JPS6325581B2 - - 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 includes:
The present invention relates to a method for producing a photosensitive compound having a pyridinium or quinolinium group in high yield. Technical background General formula (): [However, in the above formula, Y is the following general formula () and (): (However, in the above formula, R ₁ represents an alkyl group, ^and
represents an anion) represents one member selected from the quaternary ammonium group represented by] The compound represented by the following general formula () or (): [However, in the above formula, R ₁ ^and known to be obtained. In the conventional synthesis method for obtaining the compound of the general formula (), the following general formula (): [However, Y in the formula is the same as defined above] A large amount of the diolefin type compound represented by the following was produced as a side reaction product, and as a result, the yield of the compound of general formula () was unsatisfactory. . In order to reduce the production rate of the side reaction products and increase the yield of the main reaction product, generally several times the molar amount of the quaternary ammonium salt compound of the general formula () or () is used. A method using phthalaldehyde has been used. However, when such a large excess amount of phthalaldehyde is used, it is difficult to recover unreacted phthalaldehyde from the reaction mixture, and the cost is also high. That is, in the most common conventional method, methylpyridine or methylquinoline is first treated with a quaternary alkylating agent such as dimethyl sulfate or methyl toluenesulfonate in a solvent consisting of methanol or ethanol. grade ammonium chloride, which is then
A condensation reaction is carried out with a large excess of 2.5 to 5 times the mole of phthalaldehyde in the presence of a basic catalyst to obtain a compound of general formula (). However, this method has the disadvantage that it is virtually impossible to separate unreacted phthalaldehyde from the reaction mixture, and the reaction cost is high. Purpose of the invention The purpose of the present invention is to obtain the general formula () or ()
To provide a method for producing a photosensitive compound of general formula () with a high yield using a relatively small excess amount of phthalaldehyde with respect to a quaternary ammonium salt compound. be. Summary of the Invention The method of the present invention comprises the following general formulas () and (): [However, in the above formula, R ₁ represents an alkyl group, and X ^- represents an anion. ] A quaternary ammonium salt compound selected from the group of compounds represented by the above and phthalaldehyde are reacted in an organic solvent in the presence of a basic catalyst to form the following general formula (): [However, Y in the above formula is the following general formula () and (): R ₁ and X ⁻ in the above formulas () and () are respectively as defined above. ] In the method for producing a photosensitive compound represented by
(A) and gradually mix this solution into a solution of the phthalaldehyde dissolved in an organic solvent (B),
The organic solvent formed in the resulting reaction mixture
The mixed solvent of (A) and organic solvent (B) contains a highly polar solvent component consisting of at least one member selected from the group consisting of lower alcohols, polyhydric alcohol derivatives, dimethylformamide, and dimethyl sulfoxide, and aromatic hydrocarbons. a low polar solvent component consisting of at least one selected from the group consisting of chemical compounds, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, higher alcohols, ketones, esters and ethers; and the mixed solvent is characterized in that it dissolves the compounds of the general formulas () and () and the phthalaldehyde, but does not dissolve the product compound of the general formula (). be. Structure of the Invention The quaternary ammonium salt compounds of the general formulas () and () used in the method of the present invention, that is, the pyridinium compounds and quinolinium compounds, are prepared by combining the corresponding pyridine compounds and quinoline compounds with dimethyl sulfate, methyl toluenesulfonate, etc. It can be produced by converting it into a quaternary ammonium by a conventional method using an alkylating agent such as. In general formulas () and (), the alkyl group represented by R ₁ is preferably 1-6,
