CA2239119A1 - Azo compounds and process for preparing the same - Google Patents

Abstract

Novel monoazo compounds excellent in water, chemical and solvent resistances and other properties and synthesized by using 2-hydroxynaphthalene-3,6-dicarboxylic acid (or a salt thereof), amide, ureide, or an ester thereof as a coupler.

Description

CA 02239119 1998-0~-29 - SPECIFICATION
AZO COMPOUND AND PROCESS FOR PRODUCING THE SAME

TECHNICAL FIELD
The present invention relates to a novel azo compound and a process for producing the same.

BACKGROUND OF THE INVENTION
Azo pigments are synthesized by the coupling reaction of a diazonium compound and a coupler. Among the couplers used in the coupling reaction, a particularly important coupler is 2-hydroxynaphthalene-3-carboxylic acid or a derivative thereof.
Brilliant Carmine 6B (Pigment Red 57) and Watchung Red ~Pigment Red 48) which are prepared from 2-hydroxynaphthalene-3-carboxylic acid are most important red azolake pigments. These are used in the form of an insoluble metallic lake such as Ca, Ba, Mn, etc., but is inherently unstable to an acid or alkali because of metallic salts.
On the other hand, an insoluble azo pigment is synthesized using, as a coupler, 2-hydroxynaphthalene-3-anilide synthesized by the condensation of 2-hydroxynaphthalene-3-carboxylic acid and anilines. This so-called naphthol pigment has been developed for the purpose of improving the solubility and fastness, and is generally superior to an azolake pigment in properties such as light resistance, weathering resistance, chemical resistance, solvent resistance, etc.
Furthermore, an azo pigment derived from 2-hydroxynaphthalene-6-carboxylic acid which is an isomer of 2-hydroxynaphthalene-3-carboxylic acid, and characteristics thereof are known (Japanese Patent Kokai Publication No. Hei 2-302471).

DISCLOSURE OF THE INVENTION
The present invention is characterized by obtaining a novel azo coloring material, which is superior in water resistance, chemical resistance, solvent resistance, etc.
The present invention provides a novel azo compound using 2-hydroxynaphthalene-3,6-dicarboxylic acid, an ester, an amide or an ureide derivatives as a coup]er, a coloring material containing the same, and a process for producing the above azo CA 02239119 1998-0~-29 compound. That is, the present invention relates to the azo compound represented by the foDowing general formula [I]:

Z-N=N~
~(Q)m [ I ]

Y' [wherein Y represents -(CONH)n-X or -COR;
Y' represents -(CONH)n-X' or -COR';
(X and X' may be the same or different and represent an optionally substituted aromatic group, or an optionally substituted heterocyclic group having a conjugated double bond);
R and R' may be the same or different and represent a hydroxyl group, an optionally branched alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a phenyloxy group or a phenacyloxy group (provided that an acceptable salt may be formed when any one of R and R' is a hydroxyl group);
n represents an integer of 1 or 2;
R2 represents a hydrogen atom, an optionally branched alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms or a phenylallcyl group;
Q represents an optionally branched alkyl group having 1 to 6 carbon atoms, an optionally branched alkoxyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group or a nitroso group; m represents an integer of 0 to 3 (when m is 1, Q may be combined with any one of two condensed rings and, when m is 2 or 3, Q may be combined with one or both condensed rings or may be combined together with two condensed rings to form a ring); and Z represents an optionally substituted monovalent aromatic group], a process forproducing the same, and a coloring material containing this azo compound. The coloring material in the present specification means a dye, a pigment, ink, paint, printing ink, an electro-charge generating material, etc.
The present invention also relates to a process for producing an azo compound represented by the following general formula [I]:

CA 02239119 1998-0~-29 Z-N=N~
~<~(Q)m [ I ]

Y' [wherein Y represents -(CONH)n-X or -COR;
Y' represents -(CONH)n-X' or -COR';
(X and X' may be the same or different and represent an optionaDy substituted aromatic group, or an optionaDy substituted heterocyclic group having a conjugated double bond);
R and R' may be the same or different and represent a hydroxyl group, an optionaDy branched alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, aphenyloxy group or a phenacyloxy group;
n represents an integer of 1 or 2;
R2 rep,esellts a hydrogen atom, an optionally branched alkyl group having 1 to 6carbon atoms or an acyl group having 1 to 6 carbon atoms or a phenylalkyl group;Q represents an optionally branched alkyl group having 1 to 6 carbon atoms, an optionaDy branched alkoxyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group or a nitroso group; m represents an integer of 0 to 3 (when m is 1, Q may be combined with any one of two condensed rings and, when m is 2 or 3, Q may be combined with one or both condensed rings or may be combined together with two condensed rings to form a ring); and Z represents an optionally substituted monovalent aromatic group], which comprises diazotizing aromatic amines represented by the foDowing general formula [Il]:
Z-NH2 [II]
[wherein Z represents an optionally substituted monovalent aromatic group] and coupling the resulting diazonium compound with a compound represented by the following formula [III]
R20~ Y

~(Q)m [ III ]

