CA2241099C - Bisazo compounds and process for the preparation thereof - Google Patents

Abstract

The invention provides novel bisazo compounds obtained by coupling two 2-hydroxynaphthalene-3,6-dicarboxylic acid derivatives and a compound having two diazo groups, as well as a process for producing the same. The present compounds are superior in resistance to water, chemical agents, solvents, heat and the like.

Description

BISAZO COMPOUNDS AND PROCESS FOR THE
f'REPAI~,ATION 7~HEIZEOF
Technical Field The present invention relates to a novel bisazo compound and a process for producing the same.
Background of the Art Azo compounds are useful as dyes, pigments, carrier generation materials and the like, and a large number of such ccnnpounds have been provided for many years.
Particularly in recent years, many compounds suitable for use as c:>rganic photoconductors (OPC) have been developed. For example, a highly sensitive and highly durable carrier generation material which uses a hydroxynaphthalenedicarboxyimide as a coupler has been proposed in Japanese Patent Publication No. !~5-2 >45:~0 A. ~1'he inaide proposed in tihis Patent Publication is 2-hydroxynaphthalene-4,5-dicarboxyirnide.
Disclosure of the Invention The feature of the present invention is to provide a bisazo-coloring material which is superior in resistance to water, chemical agents, solvents, heat and the like.
The present invention provides a novel bisazo compound which has two azo groups in its molecule and which uses a 2-hydroxynaphthalene-3,6-dicarboxylic acid, ester, amide, or ureide derivative as a coupler, as well as a coloring material comprising the same, and a method for producing said bisazo compounds. Thus, the present invention provides a bisazo compound represented by the follawing general formula (IJ:
A-N=N-E-N= N-A' (I ) (wherein, A and A' may be the same or different, and represent the following general formula (III:
RIO Y
[I(~
_(Q)m Ye (wherein, Y is -(CONH)n-X or -COR, Y' is -(CONH)n-X' or -COR', and 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), n represents an integer of 1 or 2, R and R' may be the same or different, and represent a hydroxy group, an optionally branched alkoxy group having 1-6 carbon atoms, a benzyloxy group, a phenoxy group, or a phenacyloxy group, RZ represents a hydrogen atom, an optionally branched alkyl group having 1-6 carbon atoms, an acyl group haW ng 1-6 carbon atoms or a phenylalkyl group;
Q represents an optionally branched alkyl group having 1-6 carbon atoms, an optionally branched alkoxy group having 1-6 carbon atoms, a halogen atom, a vitro group or a nitroso group, and m represents an integer from 0 to 3, and when one of R and R' represents a hydroxy group, it may optionally form an acceptable salt;
E represents a cyclic group having a conjugated double bond, as well as a coloring material comprising said bisazo compound. In this specification, the term "coloring material" refers to dyes, pigments, inks, paints, printing inks, carrier generation materials and the like.
The present invention further relates to a process for producing said bisazo compound in which process a compound represented by the general formula (VIA:
HEN-E-NH2 (VIj (wherein, E represents a cyclic group having a conjugated double bond is diazotized, and the bisdiazonium compound so obtained is coupled with a compound represented by the general formula (VII]:

