JP3267745B2 - Novel isoindolenin compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel isoindolenin compound having a halogen atom, which has a special function different from conventionally known isoindolenin compounds. Light fastness,
It can be used as a thermal transfer recording material having high heat resistance and storage stability, or as an intermediate of a functional material such as an optical information recording medium, a dye for transfer printing, and an ink for ink jet. Among them, the present compound has a particularly excellent function as a thermal transfer recording material.

[0002]

2. Description of the Related Art Conventionally, various studies have been made on isoindolenin compounds for use in thermal transfer materials.
No. 107477, Journal of the Textile Society of Japan, Vol 47, No. 4, 19
91 and the like. However, none of these isoindolenins are completely soluble in organic solvents and have a high melting point. There is no example describing a method for producing an isoindolenine compound in which a substituent has been introduced. An isoindolenine compound having high solubility or low melting point has been demanded for the purpose of improving image stability and sensitivity of thermal paper or facilitating coating.

[0003]

Accordingly, the present invention provides a thermal transfer material having a low melting point by imparting solubility to an isoindolenin compound which has been insoluble in organic solvents until now.
In addition, these manufacturing methods are also provided. The use of various functional dyes is expanded by imparting solubility, and the soluble isoindolenin compound is also useful as an intermediate material.

[0004]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, introduced fluorine or chlorine into an aromatic ring and further substituted a part of the fluorine or chlorine with a substituent. It has been found that isoindolenine having improved solubility in organic solvents can be obtained.
That is, utilizing a nucleophilic substitution reaction of a fluorinated or chlorinated phthalonitrile, which is a starting material for isoindolenin,
It has been found that phthalonitrile can be synthesized by introducing a substituent soluble in an organic solvent and then reacted in an alcohol solvent containing ammonia to synthesize isoindolenin soluble in an organic solvent.

Accordingly, the present invention provides the following general formula (I):

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(Wherein X ₁ and X ₄ represent a halogen atom, X ₂ represents a halogen atom, a mono- or di-alkylamino group having an alkyl group having 1 to 12 carbon atoms, A mono- or di-phenylamino group, an alkoxy group having 1 to 12 carbon atoms, a phenyloxy group which may have a substituent, an alkylthio group having 1 to 12 carbon atoms, or X ₃ represents a mono- or di-alkylamino group having an alkyl group having 1 to 12 carbon atoms, a mono- or di-phenylamino group optionally having a substituent, 1 to 12 alkoxy groups, a phenyloxy group which may have a substituent, an alkylthio group having 1 to 12 carbon atoms or a phenylthio group which may have a substituent.) Renin compound (however, 4,
5,7-trichloro-1,3-diimino-6-methylmercaptoisoindoline), and a method for producing the same.

The present invention also provides the following formula (II):

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Wherein X ₁ , X ₂ , X ₃ and X ₄ have the previously defined meanings, wherein the phthalonitrile derivative is reacted in an alcoholic medium containing ammonia. A method for producing an isoindolenin compound represented by the general formula (I) (except for 4,5,7-trichloro-1,3-diimino-6-methylmercaptoisoindoline) is provided.

[0009]

DETAILED DESCRIPTION In the present invention, X ₁ , X ₂ or X ₄
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom, preferably a chlorine atom and a fluorine atom. Mono having X ₂ or X ₃ alkyl groups having 1 to 12 carbon atoms in the - or di - alkylamino group as for example monomethyl amino group, mono ethylamino group, mono -n- propylamino group, monoisopropyl amino group, mono -N-
Butylamino group, monoisobutylamino group, mono-t-
Butylamino group, n-octyloxyamino group, dimethylamino group, diethylamino group, di-n-propyl group,
Examples thereof include a diisopropyl group, a di-n-butyl group, a diisobutyl group, a di-t-butyl, and a di-octylamino group.

Examples of the optionally substituted mono- or di-phenylamino group include, for example, substituted phenyl groups such as toluyl, xylyl, N, N-dimethylanilino, N, N -Diethylanilino group and the like. Specific examples of the mono- or di-phenylamino group which may have a substituent include an anilino group, a mono-p-toluylamino group, a mono-o-toluylamino group, a monoxylylamino group, a mono (4- N, N-dimethylanilyl)
-Amino group, mono (4-N, N-diethylanilyl)-
Amino group, di-p-toluylamino group, di-o-toluylamino group, di-xylylamino group, di- (4,4'-
N, N-dimethylanilyl) -amino group, di- (4,
4'-N, N-diethylanilyl) -amino group.