Y' [wherein Y represents -(CONH)n-X or -COR;
Y' represents -(CONH)n-X' or -COR';
(X and X' may be the same or different and represent an optionally substituted aromatic group, or an optionally substituted heterocyclic group having a conjugated double bond);
R and R' may be the same or different and represent a hydroxyl group, an optionally branched alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a phenyloxy group or a phenacyloxy group;
n represents an integer of 1 or 2; and R2 represents a hydrogen atom, an optionally branched alkyl group having 1 to 6 carbon atoms or an acyl group-having i to 6 carbon atoms or a phenylalkyl group);
Q represents an optionally branched allcyl group having 1 to 6 carbon atoms, an optionally branched alkoxyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group or a nitroso group; m represents an integer of 0 to 3 (when m is 1, Q may be combined with any one of two condensed rings and, when m is 2 or 3, Q may be combined with one or both condensed rings or may be combined together with two condensed rings to form a ring)].
In the present invention, as described above, a coupler (compound represented bythe general formula [III]) is prepared from 2-hydroxynaphthalene-3,6-dicarboxy amide, ureide or carboxylate derivative as a raw material. 2-Hydroxynaphthalene-3,6-dicarboxylic acid as the raw material can be obtained by the Kolbe-Schmitt process of reacting carbon dioxide with potassium 2-naphtholate at high temperature under high pressure in the presence of a potassium salt such as potassium naphtholate, etc.The amide or ureide can be obtained by prepa~ g acid chloride from thionyl chloride in a solvent such as sulfolane according to a usual process and reacting the resulting acid chloride with amines or ureas. Alternatively, it can be obtained by reacting amines or ureas directly with phosphorous trichloride or dicyclohexylcarbodiimide.
The amines or ureas, namely compounds constituting a group X or X' in Y or Y', include optionally substituted aromatic amino compounds such as aniline (X or X' is a phenyl group), ~- or ,B-aminonaphthalene (X or X' is a naphthyl group) and aminoanthraquinone (X or X' is an anthraquinonyl group); optionally substituted CA 02239119 1998-0~-29 heterocyclic compounds having a conjugated double bond, such as aminobenzimidazolone (X or X' is a benzimidazolonyl group), aminocarbazole (X or X' is a carbazolyl group), arninopyridine (X or X' is a pyridyl group), aminothiazole (X or X' is a thiazolyl group), aminobenzothiazole (X or X' is a benzothiazolyl group) and aminoimidazole (X or X' is an imidazolyl group); and aminoindole (X or X' is an indolyl group), aminothiophene (X or X' is a thionyl group), aminophenothiazine (X or X' is a phenothiazinyl group), aminoacridine (X or X' is an acridinyl group) and aminoquinoline (X or X' is a quinolinyl group). The substituent of these compounds includes halogen, nitro group, lower alkyl group, lower alkoxy group, cyano group, phenoxy group, amide group (e.g. phenylaminocarbonyl group, etc.) and these phenoxy group and amide groups include other substituents such as halogen, lower alkyl, lower alkoxy, alkylarrlinosulfonyl, nitrile, etc.
A corresponding urea can be obtained by reacting the above amino compound with a potassium cyanate. Namely, for example, phenyl urea may be obtained from an aniline.
Y and Y' may represent -COR or -COR'. R and R' may be the same or different and represent a hydroxyl group, an optionally branched alkoxy group having 1 to 6, preferably 1 to 4 carbon atoms, particulary a methoxy group, an ethoxy group; a benzyloxy group, a phenoxy group or phenacyloxy group. ~n aromatic ring contained in thesegroups may have a substituent such as halogen atom, lower alkyl group, etc.
The group R2 is a hydrogen atom, an optionally branched alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, particularly a methyl group, an ethyl group; an acyl group having 1 to 6, preferably 1 to 4 carbon atoms, particularly an acetyl group; or a phenylalkyl group. The phenylalkyl group may have a substituent such as halogen atom, lower alkyl group, etc.
The group Q may have a substituent on a naphthalene nucleus, and examples thereof include optionally branched alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, particularly methyl group, ethyl group; optionally branched alkoxy group having 1 to 6, preferably 1 to 4 carbon atoms, particularly methoxy group, ethoxy group; halogen atom, nitro group or nitroso group. The number of the substituent m is normally 0, but may be up to 3. Provided that there is no case of having a substituent at the 1-position of the naphthalene nucleus. Furthermore, when m is 1, Q may be combined with any one of two condensed rings. When m is 2 or 3, Q may be combined with one or both of the CA 02239119 1998-0~-29 condensed rings, or may be combined together with the two condensed rings to form a ring.
The azo compound of the present invention can be obtained by diazotizing aromatic amines represented by the general formula [II] with sodium nitrite, etc., and coupl~ng the resulting diazonium compound with the above 2-hydroxynaphthalene-3,6-dicarboxylic acid and a derivative thereof (e.g. carboxyamide or carboxyureide, or ester thereof).
Furthermore, it can be obtained by forming a lake by using an appropriate metallic salt, e.g. salt of Ca, Ba, Mn, St, etc., when R or R' is a hydroxyl group.
Aromatic amines, namely compounds constituting Z in an azo group, include monoamino condensed polycyclic hydrocarbons such as aniline (Z is a phenyl group), a- or ,~-naphthylamine (Z is a naphthyl grou?), rnonGaminoanthracene (Z is an anthryl group), monoaminoindene (Z is an indenyl group) and monoarninofluolenon (Z is a fluolenyl group);
and monoaminoindole (Z is an indolyl group), monoaminobenzothiophene (Z is a benzothionyl group), monoaminoquinoline (Z is a quinolinyl group) and monoaminocarbazole (Z is a carbazolyl group). These aromatic amines may have a substituent, and examples of the substituent include halogen, lower alkyl (particularly methyl), cyano, nitro, lower allcoxy group, amido group, sulfonyl group, alkylaminosulfonyl group, arninocarbonyl group, phenoxy group, alkoxycarbonyl group, hydroxy group,benzoylamino group, etc.
Most preferred aromatic arnines are optionally substituted anilines (Z is a phenyl group) or optionally substituted a- or ,~-naphthylamines (Z is a naphthyl group).
The process of obtaining a diazonium compound from amines is not specifically limited. A general process of diazotizing aromatic primary amines with sodium nitrite may be used.
The diazonium compound is further coupled with the above-described 2-hydroxynaphthalene-3,6-dicarboxyamide, carboxyureide or an ester thereof, but this method may be a conventional method.
The azo compound of the present invention can be used in a pigment, printing ink, paint, a colorating agent for plastics, etc.
The following Examples further illustrate the present invention in detail hereinafter.
Fx~mple 1 CA 02239119 1998-0~-29 Synthesi~ of ~-hydroxy-~ -meth~l-s~-nitrophenyl~7o)-3~6 bi~phenyl~minoc~rbonyln~hth~lene CH3 HO~_~CONH~
~N--N~ t lV ]
02N ~
CONH~3 As an amine component, 4.6 g of 2-methyl-5-nitroaniline was suspended in 100 g of water and 4.0 g of 35% hydrochloric acid was added to dissolve the amine component.
Then, a solution obtained by dissolving 2.3 g of sodium nitrite in 10 g of water with maintaining at 0~C was added dropwise-to-perform diazotization. On the other hand, as a coupler component, 9.6 g of 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene was suspended in 190 g of methanol and a solution obtained by dissolving 2.0 g of sodium hydroxide in 10 g of water was added to the suspension to dissolve the coupler component and the solution was m~int~ined at 15~C. The coupling reaction was carried out by adding above diazonium solution to this coupler solution over about 20 minutes. Further, after stirring for 30 minutes, 100 g of water was added to the resulting solution to raise the temperature to 70~C and then 600 g of water was added dropwise over about 1 hour.
After cooling slowly to room temperature, the resulting solution was suction-filtrated.
The product was subjected to ultrasonic cleaning and then dried under reduced pressure to obtain 8.2 g of a bright yellowish red powder [2-hydroxy-1-(2'-methyl-5'-nitrophenylazo)-3,6-bisphenylarninocarbonylnaphthalene](melting point ~ decomposition point: 331.2~C
(with decomposition)).
An infrared absorption spectrum (KBr method) is shown in Fig. 1.
Various properties such as water resistance, chemical resistance, solvent resistance, migration resistance and light resistance as a baked paint of the azo compound obtained in Example 1, a 2-hydroxy-3-phenylaminocarbonyl derivative (Comparative Example 1) as a commercially available product and a 2-hydroxy-6-phenylaminocarbonyl derivative (Comparative Example 2) described in Japanese Patent Kokai Publication No. Hei 2-302471 are shown in Table 1.

~. ~ m t m m O ~ ~
- a ~ ~ ~
t, ~

O

O

- .
~3 ~ ~3 ~3 ~ o~ 0~ o~
,;
~3~ ~3~ ~3~
C o o o ~ , , ~'I , ~ D C ~1 , ~ ~ C ~ , ~ ~ C

dulex~ I aldwexa dulo~ z 31dwex~ dulo~

CA 02239119 1998-0~-29 ~ ~ The water resistance, chemical resistance and solvent resistance were evaluated as follows.
Water resistance: 1 Part of a sample was added to 20 parts of water and dispersed by an ultrasonic wave for 20 minutes. After boiling for 1 minute, the resulting solution was cooled and filtrated. Then, the color of the filtrate was observed and evaluated according to the following criteria A to E.
Chemical resist~nce: 1 Part of a sample was added to 20 parts of each 5 % solution of hydrochloric acid or sodium hydroxide and dispersed by an ultrasonic wave for S minutes.
After filtrating, the color of the filtrate was observed and evaluated according to the following criteria A to E.
So]vent resist~nce: 1 Part of a sample was added to 20 parts of acetorle or methanol or xylene and dispersed by an ultrasonic wave for S minutes. After filtrating, the color of the fi~trate was observed and evaluated according to the following criteria A to E.
None coloring is observed. A
Very slight coloring is observed. B
Some coloring is observed. C
Marked coloring is observed. D
Drastic coloring is observed. E
The mi~ration resist~nce was evaluated as follows.
1) To 100 parts of a compound of 100 parts of soft polyvinyl chloride, 50 parts of dioctyl phthalate, 2 parts of tin maleate, 0.4 pans of calcium stearate and 0.6 parts of barium stearate, 1 part of a sample is added, followed by kneading at 140~C for S minutes in a twin-roll mill and further pressurization at 100 kgf/cm2 to obtain a test piece having a thickness of 1 mm.

2) The test piece obtained in the item 1) is cut into pieces of 40 mm x 50 mm in size.

