JPS5821661B2 - Method for producing styryl compounds - Google Patents

Description

Detailed Description of the Invention The present invention is based on the following general formula (4). Each benzene ring has a chlorine atom, a lower alkyl group, a lower alkoxy group, a sulfonic acid group, or a salt thereof, a carboxylic acid group or a salt thereof. I can do it.

R1゜R2, R3, R4 are the same or different groups, such as a hydrogen atom, a chlorine atom, a lower alkyl group, a lower alkoxy group, a sulfonic acid group, a sulfonamide group, a sulfonic ester group, a carboxylic acid group, a carbonamide group, Represents a carboxylic acid ester group, cyano group, or phenyl group.

) The present invention relates to a method for producing a styryl compound represented by:

More specifically, in the presence of a palladium catalyst, triphenylphosphine and an acid binder, the following general formula (1) % formula % (1) (wherein A represents the same meaning as in formula (4)) is used.

1 molar ratio of the compound represented by the following general formula (2) and the general formula (3) (wherein, R15R21R3s R4 represents the same meaning as in formula (4)).

The present invention relates to a method for producing a styryl compound represented by the general formula (4), which is characterized by reacting a total of 2 molar ratios of the compounds represented by the formula (4).

Regarding the compound represented by the general formula (4), JP-A No. 4
9-14527, in the presence of a palladium catalyst and an acid binder, the general formula (5) % formula % (5) (wherein, X represents an iodine atom or a bromine atom, and A has the same meaning as in formula (4)) represents.

) has been shown to be able to be produced by reacting a compound represented by general formula (2) and a compound represented by general formula (3) in a total molar ratio of 2.

In the above invention, in the case of X-I, the reaction could be carried out smoothly using a very small amount of a very expensive palladium catalyst, but in the case of X=Br, the reactivity was Since it is considerably lower than in the case of I, stronger reaction conditions (for example, very high reaction temperature) or a large amount of palladium catalyst are required. It was more advantageous to start from I raw material.

However, the raw material general formula (6) % formula % (6) (In the formula, A represents the same meaning as in formula (4).

) and the compound represented by general formula (1), considering the advantages of the industrial production method of the compound represented by formula (1), that is, iodine is about four times more expensive than bromine, and the cost of the same 1 mole of dihalogeno compound is Considering that more iodine is required for production and that dihalogeno compounds are generally more reactive and easily obtained by bromination than by iodination, dibrome compounds are much better as raw materials. It can be manufactured advantageously.

While further studying the above invention (Japanese Unexamined Patent Publication No. 49-14527), the present inventors discovered that if a catalytic amount of triphenylphosphine is used in addition to a palladium catalyst, the reactivity of the bromine compound will be significantly increased. Then, using the compound represented by general formula (1) as a raw material, general formula (4)
Also when producing a compound represented by general formula (6)
We have discovered that it can be produced using the same amount of palladium catalyst as when using the iodo compound represented by as a raw material, and under relatively mild conditions.

This has made it possible to industrially produce the compound represented by general formula (4) at low cost.

The compound of general formula (1) used as a raw material in the present invention is produced by diazotization decomposition of an amino group or by direct bromination.

Furthermore, if necessary, other functional groups may be introduced into the reaction such as sulfonation or oxidation.

The compound of general formula (2), which is the other raw material, has the following general formula (wherein R, and R2 have the same meanings as in formula (4)).

) Dehydrogenation method of ethylbenzenes represented by
Or the following general formula (in formulas (8) and (9), R1 and R2 represent the same meanings as in formula (4), and Y represents a halogen atom.

) A method by dehydrohalogenation of a compound represented by
or the following general formula (wherein, X represents the same meaning as in formula (5)).

It can be produced by a method of reacting the compound represented by ethylene with ethylene in the presence of a palladium catalyst, triphenylphosphine and an acid binder.

Naturally, the compound represented by general formula (3) is also produced in the same manner as the compound represented by general formula (2).

As the palladium catalyst used in the present invention, palladium salts such as palladium chloride, palladium acetate, palladium sulfate, and palladium adsorbed on an adsorbent such as palladium black, activated carbon, or diatomaceous earth are used.

The appropriate amount to be used is a molar ratio of 1/1 to 15,000 to the compound of general formula (1) as a raw material.

In particular, a molar ratio of 1/1oo to '/1000 is preferred.