/ \
Q )m [~j \ /
Y' [wherein, Y is -(CONH)n-X or -COR, Y' is -(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 hydroxy group, an optionally branched alkoxy group having 1-6 carbon atoms, a beclLyloxy group, a phenoxy group, or a phenacyloxy group, n represents an integer of 1 or ~, RZ represents a hydrogen atcm, an optionally branched alkyl group having 1-6 carbon atoms, an acyl group having 1-6 carbon atoms or a phenylalkyl group;
Q represents an optionally branched alkyl group having 1-6 carbon atoms, an optionally branched alkoxy group having 1-6 carbon atoms, a halogen atom, a nitro group or a nitroso group, and m represents an integer from 0 to 3 j.
Furthermore, this bisazo compound may optionally form a lake using a metal compound, when at least one of R and R' is a hydroxy group.
As described above, a coupler in the invea~tion (a group represented by the general formula [II) or a compound repr<aented by [VIII) is prepared from 2-hydroxynaphthalene-3,6-dicarboxamide, carbonylurea or carboxylic acid derivative as a raw material. The raw material, 2-hydroxynaphthalene-:3,6-dicarboxylic acid may tae obtauied by the Kolbe-Schmitt method of reacting carbon dioxide with potassium 2-naphtholate under a high pressure and at a high temperature in the presence of a potassium salt such as potassium phenolate.
The amide or ureide may be obtained by preparing an acid chloride according to a conventional method, for example, using ihionyl chloride in a solvent such as sulfolane, and by reacting it with amines or areas. Alternatively, the same may also be obtained by directly reacting with amines or areas using phosphorous triehloride or dicyclohexylcarbo diimide.
Examples of the amines or areas, that is, a compound which constitutes X or X' in Y and Y', include an optionally substituted aromatic amino compound such as aniline (X or X' is a phenyl group), a- or ~-aminonaphthalene (X or X' is a naphthyl group), or aminoanthraquinone (X or X' is an anthraquinonyl group), and an optionally substituted heterocyclic compound having a conjugated double bond such as aminobenzimidazolone (X
or X' is a benzimidazolonyl group), aminocarbazole (X or X' is a carbazolyl group), aminopyridine (X or X' is a pyridyl group), aminothiazole (X or X' is a thiazolyl group), aminobenzothiazole (X or X' is a benzotluazolyl group), or aminoimidazole (X
or X' is an imidazolyl group) as well as aminoindole (X or X' is an indolyl group), aminothiophene (X
or X' is a thiofuryl group,), arrrir~ophenothiazine (X or ;~' is a phenothia~:inyl group), aminoacridine (X or X' is an acridinyl group), and aminoquinoline (X or X' is a quinolinyl group). Examples of substituents on these compounds are a halogen atom, a vitro group, a lower alkyl group, a cyano group, a phenoxy group, an amide group (for example, a phenylaminocarbonyl group) and the like, and these phenyl and amide groups may also have another substituent such as a halogen atom, a lower alkyl, lower alkoxy, alkylaminosulfonyl, nitrite group or the like.
The amino compound df;scribed above may be reacaed with potassium cyanate to obtain a corresponding urea. Thus, for example, phenylurea may be obtained from aniline.
Y and Y' may also represent -COR or -CC7R°. R amd R' maybe the same or different, and represent a hydroxy group, an optionally branched alkoxy group having 1-6, preferably 1-4 carbon atoms, in particular, a methoxy group or an ethoxy group; or a benzyloxy, phenoxy or phenacyloxy group. An aromatic ring contained in these groups may optionally be substituted by, for example, a halogen atom, a lower alkyl group or the like.
The group RZ is a hydrogen atom, an optionally branched alkyl group having 1-6, preferably 1-4, carbon atoms, in particular, a methyl group car an ethyl group; an acyl group having 1-6, preferably 1.-4 carbon atoms, in particular, an acetyl group; or a phenylalkyl group. The phenylalkyl group may optionally be substituted by a halogen atom, a lower alkyl group or the like.
The group Q means that the naphthalene nucleus may optionally be substituted, and examples of Q are an optionally branched alkyl group having 1-&, preferably 1-4 carbon atoms, in particular, a methyl group or an ethyl group; an optionally branched alkoxy group having 1-6, preferably 1-4 carbon atoms,'in particular, a rnethoxy graup or an ethoxy group;