3) 100 Parts of the compound obtained in the item 1) and 5 parts of titanium white are processed in the same manner as in the item 1) and then cut into pieces of 40 mm x 60 mm in size.

4) The test piece of the item 2) is laminated on the sheet of the item 3) and a load is applied so that 100 gflcm2 is obtained.
S) The laminate of the item 4) is allowed to stand at 70~C for 24 hours. The degree of CA 02239119 1998-0~-29 ~ color migration to the titanium white sheet is evaluated according to the following criteria.
None migration: A
Some migration: B
Marked migration: C
Drastic migration: D
The light resistance as baked paint was evaluated as follows.
1) 1.0 Parts of a sample, 0.7 parts of dioctyl phthalate and 0.7 parts of castor oil are kneaded by using a Hoover Muller (100 revolutions x 3 times).
2) To 1.0 parts of the mixture obtained by kneading in the item 1), 10.0 parts of a curing agent Beckosol (ER-3653-60) and 0.1 parts of m~ng~nese naphthenate are added, followed by sufficient kneading on a glass plate by using a spatula.
3) The sample obtained in the item 2) is applied on a steel plate in a thickness of 0.5 mil (1.27 x 10-5 m), followed by heating at 145~C for 30 minutes using an air dryer to obtain a test piece of baked paint.
4) A half of the piece of the item 3) is masked and exposed to light for 100 hours using a weathermeter (manufactured by Shimad~u Corp.: Suntester XF-180 ~ xenon lamp). The masked portion and non-masked portion are measured, respectively, and evaluation is performed by a color difference ~ E hetween them.
E = not more than 2 A
~E=2to3 B
~E=3toS C
~E=Sto8 D
~ E = not less than 8 E

Fx~mple 7-Synthesi~ of 7-hy~lroxy-1-(7-'-methyl-S'-nitrophenyl~7O)-3,6-bi~(7'-methylphenyl~minoc~rboT~vl)n~,rhth~lene CA 02239119 1998-0~-29 CH3 HO CONH~
~N=N~ [ V ]
O2N ~ H3C
CONH~
According to the same manner as described in Example 1 except for replacing 2-hydroxy-3,6-bispherylaln-llocarbonylnaphthalene of Example 1 by 14.3 g of 2-hydroxy-3,6-bis(2'-methylphenylaminocarbonyl)naphthalene as a coupler component, 9.2 g of anyellowish red powder [2-hydroxy-1-(2'-methyl-5'-nitrophenylazo)-3,6-bis(2'-methylphenylaminocarbonyl)naphthalene] was obtained (melting point ~ decomposition point: 307.0~C (with decomposition).

Fx~mple 3 Synthesi~ of ~-hy(lroxy-l-(~'-methyl-5'-nitrophenyl~7O)-3,6-bi~
methoxylphe"yl~ " ,i~o~rbonyl)naphthalene CH3 HO CONH~
~N=N~ [ VI ]
O2N ~ H3CO~
CONH~
According to the same manner as described in Example 1 except for replacing 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene of Example 1 by 15.1 g of 2-hydroxy-3,6-bis(2'-methoxyphenylaminocarbonyl)naphthalene as a coupler component, 9.4 g of a bluish red powder [2-hydroxy-1-(2'-methyl-5'-nitrophenylazo)-3,6-bis(2'-methoxyphenylaminocarbonyl)naphthalene] was obtained (melting point ~ decomposition point: 293.5~C (with decomposition).

CA 02239119 1998-0~-29 Fx~mple 4 Synthesi~ of 2-hydroxy-1-(?~-methoxy-s~-phenyl~minocarborlylphenyl~70)-3~6 bi~henyl~minoc~rbonyln~hth~lene OCH3 HO~ CONH~

. ~HNOC ~ tVII]
CONH~

According to the same manner as described in Example 1 except for replacing 2-methyl-S-nitroaniline of Example 1 by 7.3 g of 2-methoxy-5-phenylaminocarbonylaniline as an amine component and dispersing it ~ 50 g of water and 50 g of methanol, 6-.8 g of a bluish red powder [2-hydroxy-1-(2'-methoxy-5'-phenylaminocarbonylphenyl~o)-3,6-bisphenylaminocarbonylnaphthalene] was obtained (melting point ~ decomposition point:
282.5~C (with decomposition).

Fx~mples S to 2~
According to the same manner as described in Example 1 except for replacing 2-methyl-5-nitroaniline of Example 1 by an amine shown in Table 2 as an amine component and dis~e, ~ing it in 50 g of water and 50 g of methanol, and replacing 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene by a coupler shown in Table 2 as a coupler component, ~o compounds were synthesized. The melting point ~ decomposition point of synthesized ~o compounds are shown in Table 2.

Table 2 E~ample Amine (upper) / Color Melting point/
No. Coupler (lower) Structural formula of azo compound shade d~ lposition point 2-methoxy-5-phenylamino- [ X V m ~ NO2 carbonylaniline ~ --N=N ~
2-hydroxy-3,6- ~ Bright 294.2-C
~ HNOC ~ ~/ ,NO2 bluish red (wit~
bis~-mtropneny aminocarbonyl)- CONH
naphthalene 2-methoxy-5-phenylamino-carbonylaniline [X I X] H3CO
OCR3 HO CONH ~
____ ___________ '~=~=/--N=N ~ SO2NEt2 6 2-hydroxy-3i6- ~ OC ~ H3CO (Et= C2Hs) bluishred 312.7-C
aminosulfonyl-2'- CONH ~ ~ ~
methoxyphenyl- SO2NEt2 aminocarbonyl)-naphthalene 2-methoxy-5-phenylamino-carbonylanilLne [ X X ~ OCHb HO CONH
~ =N
__ ____ ______ , 7 2-hydroxy-3,6- ~IOC ~ Bright 325.4-C
bis(1'-naphthyl- \=/ CONH ~ ~ bluish red aminocarbonyl)-naphthalene 2-methoxy-5-phenylamino- [X X I ] H
carbollylaniline ~ 3 H ~ CONH ~ ~ ~N?

~ _____---------------------- 6~ /
8 3,6-bis(benz- ~NOC ~ Dark 354.1-C
imidazolon-5-yl- ~ \=o red all~local~onyl)-2- b~J~N/
hydroxy- H
naphthalene Table 2 (continued) mplc Amine(upper)/ Color Meltingpoint/
No. Coupler (lower) Strudural formula of azo ~,--~u.. d shade de~.... p~ ion point 2-methoxy-5-phenylarnino- t X O
carbonylaniline X II ] OCH3 HO\ CONH~,~J~
~N=N~ b~J~J
9 2-hydroxy-3,6-bis- ~NOC Q~ O Dark 324.6-C
rr.~m 11 bluish red (~ilh d r (anthraqumon-2- ~,vnn~
ylaminocarbonyl)- b~
naphthalene O

2-methoxy-carbonylaniline [ X X m ]
~NO2 H3 COOC Ho\ CONH~
lo 2-hydroxy-3 6- ~N=N~ Brownish 357.1-C
)= red (~ith bis(3'-nitrophenyl- ~, ~02 arninocarbonyl)-naphthalene COI~
2-methoxy-carbonylaniline [XX I V] H3CO
H3 COOC HO CONH~Ol~
11 2-hydroxy-3,6-bis- \J N=N~ OCH3 Brownish319.2-C
(2',5'-dimethoxy-4'- - ~ ( H3 CO orange(with melting) phenylamino- CONH--~CONH~
carbonyl-phenyl- ~=~
aln,llocall,ollyl)- OCH3 naphthalene 2-methoxy-carbonylaniline H3COOC HOxCONH--\ ~
12 2-hydroxy-3,6-~N--N~ Bri~ht288.6-C
~ yellowish ~with melting) bls(4'-phenoxy- ~ red phenylamino-[ X X V ] CONH~3 carl,ollyl)-naphthalene Table 2 (continued) r~ample Amine (upper) / . Color Melting point/
No. Coupler (lower) Structural formula of azo compound shade decomposition point 2-methoxy-carbonylaniline H3~ H~C0NH~ ?