The alkoxy group having 1 to 12 carbon atoms includes methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, t-butyloxy, n-octyloxy,
n-decyloxy group. Examples of the substituent of the optionally substituted phenyloxy group include a lower alkyl group such as a methyl group. Specific examples of the phenyloxy group which may have a substituent include a phenoxy group, an o-toluyloxy group, a p-toluyloxy group, and a xylyloxy group.

Examples of the alkylthio group having 1 to 12 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group,
Isopropylthio group, n-butylthio group, isobutylthio group, t-butylthio group, n-octylthio group, n-decylthio group. ,
p-Toluylthio group, xylylthio group and the like.
Tables 1 to 3 show specific examples of preferred compounds of the present invention.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

In the present invention, the method for synthesizing isoindolenin involves introducing various substituents into a halogenated phthalonitrile by a nucleophilic substitution reaction, and reacting the phthalonitrile derivative with an alcoholic medium containing ammonia. . The phthalonitrile derivative as a starting material for the synthesis of isoindolenin of the present invention is obtained by reacting a halogenated phthalonitrile with a ROH, RONa, ROK, RSH, RSN
_{a, RSK, RNH 2, PR'NH} (R, R ' is a phenyl group which may have an alkyl group or a substituted group, having 1 to 12 carbon atoms) can be synthesized by reacting.

In the present invention, a method for synthesizing isoindolenin is obtained by reacting such a phthalonitrile derivative with an alcoholic medium containing ammonia. A method for synthesizing isoindolenin from phthalonitrile in an alcohol solvent containing ammonia is known. However, this method cannot be used in the case of fluorinated phthalonitrile as described in JP-A-62-106076. This is because the substitution reaction between the fluorine atom of tetrafluorophthalonitrile and ammonia or alcohol is easily caused, and it is difficult to synthesize the desired isoindolenin.

Therefore, the present inventors have conducted intensive studies, and as a result, before synthesizing isoindolenin, by introducing an electron-donating substituent to lower the nucleophilicity of phthalonitrile,
We have found a method that can synthesize isoindolenin from fluorinated phthalonitrile in an alcohol solvent containing ammonia. Thus, instead of the complex synthesis method involving imidation, chlorination and amination as described in JP-A-62-106076, isoindolenine is obtained from a halogenated phthalonitrile in an alcohol solvent containing ammonia. Has been found to be able to be synthesized in one step, and it is possible to synthesize isoindolenin which is soluble in an organic solvent.

In the method for synthesizing isoindolenine of the present invention, the alcohol medium is preferably, for example, methanol, ethanol, propanol, isobutyl alcohol, t-butyl alcohol, or ethylene glycol, but the solubility of ammonia and the ease of removal are considered. And methanol are particularly preferred. The concentration of ammonia contained in the alcoholic medium in the present invention may be at least twice the molar amount of the phthalonitrile charged, and especially when heated, the solubility of ammonia in the alcoholic medium is considerably low, so Preferably, the reaction is performed under pressure using a method of blowing ammonia specifically or using an autoclave. In the present invention, the reaction temperature is -10 to 120.
C., preferably from 20 to 6 ° C.
It is good to carry out in the range of 0 ° C.

Since the solubility varies depending on the type of isoindolenine produced, some of them can be separated only by filtration after the reaction. Therefore, the concentration of phthalonitrile in the alcoholic medium is 1 to 3 depending on the type of isoindolenine. Preferably, it is changed in the range of 20% by weight. In the present invention, as a method for removing isoindolenin,
Isoindolenine having low solubility in alcoholic medium may be filtered after the reaction, and isoindolenine having high solubility can be isolated by evaporation to dryness.

[0021]

EXAMPLES The method for producing a novel substance according to the present invention will be specifically described below with reference to examples. Embodiment 1 FIG . 4-anilino-3,5,6-trifluorophthalonitrile
In a 100 ml separable flask, 5 g (0.025 mol) of 3,4,5,6-tetrafluorophthalonitrile, 9.3 g (0.1 mol) of aniline, 50 ml of acetonitrile
And reacted at 25 ° C. for 24 hours. After completion of the reaction, the insolubles were filtered off, and acetonitrile and aniline were distilled off under reduced pressure.
Then, the product was washed with 100 ml of methanol to obtain 5.2 g of the desired product as a pale yellow cake (yield based on 3,4,5,6-tetrafluorophthalonitrile: 76.2).
%).