and a halogen atom, a vitro group, or a nitroso group. A.Ithough the number of the substituent m is typically 0, it may be 3 or less. Provided that there is no case of having a substituent at the 1-position of the naphthalene nucleus.
The bisazo compound of the present invention may be obtained by diazotizing a diamine compound represented ry the gc°neral formula [VI) with sodium nitrite, etc., and coupling the resulting bisdiazoniurn compound with the above-described 2-hydroxynaphthalene-3,6-dicarboxylic acid, ester, amide or ureide.
In addition, when R or R' is a hydroxy group, the compound may optionally form a lake by means of an appropriate metal salt, for example, a salt of Ca, Ba, Mn, or St.
The diamine, that is, a compound which constitutes E, is a compound having two amino groups directly bonded to a cyclic group having a conjugated double bond, and the cyclic group may optionally have a substituent(s) such as a halogen atom, a lower alkyl, alkoxy, cyano, vitro, sulfo group or the like. A typical amine which may be used in preparing a bisazo compound of the invention is a diamine comprising an arylene group, or a basic skeleton represented by the general formula (II1] or (V);
-Ar-M-Ar'- [ I I I ]
[wherein, Ar and Ar' each independently represent an optionally substituted aryl or heterocyclic group having a conjugated double bond, M represents a group selected from a group consisting of a single band, -CHI-, -CH=C(E~- (in which E' is a hydrogen atom or a halogen atom, or a lower alkyl group, a cyano group or the like), -O-~, -S-, -S-S-, -CO-, -COO-, -SOZ-, -N(T)- (in which T is an optionally substituted phenyl group or a lower alkyl group), -N=N-, -CH=CH-c~-CH=:C:H- in which ~ is an arylene group, and a formula (IV):
N-~N
C.wJ
(in which G represents -O-, -S- or -NH-));
,L
w ( (vJ
s (wherein, L represents >N-CH3, :>C=O, car >C=S).
Specific examples of these diamines are as follows:
(1) a group of arylenedianunes may include, for example, an optionally substituted phenylenediamine, naphthylenediamine, or anthrylenediamine, (2) a group ot~H~N-Ar-M-Ar"-NHS may include, for example, when M is a single bond, H2N--~ \ / \ NH
z / \
H .~ ~~-NHz zN S
N / \
H N ~'' ! ~~.-f-NH2 H2N 1 1N~N / \ NHz N
when M is -CHZ-, H2N~~CH2 / ~ NHz when M is -CH=C(E~-, H2N~~CH=CH / \ NH2 HzN / \ CH=CH / \
NHz HzN / \ CH=C / \ NHz CN
H2N / \ CH=L /.~..\ NHz CN
\ /

~N
H2N ~ ~ C=CH ~ ~ NH2 O
CN
H2N ~ ~ C=CH ~ ~ NH2 N
H
when M is -O-, -S-, -S-S-, -COO-, -SOZ-, -N(T)- or -N=N-, H2N ~ ~ S ~ ~ NH2 H2N ~ ~ S-S ~ ~ NH2 H2N ~ ~ C ~ ~ NH2 O
H2N ~ I C ~ I NH2 O

H2N ~ ~ N ~ ~ NH2 H2N ~ ~ N ~ ~ NH2 HZN ~ ~ N=N ~ ~ NH2 when M is -CH=CH-~-CH=CH-, H2N / \ CH=CH ~. I CH=CH / \ NHz / \
H2N / \ CH=CH ~ CH=CH / \ NHz and when M is represented by the formula [IVY, H N f \ -~~~~ ! \ NHz O
N-N
HzN / \ ( I / \ NHz S
and (3) a group of those diamines having the basic skeleton work represented by the general formula (V~ may include, for example, O
H2N ~ I ~ l NHz ti H;~
HzN- 1. I N \ I NHa The method for obtaining a bisdiazonium compound from diamines is not especially restricted. A standard method in which an aromatic primary amine is diazotized with sodium nitrite may be used.
The process in which the bisdiazoniurn compound is further subjected to a coupling reaction using a 2-hydroxynaphthalene-3,b-dicarboxylic acid, ester, amide or ureide described above may also be achieved by conventional methods.
The bisazo compounds of the invention may be used in pigments, printing inks, paints, coloring agent for plastics, organic photoconducters and the like.
The invention will be explained by the following examples.

a Racamnle 11 ~"ynthes~of 1,4-bi~~?~'-h~rdroxv-'~',6'- dinhen~laminocarbonyllLaphth-1'-ylazc~ben7ene / \ HNOC OH HO CONH / \
\ N=N / \ N=N / \
\ / \ /
/ \ HNOC CONH / \
In SO g of water, 1.08 g of 1,4-phenylenediamine was suspended, and then -dissolved by adding 3.0 g of 35% hydrochloric acid. Diazotization was then conducted by adding dropwise a solution of 2.1 g of sodium nitrite dissolved in 10 g of water, while maintaining the temperature at 0°C. On the other hand, 11.5 g of 2-hydroxy-3,6-diphenylaminocarbonylnaphthalene was suspended in 230 g of N-methyl-2-pyrrolidone, dissolved by adding a solution of 1.6 g of sodium hydroxide dissolved in 10 g of water, and then maintained at 15°C. To this solution, the above diazo solution was added over about 20 minutes to conduct a coupling reaction. After stirring for additional 30 minutes, 200 g of water was added, brought to 70°C, and 800 g of water was added dropwise over about one hour. Then, the reaction mixture was gradually cooled, and filtered at room temperature with aspirating. The product was ultrasonically washed in methanol and dried under a reduced pressure to obtain 5.1 g of a dark reddish purple powder (1,4-bis(2'-hydroxy-3',6'-diphenylaminocarbonylnaphth-1'-ylazo)benzene) (melting/decomposition point: 348.0°C (decomposition)).
An IR spectrum of this compound (KBr method) is shown in Fig. 1.
F:~ca~
S~rnthesis of 1,4-bis~~ ro -3'~6'-di~2"-chlor~henyla inocarbony~l naghth-1'-,~a_z~ben~ene CI
HO CONH ~
N ~
CI
CONH ~
According to the same manner as desciribed in Example 1 with the exception that 13.5 g of 2-hydroxy-3,6-di(2'-chlorophenylaminocarbonyl)naphthalene was substituted for 2-hydroxy-3,6-diphenylaminocarbonylnaphthalene in Example 1, 6.3 g of a dark bluish purple powder [1,4-bis{2'-hydroxy-3',6'-di(2"-chlorophenylaminocarbonyl)naphth-1'-ylazo}benzene~ was obtained (melting/decomposition point: 262.3°C
(decomposition)).
Ex-a~ lie 3 8vnthesis of 1,4-bis{2'-h~,rdroxv-3',6_ '~difr "-nit onhenylaminocarbonyll,n~phth-1'-ylazolbenzene NH