13 3,6-bis(benz- [ X X V I ] Q~ Brown 341 0;C
Lmidazolon-5-yl- CON~
arninocarbonyl)-2- ~'N/
hydroxy-~ naphthalene 2-methoxy-5-diethylamino- ~~[ X X Y II ]
sulfonylaniline ~OCH3 HO~CONI~
/=rN=N //~
4 2-hydroxy-3,6- / ~( Yello~ish305.8 C
bisphenylar ~ino- Et2NO2S ~ red (~ithmelting) carbonyl- (Et= C2~s) COh~
naphthalene 2-methoxy-5-diethylamino- H3C
sulfonylaniline[ X X V m ] ~~
~oc~ ~o CO~OC~
2-hydroxy-3,6- \/~X~ C1 Bluish 304.1-C
bis(5'-chloro-2',4'-EtzNO2S ~ H3CO~ red(with melting) dimethoxy- (Et= C~s) COh~OCH3 phenylamino- \Cl carbonyl)-naphthalene 4-chloro-2-methylaniline [ X X I X ]
CH3 HO~CO~
_ _ _ _ .Cl~N=N~ ~
16 2-hydroxy-3,6- ~ Dark 278.0 C
bisphenylamino- ~ red (with melting) carbonyl- CON~
naphthalene Table 2 (conttnued) Exa~nplc Amine (upper) / Color Melling point/
No. Coupler (lower) Strudural formula of azo compound shade decomposition point 4-chloro-2-methylaniline [ X X X ] EtO
CH3 HO CONH--b 17 2-hydroxy-3,6- Cl~N=N~ Yellowisb 266.6~C
bis(2'-ethoxy- Q~ EtO\ r (with melting) phenylaminO- CONH~
carbonyl)-naphthalene 4-chloro-2-methoxylaniline H
OCH3 HO CONH~,~, Cl~N=N~ H
18 3,6-bis(benz- ~ ~ Dark 328.9-C
imidazolon-S-yl- [X X X I ] CONH~ ,D bluishred (with aminocarbonyl)-2- ~ >=o IIY~Y~ H
naphthalene 2-methyl-5-nitroaniline CH~ H
_ _ _ __ ~ ~CONH~,N~

19 3,6-bis(benz- 02N ~ Dark 334.6-C
imidazolon-S-yl- [ X X X II ] CONH~ ~NH\ brownish (with aminocarbonyl)-2- ~ /=o hydroxy- H
naphthalene 2-methyl-5-nitroaniline IXXXm] Cl CH3 HO~COh'HCONH~
2-hydroxy-3,6- ~N--N~=~ Bright 239.4-C
bis(2'-chloro- 02N y Cl~ brdownish (with phenylureido- CoNHcoNH~
carbonyl)-naphthalene Table 2 (continued) Example Arnine (uppet) / Color Melting pointt ~~ Coupler (lower) Structural forrnula of azo w~ ~ul~d shade d~""~ ion point 4-chloro-2-methoxyaniline [X X X I V] Cl ~OCH, HO~CONHCONH~
- - - - - - - - - - - - - - - -21 2-hydroxy-3,6-bis- C1~=~N=N~=~ Dark 260.2'C
(2'-chloro- ~ Cl\ purple (With d~ _ r phenylureido- CON~UU,.. ~
carbonyl)- \=/
naphthalene 2,5-dichloro-aniline [X X X V] Cl ~Cl HO CONHCONH~
--N-N--~
22 2-hydroxy-3,6-bis-\=/ )=( Brownish 231.5-C
(2'-chloro- Cl ~ Cl red (with ~ ph~ lu- ~;do- . CON~CONH~
carbonyl)-naphthalene CA 02239119 1998-0~-29 Fx~mp]e ?~
~ ;ynthesic of calcium salt of 2-hydroxy-3~6-dihy(1roxycarbonyl-l-(4l-methsulfo- phenyl~7o)-n~phth~lene H3C~N=N~ ~ 3/2 Ca2+ [ VIII ]

COO-5.0 g of 4-aminotoluene-3-sulfonic acid (4B-Acid) was dispersed in 250 g of water and 5.4 g of 35% hydrochloric acid was added to dissolve. Then, diazotization was carried out by adding dropwise the solution, obtained by dissolving 2.1 g of sodium nitrite in 10 g of water with maintaining at 0~C, over about 20 minutes. On the other hand, 6.4 g of 2-hydroxy-3,6-dihydroxycarbonylnaphthalene was suspended in 200 g of N-methyl-2-pyrrolidone and 200 g of water and 38.5 g of 10% sodium hydroxide solution, and then 24.0 g of 5% rosin solution were added. After dissolving them, the solution was m~int~ined at 13 (+2) ~C. To this solution, the diazonium solution described above was added dropwise over about 30 minutes and the solution was further stirred for 90 minutes.
After adjusting the pH of the reaction solution to 9.0 to 9.5, this solution was added dropwise to the solution obtained by dissolving 6.7 g of calcium chloride dihydrate in 125 g of water to form a lake. After 30 minutes, the temperature was raised to 70~C. The resulting solution was allowed to stand for about 30 minutes and then cooled slowly to room temperature. Thereafter, 200 g of water was added to the solution, followed by suction filtration. The product was washed with water and then dried to obtain 10.3 g of a deep red powder [calcium salt of 2-hydroxy-3,6-dihydroxycarbonyl-1-(4'-methyl-2'-sulfo-phenylazo)naphthalene (melting point ~ decomposition point: 406.1~C (with decomposition)).
An infrared absorption spectrum (KBr method) is shown in Fig. 2.

CA 02239119 1998-0~-29 Fx~mrle74 Synthesi~ of a calcium salt of 1-(s~-chloro-4l-me~hy~ -sulfo-pher~yl~7o)-2 hydroxy-3,6-dihy(1roxycarbonyl-naphth~lene Cl HO COO~
H3C~N=N~ ~ 3/2 Ca2+ [ IX ]
03S ~
COO' According to the same manner as described in Example 23 except for replacing 4-arninotoluene-3-sulfonic acid (4B-Acid) of Example 23 by 5.9 g of 4-amino-2-chlorotoluene-5-sulfonic acid (2B-Acid), 11.3 g of a deep red powder [calcium salt of 1-(S'-chloro-4'-methyl-2'-sulfo-phenylazo)-2-hydroxy-3,6-dihydroxycarbonylnaphthalene]
was obtained (melting point ~ decomposition point: 446.7~C (with decomposition).