4-anilino-3,5,6-trifluoro
Synthesis of isoindolenin 4-anilino-3,5,6-trifluorophthalonitrile 10 g (0.037 mol) was added to methyl alcohol 200 m2.
and bubbling ammonia gas with stirring.
C. for 3.5 hours. After cooling, the mixture was washed with filtered methanol and dried to obtain 3 g of an orange cake (4-g).
Anilino-3,5,6-trifluorophthalonitrile yield 30%).

Elemental analysis value C (%) H (%) N (%) F (%) Theoretical value 57.92 3.10 19.31 19.66 Analysis value 57.80 3.03 18.94 19.26 Infrared absorption spectrum (KBr plate) The infrared absorption spectrum of this substance is shown in FIG.

Embodiment 2 FIG. 3,6-difluoro-4,5-bis (normal butylthio
E ) Synthesis of phthalonitrile In a 100 mL four-necked flask, 19.6 g (0.098 mol) of 3,4,5,6-tetrafluorophthalonitrile was added.
Normal butane thiol 17.3 g (0.196 mo
l), 17.1 g (0.294 mol) of potassium fluoride and 100 mL of acetonitrile were charged, and stirring was maintained at 50 ° C. for 12 hours. Then, after cooling to room temperature, potassium fluoride was filtered and the solvent was distilled off. The obtained orange oily substance was washed with a dilute aqueous solution of sodium hydroxide and then with warm water to give 33.9 g of 3,6-difluoro-4,5-bis (normalbutylthio) phthalonitrile (3,4,5,5).
92. Yield based on 6-tetrafluorophthalonitrile
1%) as a yellow oil.

3,6-difluoro-4,5-bis (nor
Synthesis of malbutylthio) isoindolenin 5 g (0.018 mol) of 3,6-difluoro-4,5-bis ( normalbutylthio) phthalonitrile was added to 200 ml of methyl alcohol, and ammonia gas was bubbled under stirring, and the temperature was raised to 40 ° C. Hold for 10 hours. After cooling, the precipitate was washed with filtered methanol and then dried to obtain 3.7 g of a lemon-colored cake (71% yield based on 3,6-difluoro-4,5-bis (normalbutylthio) phthalonitrile).

Elemental analysis value C (%) H (%) N (%) F (%) S (%) Theoretical value 53.78 5.88 11.76 10.64 17.93 Analytical value 53.57 5. 73 11.59 10.30 17.88 Infrared absorption spectrum (KBr plate) FIG. 2 shows the infrared absorption spectrum of this substance.

Embodiment 3 FIG. 3,6-difluoro-4,5-bis (phenylthio) phenyl
Synthesis of Talonitrile In a 200 mL four-necked flask, 19.6 g (0.098 mol) of 3,4,5,6-tetrafluorophthalonitrile,
21.6 g (0.196 mol) of thiophenol, 17.1 g (0.294 mol) of potassium fluoride and 100 mL of acetonitrile were charged, and stirring was maintained at 50 ° C. for 12 hours.

After cooling to room temperature, the obtained yellow cake was filtered, and the obtained yellow cake was washed with methanol and then with warm water, and 34.5 g of 3,6-difluoro-4,5-bis (phenylthio) phthalonitrile was obtained. (19.6 g (0.098 mol) of 3,4,5,6-tetrafluorophthalonitrile, 21.6 g (0.196 mol) of thiophenol, potassium fluoride 1 in a 3,200 ml four-necked flask)
7.1 g (0.294 mol) and acetonitrile 10
0 mL was charged and stirring was maintained at 50 ° C. for 12 hours.