NH
According to the same manner as described in Example 1 with the exception that 14.2 g of 2-hydroxy-3,6-di(3'-nitrophenylaminocarbonyl)naphthalene was substituted for 2-hydroxy-3,6-diphenylaminocarbonylnaphthalene in Example 1, 6.8 g of a dark bluish purple powder [1,4-bis{2'-hydroxy-3',6'-di(3"-nitrophenylaminocarbonyl)naphth-1'-ylazo}benzene) was obtained (melting/decomposition point: 283.9°C (decomposition)).
~vnthesis of 1,4-bid(?~vdroxy-3'~6'-dinhenylaminocarbon~~ tnh h-1'-;1~~1-2-H
H
v According to the same manner as described in Example 1 with the exception that 2.4 g of 2-chloro-1,4-phenylenediamine sulfate was substituted for 1,4-phenylenediamine in Example 1, 4.7g of a deep bluish purple powder (1,4-bis(2'-hydroxy-3',6'-diphenylaminocarbonylnaphth-1'-ylazo)-2-chlorobenzene~ was obtained (melting/decomposition point: 255.7°C (decomposition)).

Cl CI
HNOC Ol NH /!~' / \ _ CI ~ j> CI

According to the same manner as described in Example 1 with the exception that 2.4 g of 2-chloro-1,4-phenylenediamine sulfate was substituted for 1,4-phenylenediamine in Example 1, and 13.5 g of 2-hydraxy-3,6-di(2'-chlorophenylaminocarbonyl)naphthalene was substituted for 2-hydroxy-3,b~-diphenyiaminocarbonylnalahthalene, '~.4g of a dark bluish purple powder [1,4-bis{2'-hydroxy-3',b'-di(2"-chloraphenylarninocarbonyl)naphth-1'-ylazo}-2-chlorobenzene~ was obtained (melting/decompasition point:
285.0°C
(decomposition)).
A spectral property of this compound is shown in Fig. 2.