Fx~mple 2~
(1) Synthesi~ of ~-hydroxy-3,6-bi~(~'-pyridyl~minocarbonyl)naphthalene HO~CONH~
[X]
N
CONH~3 14.3 g of 2-hydroxy-3,6-dihydroxycarbonylnaphthalene and 13.6 g of 2-aminopyridine were dissolved in 120 g of N-methyl-2-pyrrolidone, and 150 g of ethyl acetate and then 30.9 g of dicyclohexylcarbodiilnide were added to this solution and the reaction was performed at room temperature for about 15 hours. After insolub]e matters were removed by filtration, the filtrate was concentrated to about half of the weight, and then 30.6 g of diglyme was added and the temperature is raised to 170~C. After 2 hours, the solution was cooled to room temperature and insoluble matters were rernoved by filtration. The filtrate was concentrated and 200 g of ethyl acetate was added, and then the crystal deposited after an ultrasonic treatment was filtered. The product was dried to obtain 15.7 g of an yellowish white crystal [2-hydroxy-3,6-bis(2'-CA 02239119 1998-0~-29 pyridy]aminocarbonyl)naphthalene] (melting point: 311.2~C).
(2) Synthesi~ of ~-hydroxy-l-(s~-diethyl~minosulfonyl-2~-methoxyphenyl~7o) 3,6-bis(~'-pyridyl~minocarbonyl)-n~phth~lene OCH3 Ho~CoNH~.3 ~N=N~ [ XI ]
Et2NO2S ~ N
CONH~3 According to the same manner as described in Example 1 except for replacing 2-methyl-5-nitroaniline of Example 1 by 7.8 g of 5-diethy]aminosulfonyl-2-methoxyaniline as an amine component and d;spersing it in 50 g of water and 50 g of methanol, and replacing 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene by 9.6 g of 2-hydroxy-3,6-bis(2'-pyridylaminocarbonyl)naphthalene synthesi_ed in above (1) as a coupler component, 7.1 g of an brownish red product [2-hydroxy-1-(5'-diethylaminosulfonyl-2'-methoxyphenyl~o)-3,6-bis(2'-pyridylarninocarbonyl)-naphthalene] was obtained (melting point ~ decomposition point: 197.6~C (with decomposition)).

Fx~mple ~6 Synthesi~ of 2-hy(lroxy-3,6-bis(thia7Ol-~-'-ylaminocarbonyl)naphth~lene Ho~CONH~9 [ XII ]

CONH~9 In 50.0 g of N-methyl-2-pyrrolidone and 30.0 g of toluene, 6.3 g of 2-aminothiazole was dissolved and heated to 60~C. To this solution, a solution obtained by dissolving 5.6 g of 2-hydroxy-3,6-bischlorocarbonylnaphthalene in 120.0 g of N-methyl-2-pyrrolidone was added and the temperature was raised to 80~C. After about 24 hours, the solution was concentrated and 470 g of water was added. The deposited crystal was filtered, washed with methanol and then dried to obtain 1.7 g of a flesh color crystal [2-hydroxy-3,6-bis(thia~ol-2'-ylarninocarbonyl)naphthaleneJ (melting point: 286.6~C).

CA 02239119 1998-0~-29 Fx~n~r]e '~7 (1) Synthesi~ of '~-hy~lroxy-3,6-bis(ben7~ thi~7nl-~'-yl~minocarbonyl)narhth~lene H ONH~
O~C [ XIII ]

CONH~S~
According to the same manner as described in Example 26 except for replacing 2-aminothiazole of Example 26 by 9.4 g of 2-aminoben_othiazole, 1.9 g of a flesh color crystal [2-hydroxy-3,6-bis(ben_othia7ol-2'-ylaminocarbonyl)naphthalene] was obtained (melting point: 364.1~C).
(2) Srthesi~ of ~-hyllroxy-1-(7-~-methoxy-s~-phenylaminoc~rbonylphenyl)~
3,6-bi~(ben7,othi~7nl-'~,"-yl~minocarbonyl)n~phth~lene ~ONI~

~NO CON1~33 As an amino component, 1.46 g of 2-methoxy-5-phenylaminocarbonylaniline was dispersed in 20 g of water and 1.8 g of 35% hydrochloric acid is added. Then, the solution prepared by dissolving 0.84 g of sodium nitrite in 5 g of water with maintaining at the temperature of 0~C was added dropwise to the dispersion solution to perform diazoti7ation.
Then, 4 g of boro~uoric acid was added and a deposited diazonium salt was filtered.
On the other hand, as a coupler component, 1.19 g of 2-hydroxy-3,6-bis(benzothiazol-2'-ylaminocarbonyl)naphthalene was dissolved in 20 g of N-methyl-2-pyrrolidone and 0.25 g of sodium methoxide was added. After dissolving, the solution was m~int~ined at the temperature of 15~C. The coupling reaction was carried out by adding the solution, prepared by dissolving the diazonium salt described above in 15 g of N-methyl-2-pyrrolidone, to this solution over about 20 minutes. After stirring for 1 hour or more, 0.22 g of acetic acid was added and then 50 g of methanol was slowly added.

The product was obtained by suction filtration, washed with methanol using an ultrasonic wave, and then dried under reduced pressure to obtain 1.17 g of a dark red powder [2-hydroxy-1-(2'-methoxy-5'-phenylarmnocarbonylphenyl)azo-3,6-bis(ben_othiazol-2"-ylaminocarbonyl)naphthalene] (melting point ~ decomposition point: 316.3~C (withdecomposition)).

Fx~mple ~8 (1) Synthesis of ~-hydroxy-3,6-bis(4', S'-dicyanoimi~1~7ol-~ylaminocarbonyl)n~phthalene CN
HO~ ~CONH~CN
[XIV]
N~
CoNH~N~cN

According to the same manner as described in Example 26 except for replacing 2-arninothiazole of Example 26 by 8.3 g of 2-amino-4,5-dicyanoimidazole, 3.5 g of a flesh color crystal [2-hydroxy-3,6-bis(4',5'-dicyanoimidazol-2'-ylaminocarbonyl)-naphthalene]
was obtained (melting point: 256.8~C).
(2) Synthesi~ of ~-hvdroxy-1-(~-'-methoxy-5'-phenylaminocarbonylphenyl)a70-3,6-bi~(4", 5"-dicyanoimi~70l-2"-ylaminocarbonyl)naphthalene ~C~N ~ )~
0~ ~ N
ONH~
H--CN
According to the same manner as described in Example 27(2) except for replacing 2-hydroxy-3,6-bis(benzothiazol-2'-ylaminocarbonyl)naphthalene of Example 27(2) by 1.49 g of 2-hydroxy-3,6-bis(4',5'-dicyanoimidazol-2'-ylaminocarbonyl)naphthalene as a coupler component, 0.83 g of a dark red powder [2-hydroxy-1-(~'-methoxy-5'-phenylaminocarbonylphenyl)azo-3,6-bis(4",5"-dicyanoimidazol-2"-ylaminocarbonyl)naph~halene] was obtained (melting point ~ decomposition point: 320.6~C

CA 02239119 1998-0~-29 (with decomposition)).

Fx~mples ~9 to 73 According to the same manner as described in Example 23 except for replacing 4-aminotoluene-3-sulfonic acid of Example 23 by the amines shown in Table 3 as an amine component, and replacing 2-hydroxy-3,6-dihydroxycarbonylnaphthalene by the couplers shown in Table 3 as a coupler component, and exch~nging the usage of calcium chloride dihydrate into 1.1 to 1.2-fold equivalent weight, azo compounds were synthesized. In Examples 40, 41 and 42, barium chloride, strontium chloride, manganese chloride were used respectively in place of calcium chloride in Example 23. The melting point and decomposition point of the resulting azo compounds are shown in Table 3.