After cooling to room temperature, the obtained yellow cake was filtered, and the obtained yellow cake was washed with methanol and then with warm water to give 3,6-difluoro-4,5-bis (phenylthio) phthalonitrile. 5g (3,4,5,6
92.5 yield based on tetrafluorophthalonitrile
%). 3,6-difluoro-4,5-bis (phenylthio) i
Synthesis of soindrenine 5 g (0.018 mol) of 3,6-difluoro-4,5-bis (phenylthio) phthalonitrile was added to 200 ml of methyl alcohol, and ammonia gas was bubbled with stirring, and the temperature was maintained at 40 ° C. for 10 hours. After cooling, the precipitate was washed with filtered methanol and dried to obtain 1.8 g of a lemon-colored cake. The obtained cake was recrystallized with acetone to obtain 1.2 g of an isoindolenin compound (3,6-difluoro-
Yield based on 4,5-bis (phenylthio) phthalonitrile 57.4%).

Elemental analysis value C (%) H (%) N (%) F (%) S (%) Theoretical value 60.45 3.28 10.58 9.57 16.12 Analysis value 60.29 3. 19 10.37 9.27 16.24 Infrared absorption spectrum (KBr plate) The infrared absorption spectrum of this substance is shown in FIG.

Embodiment 4 FIG. 4-dimethylamino-3,5,6-trichlorophthaloni
Synthesis of Toril A 300 ml separable flask was charged with 50 g (0.188 mol) of 3,4,5,6-tetrachlorophthalonitrile and 220 ml of dimethylformamide and reacted under reflux for 7 hours. After completion of the reaction, the reaction solution was poured into water, and yellow crystals were separated by filtration and washed with 100 ml of hexane to obtain 50.1 g of a yellow cake. Further, the mixture was recrystallized from a mixed solution of benzene and hexane to obtain 40 g of a target yellow cake (yield based on 3,4,5,6-tetrachlorophthalonitrile: 80%).

4-dimethylamino-3,5,6-tric
Synthesis of loloisoindolenine 1 g (0.0024 mol) of 4-dimethylamino-3,5,6-trichlorophthalonitrile was added to methyl alcohol 6
0 ml, and bubbling ammonia gas with stirring.
It was kept at 0 ° C. for 4.5 hours. After cooling, it was washed with filtered methanol and then dried to obtain 0.86 g of a lemon-colored cake (82.6% yield based on 4-dimethylamino-3,5,6-trichlorophthalonitrile).

Elemental analysis C (%) H (%) N (%) Cl (%) Theoretical 41.17 3.09 19.21 36.54 Analytical 40.85 3.42 18.89 36.07 Infrared absorption spectrum (KBr plate) The infrared absorption spectrum of this substance is shown in FIG.

Embodiment 5 FIG. 3,6-dichloro-4,5-bis (phenylthio) phthalate
Synthesis of Lonitrile In a 300 mL four-necked flask, 13.3 g (0.05 mol) of 3,4,5,6-tetrachlorophthalonitrile, 11 g (0.1 mol) of thiophenol, 7 g of potassium fluoride
(0.12 mol) and 200 mL of acetonitrile were charged and stirred at 25 ° C. for 8 hours. After completion of the reaction, potassium fluoride was filtered, and acetonitrile was distilled off under reduced pressure.
14.9 g of 6-dichloro-4,5-bis (phenylthio) phthalonitrile was obtained (72% yield based on 3,4,5,6-tetrachlorophthalonitrile).

3,6-dichloro-4,5-bis ( phenyl
Synthesis of ruthio ) isoindolenine 1 g (0.0024 mol) of 3,6-dichloro-4,5-bis (phenylthio) phthalonitrile was added to 60 ml of methyl alcohol, and ammonia gas was bubbled with stirring. Hold for 5 hours. After cooling, the precipitate was washed with filtered methanol and then dried to obtain 0.86 g of a lemon-colored cake (82.6% yield based on 3,6-dichloro-4,5-bis (phenylthio) phthalonitrile).

Elemental analysis value C (%) H (%) N (%) Cl (%) S (%) Theoretical value 55.81 3.02 9.77 16.51 14.88 Analysis value 55.88 3. 28 9.66 16.33 14.63 Infrared absorption spectrum (KBr plate) The infrared absorption spectrum of this substance is shown in FIG.

Embodiment 6 FIG. 3,5,6-trichloro-4-phenoxyphthalonitrile
In a 100 mL four-necked flask, 5 g (0.019 mol) of 3,4,5,6-tetrachlorophthalonitrile, 60 mL of acetonitrile and 1.3 g of potassium fluoride (0.02 mol) were added.
(5 mol) was charged and stirred under reflux, and 20 mL of acetonitrile in which 1.8 g (0.02 mol) of phenol was dissolved was added dropwise, and the stirring was maintained under reflux for 20 hours. After completion of the reaction, the yellow cake obtained by distilling off acetonitrile under reduced pressure was washed with water, dried, and then dried with a silica gel column.
6-trichloro-4-phenoxyphthalonitrile 3.3
g was isolated (54% yield based on 3,4,5,6-tetrachlorophthalonitrile).