) Another catalyst, triphenylphosphine, is preferably used in a molar ratio of 1 to 4, particularly preferably 2 molar, to the palladium catalyst.

) triphenylphosphine, triphenylphosphine or tri(p-tolyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine,
4,6-trimethylphenyl)phosphine, tri(p-
Compounds with substituents on the phenyl group, such as (phenyl)phosphine, are used.

As acid binders, inorganic bases and organic salts are generally used, in particular potassium acetate, sodium acetate, ammonium acetate, calcium acetate, potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, potassium carbonate, sodium carbonate. , ammonium carbonate, relatively weak inorganic bases such as calcium hydroxide, or trimethylamine,
Organic bases such as triethylamine, tributylamine, pyridine, piperidine, N-methylpiperidine, 1,4-diazabicyclo[2,2,2]octane (DABCO) are suitable.

The appropriate amount to be used is 2 to 4 molar ratio to the compound of general formula (1).

As the reaction solvent, alcoholic solvents are generally preferred, but other solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, dioxane, and acetone methyl ethyl ketone are also used.

Benzene, toluene, xylene, chlorobenzene, O-
An inert solvent such as dichlorobenzene may also be used.

The reaction temperature is preferably 50 to 250°C.

Particularly advantageous is 130 to 210°C.

Specific examples of the compound represented by the general formula (1) include:

Further, as the compound represented by the general formula (2) or (3), styrene, o-, m-, p-chlorostyrene,
2,4-dichlorostyrene, 3,4-dichlorostyrene, Otrnpp-methylstyrene, 2,4-dimethylstyrene, 3,4-dimethylstyrene, o-'-, m-,
p-ethylstyrene, Otm yp-ethoxystyrene, o-, m-, p-carboxylstyrene, o-
, m-, p-etho-t-dicarbonylstyrene, o,
m-,p-methoxycarbonylstyrene, 0 11"I
I-2p-carbamoylstyrene, o-, m-, p7
N-methylcarbamoylstyrene, o-, m-, p-N
, N-dimethylcarbamoylstyrene, o-, m-
,p-N.

N-diethylcarbamoylstyrene, 2-chloro-4-
Methylstyrene, 2-methyl-4-chlorostyrene, o
-, m-, p-cyanostyrene, p-phenylstyrene, sodium styrene-〇-sulfonate, styrene-m
-Sodium sulfonate, sodium styrene-p-sulfonate, sodium p-methylstyrene-〇-sulfonate, sodium p-methoxystyrene-〇-sulfonate, p-chlorostyrene-m-sulfonic acid-1-11J
um, sodium 4'-vinylbenzoylmethanilate,
Sodium 3'-vinylbenzoylsulfanilate, o
-, m -t p-sulfamoylstyrene, sodium styrene-2,4-disulfonate, styrene-2,
Specific examples include sodium 5-disulfonate, styrene-〇-sulfonic acid phenyl ester, and the like.

Some of the compounds obtained in the present invention are known as fluorescent brighteners, but other novel compounds are also available, such as cellulose,
Natural fibers such as wool, silk or paper, and synthetic fibers or synthetic resins such as polyester, polyamide, polyacrylonitrile, cellulose acetate, polyolefin, polyvinyl chloride, polystyrene, ABS resin, melamine resin, phenolic resin, polyurethane. Useful as a fluorescent brightener.

For example, in the case of a compound of general formula (4) that does not have a water-soluble group such as a sulfonic acid group or a carboxylic acid group, it may be made into an aqueous dispersion using an appropriate dispersant, or it may be solubilized in water or an organic solvent. After that, normal dyeing method, such as ordinary dyeing method,
Methods such as pad steam dyeing, textile printing, high temperature dyeing, carrier dyeing, and thermosol dyeing can be applied.

In addition, fluorescence can be added by adding it before spinning in the production of fiber materials, by adding it before or during the processing of films, sheets, or molding materials, by dyeing it after molding, by applying a solution of a fluorescent agent, etc. photo-whitened fibers, films,
Sheets and molded products can be obtained.

In addition, in the case of compounds having water-soluble groups such as sulfonic acid groups and/or carboxylic acid groups, whitened fibers can be used by ordinary dyeing methods, resin finishing agent combination dyeing methods, thermofix continuous dyeing methods for polyamide fibers, etc. is obtained.

