JPS6212823B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to derivatives of coumarin and benzocoumarin useful as primrose yellow to orange pigments. Heavy metal yellow pigments such as lead chromate, cadmium sulfide and nickel titanate have been widely used in the paint and plastics industries for many years. However, in recent years, due to concerns about toxicity and environmental issues associated with its production and use,
Industry has sought alternatives to these heavy metal pigments. Organic yellow pigments that do not contain heavy metals represent a potential alternative to the currently used inorganic yellow pigments. However, such alternatives must provide excellent bleedfastness and durability. Moreover, it also needs to give a bright, strong color tone so that it can be mixed with white pigments such as TiO ₂ to obtain the necessary opacity while still retaining the necessary color intensity. Commercially available organic yellow pigments do not meet all of these requirements. Organic yellow pigments currently in use are classified into six basic classes. (ed. K. Venkataramen, “The
Chemistry of Synthetic Dyes”, Volume 5, J.
(See Lenoir, Academic Press, New York, 1971). That is, the six groups are monoazo, diarylide, condensed azo, isoindolinone, anthraquinone, and metal chelate pigments.
Each group has one or more difficulties. Monoazo yellow pigments generally have poor bleed fastness and marginal durability. Diarylide yellow pigments are not very durable. Condensed azo yellow pigments are marginally durable, but are expensive and impractical.
Isoindolinone and anthraquinone yellow pigments have relatively low color strength and are too expensive for practical use. Metal chelate yellow pigments are dull, often fringe pigments, and do not completely avoid heavy metal problems. The present invention relates to a new class of yellow to orange organic pigments. This new class of compounds provides even, intense color with excellent smudge fastness and durability. The pigments of the present invention are particularly useful for coloring paints, plastics and inks and can be an excellent alternative to the potentially toxic inorganic pigments currently in use. The present invention relates to derivatives of coumarin, 5,6-benzocoumarin and 7,8-benzocoumarin,
Concerning pigments represented by the following general formula: In the formula, R ₁ and R ₃ are groups selected from and;

【formula】

【formula】

[Formula] R ₂ is a group of or:

【formula】

[Formula] However, in the above general formula ~, X ₁ is selected from hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine and bromine; X ₂ is hydrogen or -CONHAr, and Ar is phenyl, or phenyl substituted with a substituent selected from alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine, bromine, carbonamide, sulfonamide, benzimidazolone, and phthalimide; X ₃ is selected from hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to ₄ carbon atoms, chlorine and bromine; X ₄ is selected from hydrogen, alkyl having 1 to 4 carbon atoms, chlorine and bromine; is selected from hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine, bromine, and nitro; Y ₁ and Y ₂ may be the same or different, and each represents hydrogen or alkyl having 1 to 4 carbon atoms; selected from alkyl, alkoxy having 1 to 4 carbon atoms, chlorine and bromine. As mentioned above, the present invention relates to a new class of organic pigments ranging in color from yellow to orange. This new group of compounds provides a strong color with excellent smudge fastness and durability and is represented by the general formula above. The compounds of the invention are derived from coumarins and benzocumarin. As can be seen from the foregoing description, the present invention encompasses benzocoumarin-derived pigments having the following general formula: In the above formula, X ₁ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₂ is hydrogen or -CONHAr, and Ar is phenyl or phenyl substituted with a substituent selected from ~4 alkyl, C1-4 alkoxy, chlorine, bromine, carbonamide, sulfonamide, benzimidazolone and phthalimide: Y ₁ and Y ₂ are each hydrogen , alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. In the above formula, X ₁ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₂ is hydrogen or -CONHAr, and Ar is phenyl or phenyl substituted with a substituent selected from ~4 alkyl, C1-4 alkoxy, chlorine, bromine, carbonamide, sulfonamide, benzimidazolone and phthalimide; Y ₁ and Y ₂ are each hydrogen , alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. The present invention also includes pigments derived from benzocoumarins having the following general formula and: In the above formula, X ₃ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₄ is hydrogen, alkyl having 1 to 4 carbon atoms, chlorine or bromine; Y ₁ and Y ₂ are each hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. In the above formula, X ₃ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₄ is hydrogen, alkyl having 1 to 4 carbon atoms, chlorine or bromine; Y ₁ and Y ₂ are each hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. The present invention further relates to compounds derived from coumarins, represented by the general formulas XI and XII below. In the above formula, X ₁ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 _carbon atoms, chlorine or bromine; It is alkoxy, chlorine, bromine or nitro, and Y ₁ and Y ₂ are each hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. In the above formula, X ₁ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 _carbon atoms, chlorine or bromine; alkoxy, chlorine, bromine or nitro; Y ₁ and Y ₂ are each hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. As can be seen from the above formula, general formula XII is a compound derived from coumarin and biphenyl or substituted biphenyldiamine. Among the compounds of the general formula ~, X ₁ , X ₃ ,
X ₄ , Y ₁ and Y ₂ are hydrogen, methyl or methoxy, X ₂ is hydrogen or -CONHAr,
Compounds in which Ar is phenyl substituted with methyl or methoxy are preferred. Among the compounds of general formulas XI and XII, X ₁ ,
Compounds in which X ₅ , Y ₁ and Y ₂ are hydrogen, chlorine, methyl or methoxy are preferred. The most preferred compounds of the invention are of general formula XI.
A compound in which X ₁ , X ₅ , Y ₁ and Y ₂ are hydrogen, chlorine, methyl or methoxy. The color of the compounds of the invention ranges from greenish yellow to reddish yellow. For example, if X ₁ and _{X 5} and Y ₁ and _{Y 2} of a compound of general formula , Y ₁ or Y ₂ is alkyl or alkoxy, the compound has a reddish hue. Therefore, by changing various substituents on the skeleton of the compound, yellow to orange pigments of various hues can be obtained. The compounds of the invention also have very low solubility in organic solvents and exhibit overstripe
