Examples. Example 1 0.50 mol of γ-picoline in 100 mol of ethyl alcohol
ml and 500 ml of toluene, and add 0.50 mol of dimethyl sulfate to this solution from the dropping funnel.
The mixture is added dropwise over a period of 30 to 60 minutes, and then the reaction solution is stirred at room temperature for 60 minutes. After dissolving 1.25 mol of terephthalaldehyde in this solution, piperidine
Add 0.1 mol and stir at 80-90°C for 3-5 hours. As a result, a large amount of yellow solid precipitates out, and the solution becomes a clear liquid with a light reddish-purple color. This reaction system is left to stand overnight and then separated into a solid and a liquid (2). The solids were washed with acetone and dried to remove the styrylpyridinium salt () and the by-product diolefin-type compound (). 145 g of yellow mixed crystals were obtained. When 145 g of this mixture was placed in a mixed solvent of 300 ml of methanol and 40 ml of water and heated to 70°C, the styrylpyridinium salt (2) dissolved and the by-product diolefin type compound (2) remained solid and did not dissolve. This solution is heated and separated into a liquid (2) in which crystals of the diolefin-type compound (1) and styrylpyridinium salt (2) are dissolved. The solvent of this liquid () was evaporated to dryness, and 131 g (0.39/ml) of pure yellow crystals of styrylpyridinium salt () was obtained.
mole) was obtained. In addition, by washing the separated diolefin-type compound () with ethanol and drying it, a bright yellow, pure crystal of the diolefin-type compound () is obtained.
14 g (0.026/mol) were obtained. In addition, the solution () was washed three times with 100 ml of saturated saline solution, then washed twice with 100 ml of 1% aqueous sodium hydroxide solution, and then washed twice with 100 ml of 1% phosphoric acid aqueous solution.
It was washed twice, and then washed with 100 ml of pure water until the washing water became neutral. Thereafter, the washing solution (2) was dried with anhydrous magnesium sulfate. The solvent was then evaporated to dryness and 91 g of pure white terephthalaldehyde crystals were recovered. This corresponds to 91% of the excess terephthaldehyde. Examples 2 to 5 were carried out in the same manner as in Example 1, and the results are summarized in Table 1.

[Table] *1 Yield comparison example for raw material methylpyridines or methylquinolines 1 0.50 mol of γ-picoline was dissolved in 250 ml of methanol, and 0.50 mol of dimethyl sulfuric acid was added dropwise to this solution from the dropping funnel over 30 to 60 minutes. , then the reaction mixture was stirred at room temperature for 60 minutes. After dissolving 1.25 mol of terephthalaldehyde in this solution, piperidine
The reaction mixture was heated at 80-90 °C by adding 0.1 mol of
When the mixture was stirred for 5 hours, crystals of a by-product, a diolefin type compound (), were precipitated. Moreover, this reaction solution became deep reddish brown and opaque. When heated, this was separated into crystals and liquid of the diolefin type compound (). This solution was mixed into a mixed solvent of 1200 ml of ethanol and 400 ml of acetone and left to stand overnight, resulting in the precipitation of styrylpyridinium salt (). This was separated, washed with acetone, and dried to obtain 75.4 g (0.225 mol) of a light brown-yellow styrylpyridinium salt (2008). Further, when the crystals of the diolefin type compound (2) were washed with ethanol and dried, 24.1 g (0.045 mol) of the bright yellow diolefin type compound (2) was obtained. Another attempt was made to recover excess terephthalaldehyde from precipitation solvents of ethanol and acetone;
Large amounts of brown viscous by-products and terephthalaldehyde could not be isolated and recovery was impossible. Hereinafter, Comparative Examples 2 and 3 were conducted in the same manner as Comparative Example 1, and the results are summarized in Table 2.

[Table] *1 Effect of the invention on yield on raw material methylpyridines or methylquinolines According to the present invention, various side reactions can be reduced and desired photosensitive compounds can be obtained in high yield. .

Claims (1)

[Claims] 1. The following general formulas () and (): [However, in the above formula, R ₁ represents a member selected from the group consisting of a hydrogen atom, an alkyl group, and an aralkyl group, and the alkyl group and aralkyl group each represent a hydroxyl group, a carbamoyl group, an ether bond, and an unsaturated bond. selected from those containing and not containing at least one member selected from the group consisting of;
R ₂ represents a member selected from the group consisting of a hydrogen atom and a lower alkyl group, and X ^- represents an anion. ] The methylpyridinium salt or methylquinolinium salt represented by and phthalaldehyde are condensed in the presence of a basic catalyst in an organic solvent to form the following general formula (): [However, in the above formula, Y is the following general formula () and (): R ₁ , R ₂ and X ⁻ in the above formulas () and () are each as defined above. ] In the method for producing the photosensitive compound shown in the following, highly polar lower alcohols, polyhydric alcohol derivatives, dimethyl formamide, or dimethyl sulfoxide and low polar aromatic hydrocarbon compounds, aliphatic hydrocarbons, alicyclic A mixed solvent consisting of a hydrocarbon, a halogenated hydrocarbon, a higher alcohol, a ketone, an ester, or an ether, and this mixed solvent dissolves the compound of the general formulas () and () and the phthalaldehyde. , a method for producing a photosensitive compound of the general formula (), characterized in that it does not dissolve the produced compound of the general formula (). 2. The manufacturing method according to claim 1, wherein the lower alcohol has 1 to 4 carbon atoms. 3. The manufacturing method according to claim 1, wherein the polyhydric alcohol derivative is capable of dissolving the compound () or the compound (). 4 The aromatic hydrocarbon compound has the general formula (In the formula, R ₃ and R ₄ represent a hydrogen atom or an alkyl group,
Z represents a hydrogen atom or a halogen atom, l is 1
Indicates an integer of ~4. ) The method according to claim 1, which is represented by: 5. The method according to claim 1, wherein the aliphatic hydrocarbon is represented by the general formula C _o H _2o+2 (wherein n represents an integer of 5 to 10). 6. The method according to claim 1, wherein the alicyclic hydrocarbon is represented by the general formula C _o H _2o (wherein n represents an integer of 5 to 10). 7 The halogenated hydrocarbon has the general formula C _p A _q H _2(p+1)-q (wherein A represents a halogen atom and p is 1
represents an integer of ~3, and q represents an integer of 1-4. ) The method according to claim 1, which is represented by: 8. The method of claim 1, wherein the higher alcohol has 5 to 10 carbon atoms. 9. The method according to claim 1, wherein the ketones are incompatible with water. 10. The method according to claim 1, wherein the ester is incompatible with water. 11. The method according to claim 1, wherein the ether is incompatible with water. 12. The method according to claim 1, wherein the mixing ratio of the reaction mixture solvent (high polarity solvent/low polarity solvent) is within the range of 0.1 to 10 in terms of volume ratio.