Alternatively, cellulose or polyamide fibers can be fluorescently brightened from washing liquors in combination with detergents.

Next, the method of the present invention will be specifically explained using examples.

In the examples, parts and % represent parts by weight and parts by weight, respectively.

Example 1 In 50 parts of ethylene glycol monoethyl ether, 4
, 4-7 parts of 4/-dibrombiphenyl, 3 parts of styrene.
4 parts, anhydrous potassium acetate 4.5 parts, palladium chloride 0.
0.02 parts of triphenylphosphine, and 0.02 parts of hydroquinone were charged and reacted for 60 hours at the boiling point under a nitrogen stream.

After cooling, it is filtered, washed with water and dried.

Next, using 150 parts of xylene, thermal extraction is performed using a Soxhlet extractor to separate and extract the palladium as a catalyst.

The xylene extract is cooled and the crystals are dried in an oven to obtain 4.9 parts of a compound having the following structural formula.

(Yield: 91%) This product has a melting point of 307-316°C.

Recrystallization from dimethylformamide gives pale yellow crystals with a yield of 84% and a melting point of 325-328°C.

4,4L dibromubiphenyl used as a raw material can be produced by various methods, examples of which are shown below.

90 parts of glacial acetic acid, 37.5 parts of concentrated sulfuric acid, 23.2 parts of biphenyl
37.4 parts of bromine was charged into a Yotsuro flask, heated to 40°C, and 16.6 parts of concentrated nitric acid was added dropwise over about 1 hour while maintaining the temperature at 40°C.

After the dropwise addition, the mixture was further stirred at 40°C for 2 hours.

Next, 100 parts of water is added, and the precipitated crystals are filtered, washed with water, and dried.

This was recrystallized from glacial acetic acid with a melting point of 165-166°C.
, 33.5 parts of 4'-dibrombiphenyl are obtained.

Reference Example When the reaction was carried out in exactly the same manner as in Example 1 except that triphenylphosphine was removed, the yield of the target product was only 2%.

In order to obtain a yield comparable to that of Example 1 without adding triphenylphosphine, it is necessary to use 5 parts or more of palladium chloride as a catalyst.

Even if the catalyst recovery rate is assumed to be 99%, palladium chloride is expensive at about 1,200,000 yen per crab, so the cost of the target product increased by more than 12,000 yen compared to Example 1. It is also extremely disadvantageous economically.

Example 2 100 parts of methanol, 6.2 parts of 4,4'-dibrombiphenyl, 9 parts of sodium styrene-〇-sulfonate, 6 parts of anhydrous sodium acetate, 0.0 parts of palladium black
1 part, triphenylphosphine 0.055 part, and hydroquinone 0.01 part, and after purging with nitrogen, 1 part under pressure.
React at 60°C for 40 hours.

*After cooling, methanol is distilled and recovered, and the residue is mixed with 100% water.
Heat extraction using

Add 10 parts of common salt to the extract, filter out the crystals, wash with 20 parts of 10% salt solution, and dry to obtain the following structural formula Example 3 In 50 parts of ethylene glycol monoethyl ether, p
-Dibromobenzene 7.1 parts, p chlorstyrene 10
1 part, palladium black 0.02 part, triphenylphosphine 0.1 part, anhydrous potassium acetate 9 parts, and hydroquinone 0.02 part, and reacted for 600 hours at the boiling point under a nitrogen stream.

After cooling, it is filtered, washed with water and dried.

Next, thermal extraction is carried out using 150 parts of xylene in a Soxhlet extraction unit, and palladium as a catalyst is separated and extracted.

The xylene extract was cooled, and the crystals were separated from P and dried to obtain 9.2 parts of a compound having the following structural formula.

This has a melting point of 281-285°C.

If recrystallized from dimethylformamide, the melting point is 296-
Pale yellow crystals at 297°C are obtained.

Example 4 In an autoclave, 50 parts of ethylene glycol monoethyl ether, 7. After charging 1 part, 0.1 part of triphenylphosphine, and 0.01 part of hydroquinone and replacing the mixture with nitrogen, the mixture was reacted under pressure at 200° C. for 15 hours.

After cooling, it is filtered, washed with 30 parts of methanol, and dried.

Next, using 150 parts of water, the palladium catalyst is separated and extracted.