Shows excellent smear resistance in typical alkyd or lacquer paints as determined by the smear test. Moreover, the compounds of the invention have excellent resistance to migration in plastics such as polyvinyl chloride. In general, when the substituents are the same, compounds of general formulas XI and It turned out to be a big deal. However, it has also been found that the thermal stability when dispersed in common plastic dispersions is generally superior to the compounds of general formulas XI and XII when the substituents are the same. did. The compounds of the present invention can be produced by various methods. A preferred method of preparing the compounds of the present invention is to combine the appropriate coumarin or benzocoumarin carbonyl chloride with the appropriate aromatic diamine in o-dichlorobenzene, a toluene/triethylamine mixture or Dowtherm A (23.5% by weight biphenyl and 76.5% by weight diphenyl oxide). It is a method of heating in the presence of a suitable solvent such as a eutectic mixture consisting of Another method for preparing the compounds of the present invention is to heat a suitable carboxylic acid ester of coumarin or benzocoumarin together with a suitable aromatic diamine in the presence of a suitable base and a suitable solvent. Example 1 A mixture consisting of 50 g of 5,6-benzocoumarin-3-carbonyl chloride, 10.5 g of p-phenylenediamine and 1000 ml of o-dichlorobenzene was
Heated to 140-150°C for 6 hours. The product was isolated by filtering the hot mixture and washed with dimethylformamide and then methanol. After drying, N・N'-p-
Phenylenebis(3-oxo-3H-naphtho[2.1-b]pyran-2-carboxamide) 50
g was obtained as a yellow crystalline solid. Analytical value: C ₃₄ H ₂₀ N ₂ O ₆ Calculated value: C 73.6; H 3.9; N 5.3 Actual value: C 73.9; H 3.7; N 5.1 Example 2 Ethyl 5,6-benzocoumarin-3-carboxylate 13.4 g , p-phenylenediamine 2.7 g, potassium acetate 4.9 g and Dowtherm A (diphenyl
A mixture consisting of 150 ml (covalent mixture of 23.5% and 76.5% diphenyl oxide) was heated to 200° C. for 10 hours. The product was isolated by filtration of the reaction mixture, washing first with methanol, then water, then hot dimethylformamide. The product is N・N′-p-phenylenebis(3-oxo-3H-naphtho[2・1-
b] pyran-2-carboxamide) 9.2 g. Infrared and elemental analysis results confirmed that the product was identical to that prepared in Example 1. Example 3 A mixture consisting of 3.0 g of 5,6-benzocoumarin-3-carbonyl chloride, 1.4 g of 2-chloro-p-phenylenediamine sulfate, 10 ml of triethylamine and 100 ml of toluene was stirred at room temperature for 1 hour, and then heated to 110°C. The mixture was heated for 4 hours. The product was isolated by filtering the hot mixture and washed sequentially with methanol, water and dimethylformamide. The product was further purified by extraction with 150 ml of boiling dimethylformamide. After drying, a reddish-yellow crystalline solid of N・N′-(2-chloro-
1,4-phenylene)bis(3-oxo-3H-
The amount was 1.1 g (naphtho[2.1-b]pyran-2-carboxamide). Analytical value: C ₃₄ H ₁₉ N ₂ O ₆ Cl Calculated value: C 69.6; H 3.3; N 4.8; Cl 6.0 Actual value: C 69.4; H 3.7; N 5.0; Cl 7.1 Example 4 2-methoxy-4-nitro 16.5 g of aniline, 1.0 g of platinum oxide, and 200 ml of o-dichlorobenzene
A mixture of
The mixture was shaken under a hydrogen atmosphere of 100 psi (7 Kg/cm ² ) until hydrogen absorption stopped. Then add the hydrogenation mixture to approximately
The hydrogenation catalyst, platinum, was removed by heating to 100° C. and filtering. The liquid is 5,6-benzocoumarin-
Mixed with 50 g of 3-carbonyl chloride and an additional 300 ml of o-dichlorobenzene and heated to 150° C. for 6 hours. The product was collected by filtration and purified by mixing with 1000 ml of dimethylformamide, filtration, washing with methanol and drying. What was produced was a reddish yellow solid N・N'-
(2-methoxy-4,4-phenylene)bis(3
-Oxo-3H-naphtho[2.1-b]pyran-
2-carboxamide) was 42.3 g. Analytical value: C ₃₅ H ₂₂ N ₂ O ₇ Calculated value: C 73.6; H 3.9; N 5.3 Actual value: C 73.9; H 3.7; N 5.1 Example 5 17.5 g of 5,6-benzocoumarin-3-carbonyl chloride, 2,5-dichloro-p-phenylene
A mixture of 6.0 g and 1000 ml of o-dichlorobenzene was heated to 150°C for 6 hours. The product was isolated by filtration and washed sequentially with dimethylformamide and methanol. What was obtained after drying was a yellow crystalline solid, N.N'-(2,5-dichloro-1,4-phenylene)bis(3-oxo-3H).
-naphtho[2.1-b]pyran-2-carboxamide) 12.8 g. Analytical value: C ₃₄ H ₁₈ N ₂ O ₆ Cl ₂ Calculated value: C 65.7; H 2.9; N 4.5; Cl 11.4 Actual value C 65.8; H 3.3; N 4.6; Cl 11.4 Example 6 5.6-benzocoumarin- 25 g of 3-carbonyl chloride, 8.1 g of 2,5-dimethoxy-p-phenylenediamine and 1000 g of o-dichlorobenzene
ml mixture was heated to 150° C. for 6 hours.
The product was isolated by filtration and the dimethylformamide was washed sequentially with methanol. After drying, the product is an orange crystalline solid, N.N'-(2,5-dimethoxy-1,4-phenylene)bis(3-oxo-
The amount of 3H-naphtho[2.1-b]pyran-2-carboxamide) was 24 g. Analytical value: C ₃₆ H ₂₄ N ₂ O ₈ Calculated value: C 70.6; H 4.0; N 4.6 Actual value: C 70.8; H 4.3; N 4.5 Examples 7 to 28 Other books listed in Table 1 below The compounds of the invention can also be prepared according to the method described in Example 1 by heating Reactants 1 and 2 to give the indicated products.