More preferably, it has 1 to 3 carbon atoms, and in general formulas () and (),
Anions represented by X ^- are generally chloride, sulfate, perchlorate, methanesulfonate, benzenesulfonate, P
- Preferably selected from toluenesulfonate ion, phosphate ion, methoxysulfate ion, etc. The basic catalyst used in the process of the invention is generally selected from piperidine, pyrrolidine, dicyclohexylamine, triphenylamine, triethylamine, tripropylamine, diethylamine, and the like. In the method of the present invention, general formula () or ()
The quaternary ammonium salt compound is dissolved in the organic solvent (A), and the phthalaldehyde is dissolved in the organic solvent (B). The basic catalyst may be contained in either or both of these solutions. Organic solvent (A) for dissolving quaternary ammonium salt compounds
is preferably made of only a highly polar solvent or a mixture of a highly polar solvent and a low polar solvent. Generally, a quaternary ammonium salt compound cannot be dissolved by a low polar solvent alone. Furthermore, the organic solvent (B) for dissolving phthalaldehyde is preferably a mixture of a highly polar solvent and a low polar solvent. When an organic solvent (B) consisting only of a low polar solvent is used, the quaternary ammonium salt compound tends to precipitate from the reaction system when both reactant solutions are mixed, and the formation of the side reaction product of general formula () is promoted. There is a tendency to To carry out the reaction of the method of the present invention, gradually add the quaternary ammonium salt compound/organic solvent (A) solution to 60%
Phthalaldehyde held at a temperature of ~100°C/
This is added dropwise to the organic solvent (B) solution while stirring, preferably over 1 to 10 hours. Then, the obtained reaction mixture was maintained at a temperature of 60 to 100 °C,
Continue stirring for 1-5 hours. In the method of the present invention, the mixed solvent formed by mixing the organic solvent (A) and the organic solvent (B) in the above reaction mixture is a mixture of a highly polar solvent component and a low polar solvent component, and , this mixed solvent is
It must be capable of dissolving the quaternary ammonium salt compounds of general formulas () and () and phthalaldehyde, but not capable of dissolving the produced photosensitive compound of general formula (). be. The highly polar solvent component is at least one selected from the group consisting of lower alcohols, polyhydric alcohol derivatives, dimethylformamide, and dimethyl sulfoxide. In addition, the above-mentioned low polar solvent components include aromatic hydrocarbon compounds, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, higher alcohols, higher ketones,
It consists of at least one member selected from the group consisting of higher esters and higher ethers. The lower alcohol used as the highly polar solvent component preferably has 1 to 4 carbon atoms,
Methyl alcohol, ethyl alcohol, n- or iso-propyl alcohol, n-, iso- or
Tert-butyl alcohol or ethylene glycol is used. Further, the polyhydric alcohol derivative is preferably one that can dissolve the compounds of general formulas () and (), and generally includes methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate,
It can be selected from polyhydric alcohol alkyl ethers and polyhydric alcohol alkyl ether esters such as diethyl cellosolve, butyl cellosolve, ethylene glycol isopropyl ether, diethylene glycol monoethyl ether, butyl cellosolve acetate, diethylene glycol diethyl ether, and diethylene glycol dimethyl ether. The aromatic hydrocarbon compound used as a low polarity solvent component has the following general formula: [However, in the above formula, R ₃ and R ₄ are each one selected from the group consisting of a hydrogen atom and an alkyl group, for example an alkyl group having 1 to 3 carbon atoms.
Z represents a hydrogen atom and a halogen atom,
For example, it represents one member selected from the group consisting of a chlorine atom, and l represents an integer of 1 to 4.] and aromatic halogenated hydrocarbons, such as benzene, toluene, xylene, Chlorobenzel or dichlorobenzene is preferred. In addition, aliphatic hydrocarbons include those represented by the following general formula: CnH _2(o+1) [where n represents an integer from 5 to 10], such as hexane, heptane, and octane. Preferably selected.