After cooling the extract, 10 parts of common salt is added, and the precipitated crystals are separated, washed with 30 parts of Group 5 brine, and dried to obtain 11.7 parts of a compound having the following structural formula.

Example 5 In an autoclave, 100 parts of ethylene glycol monoethyl ether, 13.6 parts of sodium p-dibromobenzenesulfonate, and vinyltoluene (65% in total, p
mixture) 11.8 parts, 12 parts of anhydrous sodium acetate
1 part, palladium black 0.02 part, triphenylphosphine 0.1 part, and hydroquinone 0.04 part,
After purging with nitrogen, the reaction is carried out at 200° C. for 15 hours.

After cooling, the precipitated inorganic salt crystals and palladium were separated, and the P liquid was distilled and recovered from ethylene glycol monoethyl ether.The residue was dissolved in a 20% calcium chloride aqueous solution 2
Boil for 1 hour with 0 parts.

After cooling and filtration, the obtained crude crystals were heated and dissolved in 100 parts of an aqueous solution of 50% polyethylene glycol monoethyl ether, and after removing insoluble matter, the P solution was concentrated, and the precipitated crystals were dried separately. The following structural formula (in the formula, the methyl group is located at the 3-position or 41-position with respect to the ethylene bond of the benzene ring at both ends).

Therefore, in this case, it is a mixture of four isomers.

) are obtained.

Example 6 In an autoclave, 80 parts of ethylene glycol monoethyl ether, 6.8 parts of sodium p-dibromobenzenesulfonate, 6.7 parts of p-chlorostyrene, 0.01 part of palladium black, and 0.0 parts of triphenylphosphine were added.
0.05 parts of hydroquinone, 0.02 parts of hydroquinone, and 7 parts of anhydrous sodium acetate, and after purging with nitrogen, the mixture was heated at 180°C under pressure for 2 hours.
Allow to react for 4 hours.

After the reaction, ethylene glycol monoethyl ether 120
1 part and filter hot to remove palladium and inorganic salt crystals.

The p liquid was concentrated to about 30 parts, and after cooling, the precipitated crystals were separated in a furnace, washed with 10 parts of methanol and 20 parts of water, and dried to obtain 6.3 parts of a compound having the following structural formula.

The reaction was carried out according to Examples 3, 4, 5 and 6 to obtain the following distyrylbenzene derivative represented by *.

The children are listed in the table below.

Example 7 In 100 parts of ethylene glycol monoethyl ether,
2.7-dibromofluorene 6.2 parts, styrene 4.6 parts
parts, anhydrous potassium acetate 6 parts, palladium chloride 0.015 parts
1 part, triphenylphosphine 0.04 part, and hydroquinone 0.01 part, and reacted for 60 hours under a nitrogen stream).

After cooling, rinse with water and dry.

Next, using 250 parts of xylene, palladium as a catalyst is separated and extracted using a Soxhlet extractor.

The xylene extract was cooled, and the crystals were dried individually to obtain 6.5 parts of a compound with the following structural formula.

The melting point is 308-31.5°C.

If recrystallized from dimethylformamide, the melting point is 315~
Pale yellow crystals at 313°C are obtained.

2,7-dibromofluorene used as a raw material can be produced according to 4,4L dibromo biphenyl in Example 1).

Example 8 In an autoclave, 100 parts of ethylene glycol monoethyl ether, 6.2 parts of 2,7-dibromofluorene, 10 parts of sodium styrene-m-sulfonate,
Anhydrous potassium acetate 4 parts, anhydrous potassium carbonate 2.8 parts,
0.01 part of palladium black, 0.05 part of triphenylphosphine, and 0.01 part of hydroquinone were charged, and after purging with nitrogen, the mixture was reacted at 160° C. for 40 hours under pressure.

After cooling, strain. Next, the crystals are heated and dissolved in 300 parts of water, and the palladium catalyst is separated from each other.

The solution F was cooled, 7.5 parts of common salt was added and stirred for 30 minutes, and the precipitated crystals were filtered, washed with 30 parts of water, and dried to obtain 7.8 parts of a compound having the following structural formula.

The reaction was carried out according to Examples 7 and 8 to obtain a distyrylfluorene derivative represented by the following general formula.

It is listed in the table below.