【table】

【table】

【table】

[Table] Example 29 15 g of 7,8-benzo-6-chlorocoumarin-3-carbonyl chloride, p-phenylenediamine
A mixture consisting of 2.76 g and 300 ml of o-dichlorobenzene was heated to 140°C for 5 hours. The product precipitated out and was collected by passing through the hot reaction mixture. The product was thoroughly washed with methanol and dried, yielding 15.4 g (95% of theory) of N.N'-p-
Phenylene bis(2-oxo-2H-6-chloro-naphtho[1,2-b]pyran-3-carboxamide) was obtained as a bright yellow material. Analytical value: C ₃₄ H ₁₈ N ₂ O ₆ Cl ₂ Calculated value:
C 65.71; H 2.92; N 4.51; Cl 11.41 Actual value:
C 65.78; H 3.15; N 4.49; Cl 12.00 Example 30 14 g of 7,8-benzo-6-chlorocoumarin-3-carbonyl chloride, 3.37 g of 2-methoxy-p-phenylenediamine (2-methoxy-4-nitro Prepared by hydrogenation of 4.1 g of aniline)
and 300 ml of o-dichlorobenzene was heated to 150°C for 5 hours. The product precipitated out and was isolated by filtering the hot reaction mixture.
After washing the product thoroughly with methanol and drying,
10.6 g (68% of theory) of N.N'-(2-methoxy-1,4-phenylene)bis(2-oxo-
2H-6-chloro-naphtho[1,2-b]pyran-3-carboxamide) was obtained as a bright orange substance. Analytical value: C ₃₅ H ₂₀ N ₂ O ₇ Cl ₂ Calculated value:
C 64.53; H 3.09; N 4.30; Cl 10.89 Actual value:
C 64.37; H 3.32; N 4.11; Cl 11.20 Examples 31-42 Compounds of the invention other than those listed above can also be prepared by the method described in Example 28. Then, by heating Reactant 1 and Reactant 2, the indicated product can be obtained.