Table 3 Example Arnine (upper) / Color Melting point/
No. Coupler (lower) Structural formula of azo cnmpsl-nd shade dc~ ition point aniline H OO
29 2-hydroxy-3,6-di- N=N ~ Ca Yellowtsh 363.9;C
hy~ll o~ycarbonyl-naphthalene coo ~ aniline H~ &~~

2-1ly~llù~y-3- N= ~ ln Ca+~ Yellowish 529.1 C
l~y ito~ycarbonyl- CONH~ red (with~

6-phenylamino-Iy~
~ naphthalene aniline H OO
_______________ ~ N= ~
31 2-lly~llu~y-3- ~ H~CQ~ 1n Ca+~ BrdoWnish 518 5 C
6-(5'-chloro-2',4'- CON ~ OCH~
dimethoxyphenyl- a ~min- c~rbonyl)- - -naphthalene 4-ar ~inotoluene-3-sulfonic acid ~O, H~ ,COO
32 2-hydroxy-3,6-di- H,C~N=~ 3Q Ca~ Reddish 352.3-C
hyllto~ycarbonyl- ~ purple (withd~ ,, n:~ ) naphthalene coo 4-arninotoluene-3 -sulfûnic acid ~SO~ H~ &~~
33 ----___________.H~C ~ N--N-- Q C-~+ Reddish 395.2-C
y~lt~ yC~ 0llyl- ~ purple (wtth~' , i0 ) 6-phenylarnino- CONlt carbonyl-naphthalene Table 3 (continued) E~arnplc Arnine (upper) / Color Melting point/
No. Coupler (lower) Structural formula of azo ~mpounrl shade dco~,.. position point 4-aminotoluene-3-sulfonic acid ,SO, H~ ,COO
_--------------- H,C~N~
34 2-hydloxy-3- )~ C ~+ Reddish 467.9-C
6-(5'-chloro-2',4'- ~ H~o purple (with dirnethoxyphenyl-aminocarbonyl)-naphthalene 4-aminotoluene-3 -sulfonic acid ~ 0~ H~ &~~
2-hyd~oxy-3- H3C~ Ca~ Reddish 462.7-Cy~lloxycall~onyl- CON~ o2 purple (~i~
~(3'-nitro-phenyl-. aminocarbonyl)-naphthalene 4-aminotoluene-3 -sulfonic acid ~S~3 H~&~~
36 2-hydroxy-3- - . H3c~N=N Q - Ca+~ Darkred 462.7-C
hy~l~oxycall1onyl- ~ (~ith~
6-(4'-nitrophenyl- CoN~3No2 aminocarbonyl)-naphthalene 4-anunotoluene-3 -sulfonic acid ~ ~, H~SCON~
___------------ H~ N~ ca+t Bluish 458.5-C
nurnle (~;th ~a; ~
~ ltu~yc~lrbonyl- ~. r r 3-phenylamino- coo~
C~I~OIlyl- - -naphthalene 4-aminotoluene-3 -sulfonic acid - -H~CC~

SO~ Ht~ CON~H, 38 2-11y~oxy-6- H~C~3N=N~ Cl Ca~+ Bluish 447.2-C
hydroxycarbonyl- ~ red (~ilh d~ L) 3-(5'-chloro-2',4'- ~coo~
dime~hoxyphenyl-aminocarbonyl)-naphthalene ~ Table 3 (continued) P~amplc Arrtine (upper) I Color Melting point/
No. Coupler (lower) Slrudural formula of azo enmro~ tl shade dec~".?~ition poinl 4-aminotoluene-3-sulfonie acid ~~2 ~SO3 H~ ~CONH-O
39 2-hydroxy-6-H3C~N=N--Q Ca+~ Orange 446.5-C
hytl~o~yca.l1onyl- y (With~ A)3-(3'-nitrophenyl- coo~
arninoearbonyl)-naphthalene 4-aminotoluene-3-sulfonie acid NOi ,so, H~ &ONH~
402-hydroxy-6- H3C~N=N~ Ba~ Bluish 447.0-C
lly~ yCdll~onyl- ~ red (with 3-(3'-nitrophenyl- . coo~
aminoearbonyl)-- naphthalene 4-aminotoluene-3-sulfonic acid ~ - - - -,NO2 ,SO~ H~ jCONH-O
41 2-hydroxy-6- H3C~N~ sr~ Bluish 462.2-C
lly lto~ycarbonyl- Q red (with~ . .. l~.- .. ~ ) 3-(3'-nitrophenyl- coo~
aminocarbonyl)-naphthalene 4-aminotoluene-3 -sulfonie acid N~2.
42 2-hy-droxy-6- H3C~N=~ONH-O Mn~ Dark 428.7-C
hy~ ycalbonyl- ~ bluishred (with~
3-(3'-nitrophenyl- coo~
aminocarbonyl)-naphthalene 4-aminotoluene-3 -sulfonie acid ,50~ Hq~ &ONH~No2 43 2-hydroxy-6- H3C{S~Q Ca~ Dark red 465.6-C
hy~lto~ycalbonyl- ~ ? (with i~ r ~'- ) 3-(4'-nitrophenyl- 'coo~
aminocarbonyl)-naphthalene Table 3 (continued) Examplc Arnine (upper) / Color Melting point/
~~ Coupler (lower) Structural formula of azo ~mrou~ld shade deco".l,o6ition point 4-aminotoluene-3-sulfonic acid ._ c O~ HQ CONH~
44 2-hydroxy-6- H~C{~ NO2 Ca+~ red (wtth d~
hydroxycarbonyl- r, r 3-(2'-chloro-5'- ~coo~
nitrophenyl-aminocarbonyl)-naphthalene 4-arninotoluene-3-sulfonic acid H~
_______________. 03 HQ CONH
2-hydroxy-6- H~C~S NO2 Ca~+ Yellowish 4ss.8 C
lly~lt~xy~all~ony~s red (with ~
3-(2'-methyl-5'- ~
nitrophenyl- coo~
aminocarbonyl)-naphthalene 4-amino-2-chloro~oluene-S-sulfonic acidso, H~COO-46 2-hydrox-y-3,6-di- H~C5}~ 3/2 Ca+~ Belduish 437.2 C
ytll ~ yt~ll~onyl- - O~
naphthalene 4-amino-2-chlorotoluene-S -sulfonic acid ,~so, H~COO-47 2-hydroxy-3- H~C~ Ca~+ red (With hydl o~ycarbonyl-6-phenylarnino- ~ONH~
carbonyl-naphthalene 4-amino-2-chlorotoluene-S -sulfonic acid ,~so, HQ~COO----------------- H~C~ ~N-N~
48 2-hydroxY-3- cl ~ H~CQ~ red (~ith ~ D) hydroxycarbonyl- ~ ,ONh~CH, dirnethoxyphenyl-arninocarbonyl)-naphthalene Table 3 (continued) mple Amine (upper) / Color Melting poinl/
No. Coupler (lower) Structural formula of azo compound shade ~ ition point 4-amino-2-chlorotoluene-5 - - -sulfonic acid ,~;03, H~OO-49 2-hydroxy-3- H,C;~N,~ ~2 Ca~+ rBeldUiSh 462.2 C