Example 9 In 100 parts of dimethylformamide, 7.8 parts of 4,4L dibromterphenyl, 4.6 parts of styrene, 6 parts of anhydrous potassium acetate, 0.01 part of palladium black, 0.05 part of triphenylphosphine, hydroquinone 0.02 part was charged and reacted at 150° C. for 50 hours under a nitrogen stream.

After cooling, filter, wash with water and dry.

Next, using 300 parts of chlorobenzene, palladium as a catalyst is separated and extracted using a Soxhlet extractor.

The chlorobenzene extract was cooled and the crystals were dried in an oven to obtain 7.2 parts of a compound having the following structural formula.

The melting point is 350°C or higher.

Fast flow side 9
The reaction is carried out according to the following formula to obtain a distyrylterphenyl derivative represented by the following general formula.

It is listed in the table below. Example 10 4,4L dibrome in 100 parts of ethylene glycol
2 parts of 3,3'-dimethylbiphenyl io, 13.5 parts of sodium styrene-m-sulfonate, 9 parts of sodium acetate anhydride, 0.015 parts of palladium chloride, 0.04 parts of triphenylphosphine, 0.02 parts of hydroquinone
1 part was charged and reacted for 15 hours at the boiling point under a nitrogen stream.

After the reaction is complete, ethylene glycol is distilled and recovered under reduced pressure.
Add 100 parts of 10% brine, stir for 30 minutes, and wash the crystals with 30 parts of 10% brine.

Next, using 150 parts of 20% pyridine water, the palladium catalyst is separated and extracted.

After cooling the extract, the crystals are separated in a furnace, washed with 30 parts of a 10% salt solution, and dried to obtain 14 parts of a compound having the following structural formula.

4,4'-dibromo-3,3-dimethylbiphenyl used as a raw material was synthesized as follows.

21.2 parts of o-tolidine was dissolved by heating in 200 parts of water and 103 parts of 47-thihydrobromic acid, and then cooled to 0°C.

In this, 14 parts of sodium nitrite was dissolved in 50 parts of water, and 0-5
℃ and tetrazotized.

After decomposing excess nitrous acid with sulfamic acid, 1 part of copper powder is added and the temperature is gradually raised to 60°C to completely decompose the tetrazo compound.

After cooling, it was filtered, washed with an aqueous solution of sodium thiosulfate, further washed with water, and dried under vacuum to obtain 27 parts of a crude product.

Recrystallization from methanol yields a purified product with a melting point of 63-64°C.

A reaction is carried out according to Example 10 to obtain a distyrylbiphenyl derivative represented by the following general formula.

It is listed in the table below.

SO3Na Example 11 In 100 parts of ethylene glycol monoethyl ether,
13.6 parts of sodium p-dibromobenzenesulfonate, 6 parts of p-chlorostyrene, 12 parts of anhydrous sodium acetate, 0.02 part of palladium black, 1 part of triphenylphosphine o, hydroxide.

Add 0.04 part of non-alcoholic acid and react for 40 hours at the boiling point under a nitrogen stream.

Next, 5.9 parts of vinyl toluene (a mixture of 65 parts of m and 35 parts of p) was charged and reacted for 50 hours at the boiling point under a medium atmosphere of nitrogen.

After the reaction is complete, remove the catalyst palladium and precipitated inorganic salts by distilling and recovering ethylene glycol and monoethyl ether from the r liquid. Add 200 parts of a 20% calcium chloride aqueous solution to the residue and boil for 1 hour. .

After cooling and filtering, the obtained crude crystals were heated and dissolved in 200 parts of a 50% aqueous ethylene glycol monoethyl ether solution, and insoluble materials were separated.The filtrate was concentrated, and the precipitated crystals were dried separately and prepared as follows. Structural formula (wherein the methyl group is located at the 3- or 42-position relative to the ethylene bond).

Therefore, (102) and (103) are each a mixture of two isomers.

) are obtained.

At this time, in addition to the compounds of formulas (102) and (103), f-
-m-X f--Although a small amount of the compound of the formula (104) and the compound of the formula (33) are also obtained, the main products are the compounds of the formula (102) and (103).

A reaction is carried out according to Example 11 to obtain a distyryl compound represented by the following general formula.

It is listed in the table below.

Next, an example of a method for treating fiber materials or synthetic resins using the styryl compound obtained by the method of the present invention to impart a whitening effect will be described for reference.