Further, the alicyclic hydrocarbon can be selected from those represented by the following general formula: CnH _2o [in the above formula, n represents an integer of 5 to 10], such as cyclohexane, cycloheptane, and methylcyclohexane. Furthermore, the halogenated hydrocarbon has the following general formula: CpAqH _2(p+1)-q [However, in the above formula, A represents a halogen atom, such as a chlorine atom, p represents an integer from 1 to 3, and q represents 1. represents an integer of ~4], such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, dichloropropane, trichloropropane, etc. are preferred. The higher alcohol should be selected from those having 5 to 10 carbon atoms, such as pentanol, hexanol, heptanol, octanol, cyclopentanol, cyclohexanol, cycloheptanol, etc., especially those that are incompatible with water. is preferred. Furthermore, the ketones that can be used in the method of the present invention are water-incompatible and are selected from, for example, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, diethyl ketone, ethyl butyl ketone, cyclohexanone, acetophenone, etc. It is preferable that The ethers usable in the process of the invention are preferably selected from those which are incompatible with water, such as isopropyl ether, dioxane, tetrahydrofuran, dibutyl ether, and anisole. Esters that can be used in the method of the invention include those that are incompatible with water, such as methyl acetate, ethyl acetate,
It is preferably selected from butyl acetate, amyl acetate, ethyl lactate, butyl propionate, butyl butyrate, and the like. In the method of the present invention, the volume ratio of the high polarity solvent component to the low polarity solvent component in the mixed solvent is 0.1 to
It is preferably within the range of 10, and more preferably within the range of 0.2 to 5. In the method of the present invention, for the quaternary ammonium salt compounds of general formulas () and (),
The amount of phthalaldehyde used is 1.0 to 1.5 times the mole amount, and there is no need to use a large amount of 2.5 to 5 times the mole as in the conventional method. In the method of the present invention, the reaction product is insoluble in the mixed solvent and is therefore precipitated from the reaction mixture.
This precipitated reaction product is separated from the reaction mixture, washed and dried. When this reaction product contains a small amount of by-product, for example, a diolefin type compound in addition to the compound of general formula () (main product), this reaction product can be combined with the compound of general formula () and the by-product. A solvent that dissolves only one of the products;
For example, the two are separated by treatment with methyl alcohol. The method of the present invention will be further explained below with reference to Examples. Example 1 Preparation of quaternary ammonium salt solution 0.50 mol of 4-methylpyridine was dissolved in a mixed solvent (A) of 80 ml of i-propyl alcohol and 50 ml of benzene, and 0.50 mol of dimethyl sulfuric acid was added into this solution from the dropping funnel. The mixture was added dropwise over a period of 30 to 60 minutes, and then the reaction solution was stirred at room temperature for 60 minutes to convert 4-methylpyridine into quaternary ammonium. Preparation of terephthalaldehyde solution In a reaction tank equipped with a condenser and a stirrer, 0.75 mol of terephthalaldehyde and 0.1 mol of piperidine were dissolved in a mixed solvent (B) of 100 ml of i-propyl alcohol and 130 ml of benzene. Synthesis of N-methyl-γ-(P-formylstyryl)pyridinium methosulfonate The reaction tank for the above terephthalaldehyde solution was heated to 90°C.
The mixture was heated and stirred. The above-mentioned quaternary ammonium salt solution was added dropwise into this reaction tank over a period of 3 hours. A yellow precipitate began to precipitate at the same time as the dropping started. After the dropwise addition was completed, heating and stirring at 90°C was continued for 2 hours, and after cooling overnight, the precipitate was separated. The precipitated solid was washed with acetone and dried to obtain 142 g of yellow mixed crystals of the styrylpyridium salt (a) of the following formula and the by-product diolefin type compound (a). 142g of this mixture, 300ml of methanol and 40ml of water
When the mixture was dispersed in a mixed solvent and heated to 70°C, the styrylpyridinium salt (a) was dissolved, but the by-product diolefin type compound (a) remained solid and did not dissolve. This solution was separated hot,
Crystals of the diolefin type compound (a) were separated from the liquid in which the styrylpyridinium salt (a) was dissolved. When this liquid is evaporated to dryness,
132 g (0.39 mol) of yellow crystals of styrylpyridinium salt (a) were obtained. When the separated diolefin compound (a) was washed with ethanol and dried, 10 g (0.0187 mol) of bright yellow crystals of the diolefin compound (a) were obtained. The respective yields are shown in Table 1. Examples 2-4 A method similar to Example 1 was carried out. However, the types and amounts of the reactants and solvents, and the yield and melting point of the products were as shown in Table 1.