3,5,6-trichloro-4-phenoxy
Synthesis of Isoindolenin 3,5,6-Trichloro-4-phenoxyphthalonitrile (1 g, 0.0031 mol) in methyl alcohol (60 ml)
Ammonia gas is bubbled under stirring and the mixture is heated to 50 ° C.
For 8 hours. After cooling, filtration, washing with methanol and drying, 0.67 g of a light brown cake was obtained (3,5,5).
(64% yield based on 6-trichloro-4-phenoxyphthalonitrile).

Elemental analysis C (%) H (%) N (%) Cl (%) Theoretical 49.34 2.35 12.33 31.28 Analytical 48.98 2.28 12.66 30.84 Infrared absorption spectrum (KBr plate) The infrared absorption spectrum of this substance is shown in FIG.

Embodiment 7 FIG. 4-octyloxy-3,5,6-trichlorophthaloni
Synthesis of Tril In a 100 ml separable flask, 20 g (0.075 mol) of 3,4,5,6-tetrachlorophthalonitrile, 18.9 g (0.33 mol) of potassium fluoride, and 200 ml of acetonitrile were charged and refluxed. 19.6 g (0.15 mol) of n-octyl alcohol was slowly added dropwise, and the mixture was reacted under reflux for 8 hours. After the completion of the reaction, the insolubles were filtered off, and then acetonitrile and n-octyl alcohol were distilled off under reduced pressure.
Was obtained (56.0% yield based on 3,4,5,6-tetrachlorophthalonitrile).

4-octyloxy-3,5,6-tric
Synthesis of loloisoindolenin 1 g (2.8 mmol) of 4-octyloxy-3,5,6-trichlorophthalonitrile was added to 30 ml of methyl alcohol, ammonia gas was bubbled under stirring, and the temperature was maintained at 50 ° C. for 14.5 hours. . After cooling, the mixture was filtered and washed with methanol to obtain 0.8 g of a yellow cake (yield based on 4-octyloxy-3,5,6-trichlorophthalonitrile: 75.9%).

Elemental analysis value C (%) H (%) N (%) Cl (%) Theoretical value 51.00 5.31 11.16 28.29 Analytical value 50.81 5.42 11.03 27.84 Infrared absorption spectrum (KBr plate) The infrared absorption spectrum of this substance is shown in FIG.

Embodiment 8 FIG. 4-octyloxy-3,5,6-trifluorophthalo
Synthesis of nitrile In a 100 ml separable flask, 5 g (0.025 mol) of 3,4,5,6-tetrafluorophthalonitrile, 1.5 g (0.025 mol) of potassium fluoride, 3.3 g of n-octyl alcohol ( 0.025 mol) and 50 ml of acetonitrile, and reacted under reflux for 8 hours. After completion of the reaction, the insoluble matter was filtered off, and acetonitrile and n-octyl alcohol were distilled off under reduced pressure to obtain 6.1 g of a light yellow oily substance as a target substance (based on 3,4,5,6-tetrafluorophthalonitrile). Yield 78.4%).

4-octyloxy-3,5,6-trif
Synthesis of Fluoroisoindolenine 1 g (0.0031 mol) of 4-octyloxy-3,5,6-trifluorophthalonitrile was added to 60 ml of methyl alcohol, and ammonia gas was bubbled under stirring.
It was kept at 50 ° C. for 5.5 hours. After cooling, methanol was distilled off under reduced pressure, and 0.4 g of a yellow-green cake was obtained from the column (38.1% yield based on 4-octyloxy-3,5,6-trifluorophthalonitrile).