Th1 Measurement apparatus: Macbeth Spectrophotometer CE-7000 System (Macbeth).
Method of measurement: a polyvinyl chloride) molding for evaluation, obtained according to the method described in "Preparation of PVC sheet", one of the evaluation methods for bisazo compounds described in the Experiments section, was used to examine spectral property.
It is observed that the absorption wavelength has been red-shifted to around 670 nm, suggesting an application of this compound to organic photoconducting materials or the like.
02N NOz / \ HNOC OH CI HO CONH /_ / \ N=N / \ N=N- / \
02N \ l \ ~" NO2 J
/ \ HNOC CONH ~ \
According to the same rnanner as described in Example 1 with the exception that 2.4 g of 2-chloro-1,4-phenylenediamine sulfate was substituted for 1,4-phenylenediamine in Example 1, and 14.2 g of 2-hydroxy-3,6-di(3'-nitrophenylaminocarbonyl)naphthalene was substituted for 2-hydroxy-3,f~-diphenylaminocarbonylnaphthalene, 5.0 g of a dark bluish purple powder [1,4-bis~2'-hydroxy-3',6'-di(3"-nitrophenylaminocarbonyl)naphth-1'-ylazo}-2-chlorobenzene~ was obtained (naelting/decomposit:ion point:
2'92.3°C
(decomposition)).
E~~n In a 7 ;rnthesis of biSl4 l~'-h~droxv-3'.6'~di.~,~vlamyocarbo~yl~r~hr th-1'-; ll 370).nhenvllmethane HNOC OH HO CONH
N=N ~ ~ CH2 ~ ~ N=N
w ~i HNOC CONH
According to the same manner as described in Example 1 with the exception that 2.0 g of bis(4-aminophenyl)methane was substituted for 1,4-phenylenediamine in Example 1, 5.7 g of a dark bluish red powder [bis{4-(2'-hydroxy-3',6'-diphenylaminocarbonylnaphth-1'-ylazo)phenyl}methane) was obtained (melting/decomposition point:
204.5°C
(decomposition)).
The spectral property of this compound is shown in I~ig. 3. The spectral property was measured according to the same procedure as described in Exarr.~ple 5. It is observed that the absorption wavelength htis been red-shifted tc> around 5$0-6$0 nm, suggesting an application of this compound to organic photoconducting materials or the like.
F~
HNOC~ OH ~ ~ HO,'~ ONH
HNOC CONH
According to the same manner as described in Example ~ w :ith the exception that 2.0'g of bis(4-aminophenyl) ether was substituted for 1,4-phenylenediamine in Example 1, 4.4g of a dark bluish red powder (bis{4-(2'-hydroxy-3',6'-cliphenylaminocarbonylnaphth-1'-ylazo)phenyl} ether) was obtained (melting/decomposition point: 297.5°C
(decomposition)).

~;tnthesis of bis{~2'-hvdroxy-3',6'-di enylaminocarbon,~lnanhth-1'~ l~h~n~}
sulfone NH
NH
According to the same manner as described in Example 1 with the exception that 2.5 g of bis(4-aminophenyl) sulfone was substituted for 1,4-phenylenediamine in Example 1, 6.7 g of a dark bluish red powder [bis{4-(2'-hydroxy-3',6'-diphenylaminocarbonylnaphth-1'-ylazo)phenyl} sulfone~ was obtained (melting/decomposition point:
298.5°C
(decomposition)).
Synthesis of 1,4-bis{3',~'-diybenzimidazolon -5"-Ylaminocarbon~~ydroxvtlanhth-1'-H
NH ~ N
~I ~O
N
H
H
N H ~ N
O~ \ I \ I N O
H H
According ~o the~ame manner as described in_ E_x_a__m__pl_e i wJth the excepti_o_n_ t_h_a_t 14.8 g of 3,6-di(benzimidazolon-5'-ylaminocarbonyl)-2-hydroxynaphthalene synthesized according to Japanese Patent Application No. 96-530874 was substituted for 2-hydroxy-3,6-diphenylaminocarbonylnaphthalene in Example 1, 7.9 g of a dark bluish purple powder (1,4-bis{3',6'-di(benzimidazolon-5"-ylaminocarbonyl)-2'-hydroxynaphth-1'-ylazo)-benzene was obtained (melting/decomposition point: 284.1°C (decomposition)).

EXp~rim~nts T'he bisazo compound obtained in Example 10 was used to evaluate its resistance to water, chemical agents, solvents, light, heat, and migration, and the results obtained are shown in Table 1.
Table 1 Bisazo Color Water-ResistanceSolvent-resistanceL.aghtlastnessThermostabilityResistaace to compound rtsistaoachemica) acetone/ metbanol/xylene to agent/
S%

HCI migration - ~.._~..r_. --.

Bisam Dull . .