【table】

[Table] Example 43 Coumarin-3-carbonyl chloride 10g, p-
A mixture consisting of 2.6 g of phenylenediamine and 250 ml of o-dichlorobenzene was heated to 140-150°C for 6 hours. The product precipitated out and was isolated by filtering the hot reaction mixture, washed with methanol and dried. The product is a bright yellow N・N'-p-
10.3 g (theoretical amount) of phenylene bis(2-oxo-2H-1-benzopyran-3-carboxamide)
96%), which did not melt at temperatures below 350°C. Analytical value: C ₂₆ H ₁₆ N ₂ O ₆ Calculated value: C 69.2; H 3.6; N 6.2 Actual value: C 69.0; H 3.8; N 6.4 Example 44 Ethyl coumarin-3-carboxylate 21.8 g, p-
5.4g of phenylenediamine and sodium carbonate
A mixture of 5.3 g added to 200 ml of Dowtherm A (eutectic mixture of 23.5% diphenyl and 76.5% diphenyl oxide) was heated to 200±5° C. for 6 hours. A cooling tube with a steam jacket was attached to facilitate removal of ethanol from the reaction mixture. The product precipitated out and was isolated by filtering the hot reaction mixture and washed with methanol, water and dimethylformamide. After drying, 21.5g
(95% of the theoretical amount) of N.N'-p-phenylenebis(2-oxo-2H-1-benzopyran-3-carboxamide) was obtained. Similar results can be obtained by using, for example, potassium acetate or sodium ethoxide instead of sodium carbonate. Example 45 Salicylaldehyde 12.2g, ethyl malonate
Dowtherm 16.0g and 9.8g potassium acetate
The mixture added to 200ml of A was heated to 175°C for 6 hours. A condenser with a steam jacket and a mild vacuum (approximately 40 mm Hg) were used to facilitate the removal of water and ethanol from the reaction mixture. After the reaction mixture was cooled to room temperature, 5.4 g of p-phenylenediamine was added. After that, the reaction system
Reheated to 200±10°C for 6 hours. After cooling to 100℃,
The precipitated product was separated, washed with methanol and water, and dried. The product contained 15.4 g (68.5%) of N.
N'-p-phenylenebis(2-oxo-2H-1
-benzopyran-3-carboxamide). Example 46 Coumarin-3-carbonyl chloride 35g, 2-
A mixture consisting of 12 g of chloro-p-phenylenediamine and Dowtherm A1 was heated to 100 DEG C. for 6 hours under a vacuum of about 60 mm Hg. The product was isolated by filtering the hot reaction mixture, washed well with methanol, and dried. The product is a yellow N・N′-(2′-chloro-1′・4′-phenylene)bis(2-oxo-
2H-1-benzopyran-3-carboxamide)
It weighed 38.3g. Analytical value: C ₂₆ H ₁₅ N ₂ O ₆ Cl Calculated value:
C 61.14; H 3.11; N 5.75; Cl 7.28 Actual value:
C 64.45; H 3.30; N 5.61; Cl 7.22 This product was dispersed in a thermoplastic acrylic lacquer paint by ball milling. A portion of this paint was mixed with an amount of titanium dioxide pigment such that the final toner/white pigment ratio was 5/95. Another portion of the same paint was mixed with aluminum flakes in an amount such that the toner/metal ratio was 90/10. The above three types of paints were spray applied to primed aluminum panels. The panels were placed outdoors facing south to test the durability of the paint. After 6 months, the durability of these paints was compared with Irgazin, a commercially available yellow pigment similar in tone to the product of Example 46.
It was superior to a paint similarly prepared from Yellow2GLT. Measurement of smear fastness of the product of this example in thermoplastic acrylic lacquer paint was performed on a primed aluminum panel with a masstone
This was done by spraying a white overstripe lacquer coat and baking the panel in a heater at 150°C for 30 minutes. No migration of yellow pigment into white overstripe could be observed. Example 47 Salicylaldehyde 12.2g, ethyl malonate
A mixture of 16.0 g and 5.3 g of anhydrous sodium carbonate in 250 ml of Dowtherm A was heated under a weak vacuum (approximately
60 mmHg) and heated to 150°C for 4 hours. The vacuum was removed and 7.1 g of slurried 2-chloro-p-phenylenediamine was added to 50 ml of Dowtherm A in one portion. The reaction temperature was raised to 210°C and held for 2 hours. The reaction mixture was then cooled to 100°C and filtered. The product is washed with methanol and water and dried to give a greenish-yellow N・N′-(2′-chloro-1′・4′-phenylene)bis(2-oxo-2H-
1-benzopyran-3-carboxamide) 19.6g
was gotten. The material prepared in this manner is a structural isomer of the product described in Example 46. The products of Examples 46 and 47 had the same chemical composition but exhibited different X-ray spectra. Conversion of the material prepared in this example to the more desirable form obtained in Example 46 can be accomplished by various processing methods common in the pigment industry, such as acid pasting or solvent milling. Example 48 6-Nitrocoumarin-3-carbonyl chloride
10 g, p-phenylenediamine 2.1 g and o-
A mixture consisting of 250 ml of dichlorobenzene was added to 150 ± 5
℃ for 6 hours. The product was separated, washed with methanol and dried. Bright yellow N・N'-p-
Phenylene bis(2-oxo-6-nitro-2H
-1-benzopyran-3-carboxamide) 7.6
g was obtained. Analytical value: C ₂₆ H ₁₄ N ₄ O ₁₀ Calculated value: C 57.57; H 2.60; N 10.33 Actual value: C 57.30; H 2.81; N 9.98 Examples 49-76 General other than the above listed in Table 3 below Compounds of formula XI or XII can also be prepared according to the method described in Example 43 by heating Reactants 1 and 2 to yield the indicated products.