[Table] Note: Yield - Ratio of the molar amount of the product to the molar amount of the quaternary ammonium salt compound used (%)
Comparative Example 1 0.50 mol of 4-methylpyridine was dissolved in a mixed solvent of 180 ml of isopropyl alcohol and 180 ml of benzene, 0.50 mol of dimethyl sulfuric acid was added dropwise to this solution from a dropping funnel over 30 to 60 minutes, and the reaction mixture was then allowed to stand at room temperature. Stir for 60 minutes. After 0.75 mol of terephthalaldehyde was dissolved in this solution, 0.1 mol of piperidine was added and the reaction mixture was stirred at 90°C for 5 hours, resulting in a large amount of yellow precipitate.
The reaction mixture was left to cool overnight, and the precipitate was separated. The obtained solid was washed with acetone and dried to obtain 120 g of yellow mixed crystals of the styrylpyridinium salt (a) described in Example 1 and the by-product diolefin type compound (a). When the main product (a) and by-product (a) were separated from 120 g of this mixture in the same manner as in Example 1, 99 g (0.296 mol) of crystals of styrylpyridinium salt (a) and the by-product were separated. 21 g (0.0392 mol) of crystals of a certain diolefin type (a) were obtained. The respective yields are shown in Table 2. Comparative Examples 2 to 4 The same method as Comparative Example 1 was carried out. However, the quaternary ammonium salt compound, the type and amount of the solvent, and the yield and melting point of the product were as shown in Table 2.

[Table] Effects of the Invention In the method of the present invention, quaternary
Since the quaternary ammonium salt/organic solvent (A) solution is mixed (dropwise) little by little, the quaternary ammonium salt compound reacts with a large excess of phthalaldehyde. Therefore, the quaternary ammonium salt compound reacts with only one of the two aldehyde groups of phthalaldehyde, and this reaction proceeds efficiently until the quaternary ammonium salt compound is completely consumed. Moreover, since the reaction product is insoluble in the mixed solvent of organic solvents (A) and (B), it immediately precipitates out of the reaction system. Therefore, the yield of the reaction product obtained by the method of the present invention is high. Moreover, in the method of the present invention, since a mixed solvent of a specific high polarity solvent and a low polarity solvent is used, the fourth
It is sufficient that the molar amount of phthalaldehyde used is 1.0 to 1.5 times the molar amount of the class ammonium salt compound, and therefore, the loss of phthalaldehyde is extremely small compared to the conventional method. Furthermore, the amount of by-products produced is also extremely small. Comparative Example 5 0.50 mol of 4-methylpyridine in 80 ml of methanol
0.50 mol of dimethyl sulfuric acid was added dropwise to this solution from the dropping funnel over a period of 30 to 60 minutes, and the reaction solution was then stirred at room temperature for 60 minutes to convert 4-methylpyridine into quaternary ammonium chloride. did. Separately, in a reaction vessel with a condenser and a stirrer, 0.75 mol of terephthalaldehyde and piperidine were added.
0.1 mol was dissolved in 170 ml of methanol. The above terephthaldehyde solution was heated to 85°C and stirred. In this terephthalaldehyde solution, the above-mentioned fourth
A solution of a class ammonium salt compound was added dropwise over a period of 3 hours. After the dropwise addition was completed, heating and stirring at 85° C. was continued for an additional 2 hours, and crystals of a by-product, a diolefin type compound, were precipitated. The reaction solution turned into a deep reddish brown opaque liquid. This was separated under heat to separate the crystals of the diolefin type compound from the liquid. This liquid was mixed into a mixed solvent of 1200 ml of ethanol and 400 ml of acetone and left overnight, and a styrylpyridinium salt compound precipitated out. Separately, after washing with acetone and drying, 60g (0.179 mol) of light brown-yellow styrylpyridinium salt compound is obtained.