compoundreddish A A A A A A A A
of Examplepurple Method for evaluation (Water-resistance]
One g of the sample is added to 20 g of water, and dispersed by sonicating for minutes. After boiling for one minute, the mixture is cooled, filtered, and the filtrate is observed.
No coloring is observed at all A
Very slightly colored B
Slightly colored C
Colored D
Remarkably colored E
(Resistance to solvents and chemical agents]
One g of the sample is added to 20 g of a test liquid t'~, and dispersed by sonicating for S minutes. After filtration, the filtrate is observed.
~l~ Test liquid: acetone, methanol, xylene, S~.~o aqueous HCI.
No coloring is observed at all A
Very slightly colored B
Slightly colored G
Colored D
Remarkably colored E
7Pr~. aratio of PVC sheet for evaluation One part of the sample is added to 100 parts of a compound consisting of 100 parts of PVC, 50 parts of dioctyl phthalate, 2 parts of tin maleate, U.4 parts of calcium stearate, and 0.6 parts of barium stearate, mixed for 5 minutes at 1~U°C by means of a two-roll mixer, and then compressed at 100 kgflcm2 to obtain a 1 mm thick PVC test sheet.
[Lightfastness]
1) The above-described PVC. test sheet for evaluation is cut into 35 mm x 110 mm sheets.
2) A half of a test sheet of 1) is masked, and irradiated in a weather-omelet (K.K.
'f M
SHIMADZU SEISAKUSHO ; Suntester XF-180/xenon lamp) for 100 hours. Both of the masked and unmasked areas were colorimetrically measured, and the lightfastness was evaluated on the basis of its DE, the color difference between the two areas.
DE<2 A
DE=2-3 B
D E=3-5 C
OE=5-8 U
DE>8 E
[Thermostability]
1) The above-described PVC test sheet for evaluation is cut into 30 mm x 30 mm sheets.
2) A test sheet of 1) is left in a thermostatic chamber at 170°C for 60 minutes.
The test sheet was then colorimearically measured t~elc>re and after th.e heat-treatment, and the thermostability was evaluated on the basis of the color difference, OE
before and after the heat-treatment.
L~E<2 A
DE=2-3 B
DE=3-5 C
OE=5-8 D
hE>8 E
[Resistance to migration]
1) The above-described PVC test sheet for evaluation is cut into 40 mm x 50 mm sheets.

2) A hundred parts of the compound used in the above section and 5 parts of titanium white are processed as above, and cut into 40 mm x 60 mm sheets.
3) The sheet of 2) is layered onto the sheet of 1) with a side of one sheet being matched with a side of another sheet, and loaded with weighted at 100 gf/cm2.
4) 3) is left at 70°C for 24 hours. The resistance to migration was evaluated on the basis of the degree to which the migration into the titanium white sheet has occurred.
No transfer A
Slightly transferred B
Transferred C
Considerably transferred D

synthesis ~f 1,4-bis{2'-h_ dry-_3',6'-~~ "-ch Qrp~ henvlu_reidocarbon;
llnanhth-1'-CI CI
HNOCHNOC OH HO CONHCONH / \
/ \ N~N / \ N~N / \
CI \ / \ f Ci HNOCHNOC CONHCONH ~ \
According to the same manner as described in Example 1 with the exception that 16.2 g of 2-hydroxy-3,6-di(2'-chlorophenylureidocarbonyl) naphthalene was substituted for 2-hydroxy-3,6-diphenylaminocarbonylnaphthalene in Example l, 7.1 g of a dark bluish purple powder [1,4-bis{2'-hydroxy-3',6'-di(2"-chlorophenylureido-carbonyl)naphth-1'-ylazo}benzene~ was obtained (melting/decomposition point: 220.3°C
(decomposition)).
' ~ ' ' " ' lazo -2-/ N HNO HO G:,ONH ~ \
=N / \
\ /
/ N HNO CONH N \
According to the same manner as described in Example 1 with the exception that 2.4 g of 2-chloro-1,4-phenylenediamine sulfate was substituted for 1,4-phenylenediamine in Example l, and 11.5 g of 2-hydroxy-3,6-cli(2'-pyridylaminocarbonyl )naphthalene synthesized according to Japanese Patent Application No. 96-269985 was used, 4.7 g of a deep bluish purple powder [1,4-bis{2'-hydroxy-3',6'-di(2'-pyridylaminocarbonyl)naphth-1'-ylazo}-2-chlorobenzene) was obtained (melting/decomposition point:
266.4°C
(decomposition)).