Elemental analysis C (%) H (%) N (%) F (%) Theoretical 58.72 6.12 12.84 17.43 Analytical 58.85 5.92 12.69 17.23

Comparative Example 1 Synthesis of tetrachloroisoindolenin 39.9 g (0.15 mol) of tetrachlorophthalonitrile in a 500 mL stainless steel autoclave and 7.7 g of ammonia (0.45 mol) in 210 g of methanol
l) was charged to a solution which had been previously absorbed, and then kept at 110 ° C. for 6 hours with stirring. Then, after cooling, a methanol suspension having a slightly brown solid substance was taken out of the autoclave and filtered. The obtained cake is 40 ° C
Washing was sufficiently performed using 200 g of methanol kept under the above conditions, followed by drying to obtain 37.7 g of tetrachloroisoindolenine.

[0047]

The solubility (in chloroform solvent) and the melting point of each of the isoindolenin compounds of Examples 3 and 6 and Comparative Example 1 were measured, and the results are shown in Table 4.

[0048]

[Table 4]

The conventional isoindolenin was prepared according to Comparative Example 1 in Table 4.
Is almost insoluble in organic solvents and has a high melting point, as shown by the tetrachloroisoindolenine. In contrast, the compounds of the present invention have improved solubility and significantly lower melting points by introducing various substituents. Isoindolenine compounds that are soluble in organic solvents and have a low melting point in terms of ease of coating are also effective as thermal transfer materials, and can be used in other applications such as optical recording media and ink-jet inks. The soluble isoindolenin compound is a useful intermediate of various functional dyes.

[Brief description of the drawings]

FIG. 1 shows 4-anilino-3, produced in Example 1,
FIG. 3 is an infrared absorption spectrum diagram of 5,6-trifluoroisoindolenine.

FIG. 2 is an infrared absorption spectrum of 3,6-difluoro-4,5-bis (normalbutylthio) isoindolenin produced in Example 2.

FIG. 3 is an infrared absorption spectrum of 3,6-difluoro-4,5-bis (phenylthio) isoindolenin produced in Example 3.

FIG. 4 is an infrared absorption spectrum of 4-dimethylamino-3,5,6-trichloroisoindolenine produced in Example 4.

FIG. 5 shows 6-dichloro-4, produced in Example 5.
FIG. 3 is an infrared absorption spectrum of 5-bis (phenylthio) isoindolenin.

FIG. 6 is an infrared absorption spectrum of 3,5,6-trichloro-4-phenoxyisoindolenin produced in Example 6.

FIG. 7 is an infrared absorption spectrum of 4-octyloxy-3,5,6-trichlorophthaloisoindolenin produced in Example 7.

────────────────────────────────────────────────── (5) References JP-A-6-2977851 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 209/44 CA (STN) REGISTRY (STN) )

Claims (2)

(57) [Claims] 1. The following general formula (I): (Wherein, X ₁ and X ₄ represent a halogen atom, and X ₂ represents a halogen atom, a mono- or di-alkylamino group having an alkyl group having 1 to 12 carbon atoms, -Or di-phenylamino group, having 1 to 1 carbon atoms
X represents 12 alkoxy groups, a phenyloxy group which may have a substituent, an alkylthio group having 1 to 12 carbon atoms, or a phenylthio group which may have a substituent;
₃ is a mono- or di-alkylamino group having an alkyl group having 1 to 12 carbon atoms, a mono- or di-phenylamino group which may have a substituent, an alkoxy group having 1 to 12 carbon atoms, A phenyloxy group which may have a group, an alkylthio group having 1 to 12 carbon atoms or a phenylthio group which may have a substituent. ) Is an isoindolenin compound (provided that 4,
5,7-trichloro-1,3-diimino-6-methylmercaptoisoindoline). 2. The following general formula (II): (Wherein, X ₁ and X ₄ represent a halogen atom, and X ₂ represents a halogen atom, a mono- or di-alkylamino group having an alkyl group having 1 to 12 carbon atoms, -Or di-phenylamino group, having 1 to 1 carbon atoms
X represents 12 alkoxy groups, a phenyloxy group which may have a substituent, an alkylthio group having 1 to 12 carbon atoms, or a phenylthio group which may have a substituent;
₃ is a mono- or di-alkylamino group having an alkyl group having 1 to 12 carbon atoms, a mono- or di-phenylamino group which may have a substituent, an alkoxy group having 1 to 12 carbon atoms, A phenyloxy group which may have a group, an alkylthio group having 1 to 12 carbon atoms or a phenylthio group which may have a substituent. 2. The method according to claim 1, wherein the phthalonitrile derivative is reacted in an alcohol medium containing ammonia.