【table】

【table】

【table】

[Table] Examples 77-166 The compounds of the invention listed in the following Table 4 were prepared according to the method described in Example 1 with the indicated Reactant 1.
and Reactant 2 to obtain the indicated product.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. Compound of the following general formula: In the formula, R ₁ and R ₃ are selected from the following groups: [Formula] [Formula] and [Formula] R ₂ is selected from the following divalent groups: [Formula] and [Formula _] is selected from hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine and bromine; X ₂ is hydrogen or -CONHAr, and Ar is phenyl or alkyl having 1 to 4 carbon atoms; phenyl substituted with a substituent selected from alkoxy having 1 to 4 carbon atoms, chlorine, bromine, carbonamide, sulfonamide, benzimidazolone and phthalimide; X ₃ is hydrogen, alkyl having 1 to 4 carbon atoms, selected from alkoxy having 1 to 4 carbon atoms, chlorine and bromine; X ₄ is selected from hydrogen, alkyl _having 1 to 4 carbon atoms, chlorine and bromine; Y ₁ and Y ₂ are each selected from hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine and bromine. 2. A compound according to claim 1, which is represented by the following general formula: In the above formula, X ₁ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₂ is hydrogen or -CONHAr, and Ar is phenyl or phenyl substituted with a substituent selected from ~4 alkyl, C1-4 alkoxy, chlorine, bromine, carbonamide, sulfonamide, benzimidazolone and phthalimide; Y ₁ and Y ₂ are each hydrogen , alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. 3. The compound according to claim 2, wherein X ₁ is hydrogen, methyl, methoxy, chlorine or bromine; X ₂ is hydrogen or -CONHAr, and Ar is phenyl or has 1 to 4 carbon atoms. phenyl substituted with alkyl, alkoxy having 1 to 4 carbon atoms, chlorine, bromine, carbonamide, sulfonamide, benzimidazolone or phthalimide; Y ₁ and Y ₂ are each hydrogen, methyl, methoxy, chlorine or bromine something that is. 4. A compound according to claim 1, which is represented by the following general formula: In the above formula, X ₃ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₄ is hydrogen, alkyl having 1 to 4 carbon atoms, chlorine or bromine; Y ₁ and Y ₂ are each hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. 5 The compound according to claim 4, wherein X ₃ is hydrogen, methyl, methoxy, chlorine or bromine; X ₄ is hydrogen, methyl, chlorine or bromine; Y ₁ and Y ₂ are each Hydrogen, methyl, methoxy, chlorine or bromine. 6. A compound according to claim 1, which is represented by the following general formula: In the above formula, X ₁ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₂ is hydrogen or -CONHAr, and Ar is phenyl or phenyl substituted with a substituent selected from ~4 alkyl, C1-4 alkoxy, chlorine, bromine, carbonamide, sulfonamide, benzimidazolone and phthalimide; Y ₁ and Y ₂ are each hydrogen , alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. 7 The compound according to claim 6, wherein X ₁ is hydrogen, methyl, methoxy, chlorine or bromine; X ₂ is hydrogen or -CONHAr, and Ar is the compound according to claim 6 As defined above; Y ₁ and Y ₂ are hydrogen, methyl,
Those that are methoxy, chlorine or bromine. 8. A compound according to claim 1, which is represented by the following general formula: In the above formula, X ₃ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine; X ₄ is hydrogen, alkyl having 1 to 4 carbon atoms, chlorine or bromine; Y ₁ and Y ₂ are each hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. 9 The compound according to claim 8, wherein X ₃ is hydrogen, methyl, methoxy, chlorine or bromine; X ₄ is hydrogen, methyl, chlorine or bromine; Y ₁ and Y ₂ are each Hydrogen, methyl, methoxy, chlorine or bromine. 10 A compound according to claim 1, which is represented by the following general formula: In the above formula, X ₁ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 _carbon atoms, chlorine or bromine; alkoxy, chlorine, bromine or nitro; R ₄ is [Formula] or [Formula], where Y ¹ and Y ² may be the same or different, and each represents hydrogen and has 1 to 4 carbon atoms. alkyl, alkoxy having 1 to 4 carbon atoms, chlorine or bromine. 11. The compound according to claim 10, wherein X ₁ , X ₅ , Y ₁ and Y ₂ are selected from the group consisting of hydrogen, methyl, methoxy and chlorine. 12. A compound according to claim 10, wherein R ₄ is [Formula]. 13. A compound according to claim 11, wherein R ₄ is [Formula]. 14. A compound according to claim 10, wherein R ₄ is [Formula]. 15. The compound according to claim 11, wherein R ₄ is [Formula]. 16 A compound according to claim 10, which is represented by the following general formula: In the above formula, X ₁ is hydrogen or chlorine; X ₅ is hydrogen or chlorine; Y ₁ is hydrogen or chlorine; Y ₂ is hydrogen. 17. The compound according to claim 16, which is N.N'-(2'-chloro-1'.4'-phenylene)bis(2-oxo-2H-1-benzopyran-3-carboxamide).