lly~lto~c.ycarbonyl- CON~
6-(3'-nitrophenyl-~minr)c~rbonyl)- - -naphthalene 4-amino-2-chlorotoluene-5-sulfonic acid ~iio3 HQ~CONH~
2-hydroxy-6- H3C;~ Ca~ Bluish 478.8 C
hyllloxycarbonyl- c ~ -~
3-phenyl- ~~
~mimx~rbonyl-naphthalene 4-amino-2-chlorotoluene-5-sulfonic acid .H3CQ
______. ,S03 HQ CONH~OCH~
51 2-hydroxy-6- H3C~ Cl C red s29.2;C
Ity~lo~ycarbonyl- cl ~
3-(5'-chloro-2',4'- ~ oo~
dimethoxyphenyl-aminocarbonyl)-naphthalene 4-amino-2-chlorotoluene-S-sulfonic acid ~No2 ,SO~ HQ ,~ONH~
_______________. ,~ l s2 2-hydroxy-6- H3C~ ~ _ ~ Ca~+ Darkh d (wlthd .. ~; ~;u.. ) hy~llo~y~rbonyl- a ~
3-(3'-nitrophenyl- 'coo~
~minoc~rbonyl)-naphthalene S-arnino-2-chlorotoluene-4-sulfonic acid ~so, WQ~COO-53 2-hydroxy-3,6-di- ~ 3/2 Ca+~ Dark 422.s C
hydroxycarbonyl- oo brownish (~ilh d ~ ~L~
naphthalene Table 3 (eontinued) Example Arnine (upper) / Color Melting point/
No. Coupler(lower) Structural formulaof azocompound shade dc~"")o~ition point 5-amino-2-chlorotoluene-4-sulfonie acid ,so, H4 COO~
c~5 54 2-hydroxy-3- H~C O Ca rBelduish 488.s C
hydroxyearbonyl- ~CONH-O
6-phenylarnino-carbonyl-naphthalene 5-arnino-2-chlorotoluene-4-sulfonie acid ,50~ HC~ &~~
~ , ,~
2-hy~oxy-3- c~ Dark 46s.9 C
hydlo~ycarbonyl- H3C ~ H3CQ~ Ca bluish red (Wilhd -6-(5 -ehloro-2 ,4 - CONH~OCH~
dimethox-yphenyl- ~u aminoearbonyl)-naphthalene S-arnino-2-chlorotoluene-4-sulfonicacid ,503 H~ ~COO~
~~~~~~~~~~~~~--- CI~N~
56 2-hydlla~y-3- ~=/ ~ Ca~+ Dark 513.7-C
hy~ito~yc~lbonyl- H3C ~ ~~2 bluish red (with 6-(3'- CONH~
nitrophenylarnino-earbonyl)-naphthalene S-arnino-2-chlorotoluene-4-sulfonie acid _ 5~3 H~ &
--------------- Cl~ ~N--~, +~
57 2-hy~lt o~y-6- y ~ Ca Bluish 480.0-C
hydlo~ycarbonyl- H~C ~ red (w 3-phenylamino- coo~
earbonyl-naphthalene 5-arnino-2-chlorotoluene-4-sulfonic acid H3C~
,SO~ H~ ,CONH~OCH~
58 2-hydroxy-6- Cl~--N=N~ '=SCI ca~ Bluish 461.8-C
hydroxycarbonyl- H3~/ ~ red (~ith ~ ") dimethoxyphenyl- ~~
aminocarbonyl)-naphthalene Table 3 (continued) Examplc Arnine (upper) / Color Melting point/
No. Coupler (lower) Structural forrnula of azo ~.. I~uu~d shade d~""~ition point S-amino-2-chlorotoluene-4-sulfonlc acid ,~o, Hq~. ~CONH~
_______________. ~ ~ +~
59 2-hydroxy-6- -CI~N--_~ Ca Bluish 465.3-C
- H3C ~C red (Witb I . ~-3-(3'-nitrophenyl- ~~
~min~x~rbonyl)-naphthalene 2-arnino-1- _ _ naphthalene-sulfonic acid ~;o3 H~&oo-2-hydroxy-3,6-di- ~ 3R Ca+~ Reddish 438.3-Chydloxy~ arbonyl- coo~ purple (with ~' r ' ) ~ naphthalene 2-a_ino-1-naphthalene-sulfonic acid ~;o3 HC~ &~~-,~ ~
61 2-hydroxy-3- W =~ Ca~+ Dark 474.5-C
tOxyCarbOrlyl- CONH O ptlurpleh (With d~
6-phenylam no-carbonyl-naphthalene 2-amino-1-naphthalene- _ _ - -sulfonic acid 0,H~ &~~-62 2-hydroxy-3- ~ ~ H- Dark 486.7-C
hydloxy-;arbonyl- ~ H,C~, ca Bluish (~i 6-(5'-chloro-2',4'- CON11~CICH, purple dimethoxyphenyl- _ c ,tminnc~rbonyl)-naphthalene 2-amino-1-naphthalene-sulfonicacid ~o~H~&oo~
63 2-hydroxy-3- ~ ~2 ca Dark 564.9-C
hytlt oxycarbonyl- CON~ pBuurpsleh (with~ ~ ai~ ~) 6-(3 '-nitrophenyl-aminocarbonyl)-- Table 3 (continued) Example Amine (upper) / Color Melting point/
No. Coupler (lower) Structural formula of azo ~rn~lnd shade dcc~,.. ~ition point 2-arnino-1-naphthalene- - -sulfonic acid o3 Hq_&~NH-O
64 2-hydroxy-6- ~ ca~ pDuarrpkle 507.1-C
hydroxycarbonyl- ~
3-phenylarnino- ~~~
carbonyl-naphthalene 2-arnino-1-naphthalene-sulfonic acid H~
2-hydroxy-6- ~o3 H~&ONll~ocH~ H Dark 530.6-C
O~ ~ I ca purple (With d n_ ) hyd,u~ycarbonyl-3-(5'-chloro-2',4'- ~
dimethoxyphenyl- coo ~min-)c~rbonyl)-naphthalene 2-arnino-1-naphthalene-sulfonic acid NO2 ,SO3 H~ &ONH~
66 2-hydroxy-6- ~--N=N-A ' ca~+ Dark 471.9-C ~W =( reddish (with d-hy l oxycarbonyl- , _~ purple 3-(3'-nitrophenyl- coo~
arninocarbonyl)-naphthalene 2-nitroaniline-4-sulfonic acid J~~2 H~ &~~
____ __________.03S{~N~ ~2 Ca+~
67 2-hydroxy-3,6-di- ~ ~ Dark 547.5-C
~ bluish red (with a~
hy~ltoxycall~onyl- ~oo~
naphthalene 2-nitroaniline-4-sulfonic acid )'1~2 H~ ~:OO
68 2-hydroxy-3- 03S~ ca~ Yellowish 453.8-C
- CONH-O re~t (with d~-6-phenylarnino-carbonyl-naphthalene Table 3 (continued) Example Arrtine (upper) / Color Melting point/
No. Coupler (lower) Stru~ural formula of azo compound shade decomposilion point 2-r~itroaniline-4-sulfonic acid ~~2 HQ~coo--03S~
69 2-hydroxy-3- r H3C .Ca+~ Brownish435.7-C
llytLI)xy-,arbonyl- ~_ ,ON~C red(with A~- y ~y ~-;yll)6-(5'-chloro-2',4'- ~c ~lim~1h aminocarbonyl-naphthalene 2-nitroaniline-4-sulfonic acid J~02 H~ ,COo~
2-hydroxy-3- 03S~ N~2 red (with ~ A) ~ytltu~yCarbûnyl- ONH~S
6-(3'-nitrophenyl-a-m-inocall)ollyl) naphthalene 2-nitroarliline-4-sulfonic acid ,NO2 HQ CONI~O
71 2-hydroxy-6- ~N=N~ . Cat+ srowrtish 450.1~C
hy~lloxy~arbonyl- y red (with~ ~
3-phenylarnino- . oo carbonyl-naphthalene 2-nitroaniline-4-sulfonic acid - _ H3C~
_______________, J~~2 H~ ~CONH~OCH~ -72 2-hydroxy-6- -03S~N~ ~i Ca~+ Dark 434.9-C
hytlloxyc~lbonyl- ~ . brownish (with.l.. v~ .. ,;Ar.
3-(5'-chloro-2',4'- ~ _ re dirnethoxyphenyl- _ coo arntnocarbonyl) naphthalene 2-nitroaniline-4-sulfonic acid ,No2 ,NO2 HC~ ~CONH~

73 2-hydroxy-6- o3S{~Q red (with A - v~
hydroxycarbonyl- ~ ~
3-(3 '- ~c nitrophenylamino- ~~
carbonyl)-naphthalene -Fxperiment Fx:lmple With respect to azo compounds obtained in Examples 39, 54 and 64, each printing ink was prepared according to JIS K5101 and a color is extended. The color data are shown in Table 4. As the color data, the dominant wavelength (Ad), the excitation purity (pe) and the brightness (Y) defined in JIS Z8701 are shown.

Table 4 Dominant wavelengthExcitation purity Brightness A d (nm) Pc (%) Y (%) Example 39 610 58.1 14.5 Example 54 619 47.6 8.5 Example 64 645 32.2 6.8 Fx~mple 74 Synthesi~ of ~-hy(lroxy-~ -methoxy-s~-phenyl~minocarbonylphenyl)~7o-3 methoxy~rbonyl-6-(3"-nitrophenyl)aminocarbonylnaphthalene ,OCH3 H~ &OOCH3 N-N
~NOC - CON:~

According to the same manner as described in Example 27(2) except for replacing 2-hydroxy-3,6-bis(ben~othia_ol-2'-ylaminocarbonyl)naphthalene of Example 27(2) by 1.10 g of 2-hydroxy-3-methoxycarbonyl-6-(3'-nitrophenyl)aminocarbonylnaphthalene as acoupler component, 1.44 g of a red powder [2-hydroxy-1-(2'-methoxy-5'-phenylaminocarbonylphenyl)a_o-3-methoxycarbonyl-6-(3"-nitrophenyl)aminocarbonylnaphthalene] was obtained (melting point ~ decomposition point: 315.8~C (with decomposition)).

CA 02239119 1998-0~-29 Fx~mple 75 Synthesi~ of ?-hy(lroxy-~ methoxy-s~-phenyl~rninocarbonylr)henyl)~7o-3 methoxyc~rbonyl-6-ben7,yl0xycarbonylnaphth~lene ~CH3 H~&OOCH~

~NOC
OOCH~