Obtained. Furthermore, when the crystals of the diolefin type compound were washed with ethanol and dried, 64 g (0.119 mol) of a bright yellow diolefin type compound was obtained. The respective yields are shown in Table 3. Comparative Examples 6-8 The same method as Comparative Example 5 was carried out. However, the type and amount of reactants and solvents, and the yield of products are subject to the third
It was as shown in the table.

【table】

Claims (1)

[Claims] 1. The following general formulas () and (): [However, in the above formula, R ₁ represents an alkyl group,
X ^- represents an anion. ] A quaternary ammonium salt compound selected from the compound group represented by the above and phthalaldehyde is reacted in an organic solvent in the presence of a basic catalyst to form the following general formula (): [However, Y in the above formula is the following general formula () and (): R ₁ and X ⁻ in the above formulas () and () are each as defined above. ] In the method for producing a photosensitive compound represented by
(A) and gradually mix this solution into a solution of the phthalaldehyde dissolved in an organic solvent (B),
The organic solvent formed in the resulting reaction mixture
The mixed solvent of (A) and organic solvent (B) contains a highly polar solvent component consisting of at least one member selected from the group consisting of lower alcohols, polyhydric alcohol derivatives, dimethylformamide, and dimethyl sulfoxide, and aromatic hydrocarbons. a low polar solvent component consisting of at least one member selected from the group consisting of chemical compounds, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, higher alcohols, ketones, esters and ethers; , and the mixed solvent dissolves the compounds of the general formulas () and () and the phthalaldehyde, but does not dissolve the product compound of the general formula (), A method for producing a photosensitive compound of general formula (). 2. The method according to claim 1, wherein the organic solvent (A) consists only of the highly polar solvent. 3. The method according to claim 1, wherein the organic solvent (A) comprises a mixture of the high polarity solvent and the low polarity solvent. 4. The method according to claim 1, wherein the organic solvent (B) comprises a mixture of the high polarity solvent and the low polarity solvent. 5. The method according to claim 1, wherein the lower alcohol has 1 to 4 carbon atoms. 6. The method according to claim 1, wherein the polyhydric alcohol derivative is capable of dissolving the compounds of the general formulas () and (). 7 The aromatic hydrocarbon compound has the following general formula: [However, in the above formula, R ₃ and R ₄ each represent a member selected from the group consisting of a hydrogen atom and an alkyl group, and Z represents a member selected from the group consisting of a hydrogen atom and a halogen atom] A method as claimed in claim 1. 8. The method according to claim 1, wherein the aliphatic hydrocarbon is represented by the following general formula: CnH _{2 (o+1)} [wherein n represents an integer of 5 to 10]. 9. The method according to claim 1, wherein the alicyclic hydrocarbon is represented by the following general formula: CnH ₂ n [wherein n represents an integer of 5 to 10]. 10 The halogenated hydrocarbon has the following general formula CpAqH _{2(p+1)-q [} wherein A represents a halogen atom, p represents an integer of 1 to 3, and q represents an integer of 1 to 4. The method according to claim 1, wherein the method is represented by: 11. The method according to claim 1, wherein the higher alcohol has 5 to 10 carbon atoms. 12. The ketone is incompatible with water;
A method according to claim 1. 13. The method of claim 1, wherein the ester is incompatible with water. 14. The method of claim 1, wherein the ether is incompatible with water. 15. The method according to claim 1, wherein the volume ratio of the high polarity solvent component to the low polarity solvent component in the mixed solvent is within the range of 0.1 to 10.