Reference Example 1 Synthetic detergent (consisting of 33 parts of sodium dodecylbenzenesulfonate, 31 parts of sodium tripolyphosphate, 5 parts of sodium silicate, 1 part of CMC, and 30 parts of anhydrous sodium sulfate) in 1000 parts of water.
2 parts, 0.02 part of the compound of structural formula (33) was added, and 40
Add 20 parts of cotton gold cloth that has been heated to ℃ and chemically bleached.
Wash at the same temperature for 30 minutes.

Rinse with water and dry to obtain a cotton cloth with a strong whitening effect.

Reference Example 2 Synthetic detergent (consisting of 33 parts of sodium dodecylbenzenesulfonate, 31 parts of sodium tripolyphosphate, 5 parts of sodium silicate, 1 part of CMC, and 30 parts of anhydrous sodium sulfate) in 1000 parts of water.
2 parts, 0.01 part of the compound of structural formula (34) was added, and 60
Heat to ℃, add 20 parts of nylon fabric, and wash at the same temperature for 30 minutes.

Rinse with water and dry to obtain a nylon cloth with a strong whitening effect.

Reference Example 3 10 parts of glyoxal resin was dissolved in 100 parts of water, 1.5 parts of zinc nitrate catalyst was added, and structural formula (69)
Dissolve 0.2 part of the compound.

Soak a bleached cotton broadcloth and squeeze to a squeezing rate of 70%.

This process is repeated once again to perform intermediate drying at 70°C for 10 minutes, and then dry heat treatment at 150°C for 3 minutes.

Soap and dry in the usual manner.

This processed cloth has an excellent whitening effect under sunlight, and also has excellent washing resistance and wrinkle resistance.

Reference Example 4 0.5 part of the compound of structural formula (37) was mixed with 0.2 parts of naphthalene sulfonic acid formalin condensate, 0.1 part of polyoxyethylene sorbitol, and 0 of sodium alkylbenzenesulfonate.
．． 1 part and sufficiently kneaded with a small amount of water to obtain a dispersion liquid with a total amount of 10 parts.

A dyebath is prepared by diluting this with water to 5000 parts.

This bath is padded with a mixed broadcloth of polyester-cotton (65:35), squeezed to 65%, and dried at 70°C for 10 minutes.

- Next, dry at 180°C for 1 minute, and add 100% water.
Soaping is carried out at 80° C. for 10 minutes in a solution containing 0 parts and 2 parts of higher alcohol sulfate ester, followed by washing with water and drying to obtain a beautifully whitened dyed cloth.

9 Reference Example 5 Add 0.01 parts of the compound of structural formula (44) to 100 parts of water, and adjust the pH to 3 by adding acetic acid.

Add 2 parts of nylon taffeta at 60℃, and 40℃ at 95℃.
Process for minutes.

Then, by washing with water and drying, a nylon cloth having an excellent light fastness of 5 is obtained.

Reference Example 6 0.1 part of the compound of structural formula (68) was heated and melted with 200 parts of titanium oxide-containing polystyrene pellets at a temperature of 200°C.
The whitened O pellets are obtained by passing through an extruder maintained at a constant temperature.

If this is put into an injection molding machine with a cylinder temperature of 200°C and injection molded, a clear milky white polystyrene product will be obtained.

Claims (1)

[Claims] 1. In the presence of a palladium catalyst, triphenylphosphine and an acid binding agent, the benzene ring of the following general formula (1) is a chlorine atom, a lower alkyl group, a lower alkoxy group, a sulfonic acid group or a salt thereof. , can have a carboxylic acid group or a salt thereof. ) to 1 molar ratio of the compound represented by the following general formula (2) and the compound represented by the general formula (3) (in the formula, Rt, R2, R3t and R4 are the same or different). Hydrogen atoms, chlorine atoms, lower alkyl groups,
Represents a lower alkoxy group, a sulfonic acid group or a salt thereof, a sulfonamide group, a sulfonic acid ester group, a carboxylic acid group or a salt thereof, a carbonamide group, a carboxylic acid ester group, a cyano group, or a phenyl group. ) is reacted with the following general formula % formula % (wherein A represents the same meaning as in general formula (1), R1, R2j R3, R4 are general formula (2) and general formula ( It has the same meaning as in 3).) A method for producing a styryl compound represented by .