According to the same manner as described in Example 27(2) except for replacing 2-hydroxy-3,6-bis(ben_othia7ol-2'-ylaminocarbonyl)naphthalene of Example 27(2) by 1.01 g of 2-hydroxy-3-methoxycarbonyl-6-ben_yloxycarbonylnaphthalene as a coupler component, 1.42 g of a red powder [2-hydroxy-1-(2'-methoxy-5'-phenylaminocarbonylphenyl)azo-3-methoxycarbonyl-6-ben_yloxycarbonylnaphthalene] was obtained (melting point ~ decomposition point: 332.6~C (with decomposition)).

Fx~mple 76 Synthesi~ of ~-hydroxy-1 -(2'-methoxy-5'-phenylaminocarbonylphenvl)~o-3,6-bi~(phenoxycarbonyl)naphthalene OCH, H
N~
~HNOC co~

According to the same manner as described in Example 27(2) except for replacing 2-hydroxy-3,6-bis(ben_othiazol-2'-ylaminocarbonyl)naphthalene of Example 27(2) by 1.15 g of 2-hydroxy-3,6-bis(phenoxycarbonyl)naphthalene as a coupler component, 1.23 g of a red powder [2-hydroxy-1-(2'-methoxy-5'-phenylaminocarbonylphenyl)azo-3,6-bis(phenoxycarbonyl)naphthalene] was obtained (melting point ~ ~decomposition point:
328.8~C (with decomposition)).

CA 02239119 1998-0~-29 Fx~mple 77 Synthesi~ of ~-methoxy~ 2'-methoxy-S'-phenyl~minocarbonylrhenyl)~7o-3-(ben7imid~7,010n-S"-ylaminocarbonyl)-6-phenyl~minocarbonylnarhthalene H, H3C N

~HNOC ~/
oNH~3 According to the same manner as described in Example 27(2) except for replacing 2-hydroxy-3,6-bis(benzothia_ol-2'-ylaminocarbonyl)naphthalene of Example 27(2) by 0.95 g of 2-methoxy-3-(ben_imidazolon-5"-ylaminocarbonyl)-6-phenylaminocarbonylnaphthalene as a coupler component, and ch~nging the stirring time to 100 hours or more, 0.41 g of a dark subdued red powder [2-methoxy-1-(2'-methoxy-5'-phenylaminocarbonylphenyl)a_o-3-(benziinidazolon-5"-yl)-6-phellylalllinocarbonylnaphthalene] was obtained (melting point ~ decomposition point:
314.3~C (with decomposition)).

Fx~mple 78 Synthesi~ of 7-methoxy-1-(4'-nitrophenyl~7O)-3-(ben7imi(1~7olon-5"-ylaminocarbonyl)-6-phenyl~minocarbonyln~rhthalene H3CQ ,CONH~
02N~N=N~

CONH~

According to the same manner as described in Example 77 except for replacing 2-methoxy-s-phenylar~ ocarbonylaniline of Example 77 by 0.42 g of 4-nitroaniline as an amine component, 1.12 g of a bluish red powder [2-methoxy-1-(4'-nitrophenylazo)-3-(benzimidazolon-5"-yl)-6-phenylaminocarbonylnaphthalene] was obtained (melting point -decomposition point: 323.3~C (with decomposition)).
The azo compound of the present invention is characterized by having two CA 02239119 1998-0~-29 carboxyl groups (which may form a salt), carboxyamides, carboxyureides or esters at the 3-and 6-positions of 2-hydroxynaphthalene as a coupler. The coloring material obtained from the compound shows higher solvent resistance, water resistance and chemicalresistance in comparison with the case of using a coupler having these groups in other positions of 2-hydroxynaphthalene, or the case of having one carboxyamide, carboxyureide or ester.

BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows an infrared absorption spectrum of the azo compound of Example l; and Fgure 2 shows an infiared absorption spectrum of the calcium salt of the azo compound of Example 23, respectively.

Claims (9)

1. An azo compound represented by the following general formula [I]:

[wherein Y represents -(CONH)n-X or -COR;
Y' represents -(CONH)n-X' or -COR';
(X and X' may be the same or different and represent an optionally substituted aromatic group, or an optionally substituted heterocyclic group having a conjugated double bond);
R and R' may be the same or different and represent a hydroxyl group, an optionally branched alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a phenyloxy group or a phenacyloxy group (provided that an acceptable salt may be formed when any one of R and R' is a hydroxyl group);
n represents an integer of 1 or 2;
R2 represents a hydrogen atom, an optionally branched alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or a phenylalkyl group;
Q represents an optionally branched alkyl group having 1 to 6 carbon atoms, an optionally branched alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group or a nitroso group; m represents an integer of 0 to 3 (when m is 1, Q may be combined with any one of two condensed rings and, when m is 2 or 3, Q may be combined with one or both condensed rings or may be combined together with two condensed rings to form a ring); and Z represents an optionally substituted monovalent aromatic group].

2. The azo compound according to claim 1, wherein Y is -(CONH)n-X, and Y' is -(CONH)n-X' (n, X and X' are defined as above).

3. The azo compound according to claim 1, wherein Z is a phenyl group or a naphthyl group.

4. A pigment comprising the azo compound of claim 1.

5. A printing ink comprising the azo compound of claim 1.

6. A coating composition comprising the azo compound of claim 1.

7. A colorating agent for plastics, comprising the azo compound of claim 1.

8. A process for producing the azo compound of claim 1, which comprises diazotizing an aromatic amine represented by the following general formula [II]:
Z-NH2 [II]
[wherein Z represents an optionally substituted monovalent aromatic group] and coupling the resulting diazonium compound with a compound represented by the following formula [III]:

[wherein Y represents -(CONH)n-X or -COR;
Y' represents -(CONH)n-X' or -COR';
(X and X' may be the same or different and represent an optionally substituted aromatic group, or an optionally substituted heterocyclic group having a conjugated double bond);
R and R' may be the same or different and represent a hydroxyl group, an optionally branched alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a phenyloxy group or a phenacyloxy group;
n represents an integer of 1 or 2; and R2 represents a hydrogen atom, an optionally branched alkyl group having 1 to 6 carbon atoms or an acyl group having 1 to 6 carbon atoms or a phenylalkyl group; and Q represents an optionally branched alkyl group having 1 to 6 carbon atoms, an optionally branched alkoxyl group having 1 to 6 carbon atoms, a halogen atom, a nitro group or a nitroso group; m represents an integer of 0 to 3 (when m is 1, Q may be combined with any one of two condensed rings and, when m is 2 or 3, Q may be combined with one or both condensed rings or may be combined together with two condensed rings to form a ring)] (provided that a lake may be formed by using a desired metallic salt, when R
or R' is a hydroxyl group.).

9. The process according to the claim 9, wherein Z is a phenyl group or naphthyl group.