, , ,.
,~~ILPSl~ Of 2.
~-HN H H ONti-\ ~ N=N i O t'~ /
\ / ~ '~ \ /
~--HNOC c;ON
In 20 g of water, 1.23 g of 2,7-diamino-9-fluorenone was suspended, and dissolved by adding 1.S g of 3S% hydrochloric acid. Diazotization way then conducted by adding dropwise a solution of 0.73 g of sodium nitrite dissolved in 5 g of water, while maintaining the temperature at 0°C. Then, 4 g of 42°lcl ffuoroboric acid was added, and the bisdiazonium salt precipitated was filtered. On the other hand, 3.82 g of 2-hydroxy-3,6-bis(phenylaminocarbonyl)naphthalene was dissolved in 80 g of N-methyl-2-pyrrolidone, followed by adding O.S 7 g of sodium mc;thoxide, dissolved, and then maintained at LS°C.
To this solution, a solution of the above tetrazolium salt dissolved in 20 g of N-methyl-2-pyrrolidone was added over about 20 minutes to conduct a coupling reaction.
After stirring for one additional hour, 0.8 g of acetic acid was added, and then 1S0 g of methanol was slowly added. The product was isolated by filtration with aspirating, ultrasonically washed in water and methanol, <p,nd dried under a reduced pressure to obtain 3.4 g of a dark bluish purple powder (2,7-bis(2'-hydroxy-3',6'-diphenylaminocarbonylnaphth-1'-ylazo)-9-ffuorenone~ (melting/decomposition poin t: 333.6°C (decomposition)).
Fxam 1 1 - .
.,,. , ., , , One part of the azo compound obtained in Example 13 was dispersed with one part '1'M
of a polyvinyl butyral) (Sekisui Chemical Co., S-LEC BH-3) and 10 parts of cyclohexanone by means of a ball mill. This dispersed azo compound was applied onto an aluminum plate using a bar coate:r, and then dried. At this stage, the thickness of the film was about 0.5 pm. Onto the carrier generation layer so obtained, a solution consisting of one part of N-ethylcarbazole-3-aldehyde diphenylhydrazone and one part of a Thi polycarbonate resin (TEIJIN Chemicals Co., Panlite K-1285) dissolved in 20 parts of 1,2-dichloroethar_e was applied so that, when dried, a 20 Nm thick film would be obtained to form an carrier transport layer. 1n this way, an electrophotosensitive material consisting of two layers was obtained.
A half exposure (Er,z) as a sensitivity of a photosensitive material was measured for the above photosensitive material by means of an electrostatic copy paper tester (Kawaguchi Denki Seisakusho Model EPA-8100). The material was firstly electribed by corona discharge at -5.0 kV in a dark place , and then exposed to white light at an illumination of 20 tuxes in order to determine the amount of exposure required to decrease the surface potential to the half of the initial value.
The half exposure (Ern) so determined was 2.3 lux~sec. The surface potential after sufficient exposure (residual potential) (after exposed to 200 lux~sec) was -1 V.
Fxa les 1~4-38 According to the same manner as described in Example 13 with the exception that as diamine components, amines shown below Table 2 were substituted for 2,7-diamino-9-fluorenone in Example 13, and as coupler components, couplers shown below Table 2 were substituted for 2-hydroxy-3,6-bis(phenylanunocarbonyl)naphthalene, azo compounds were synthesized. Melting/decomposition points of the synthesized azo compounds are shown in Table 2.
Furthermore, photosensitive materials were prepared as in Example 13-2 with the exception that each of the azo compounds synthesized in Examples 17, 20, 22, 23, 28, 32 and 33 was used instead of the azo compound used in Example 13-2, and their sensitivities (half exposure Ern) were determined. The determined E,EZ and residual potentials are shown in Table 2.

..
U
id C .
a G N
Ca U V U
00 °
vs o O q M M M
U
.d ~' _y~ 'H N
O ~ '~ "~
b ~' 'b N p w ø, w P..
N N

I I i ~I i I
p ~ Z Z
O O / I .~ OU
I _ _~

r I

z o i ~i I
z z = 'z z i w w i ~ w I ~ w I
z z o z z z = ~.
I I ~I

V
d U
'.cuss '~~. 00 N
iG ~ b N N ~ ~
~~ O
G w Ca O

o, b M ~V
'b w 'N d . N "OJ' .ta O
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. r. O. P.. O .O O.
U r I U
x x I I O ~ ~ CSC
U U i I
Z Z O O
O O U
I I O ~ O
U
T II I
a. .~ Z . /
T
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'°
o Z
Z O
I
id '~ Z
I
x ~"'n z / I \ .- ,.. I
/ U

z z z x Z S ~U U
/ I / I. _ = z ~ I ~ I
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I
y t~ oo v, as o ,~ .... .1 ~z U
H
N ~ cV ~ ~i 'y~ o b .N U U U

00 tn M
N N
.b M M
'UO
v, "p N N H U
~b U .l U / I.
r I z z w I ci.i \ I U~ U O O
Z Z Z Z
0 0 ~ r ~ o a o \ U
o I ~ \ /
Z = Z
z / \ / / \
w \ / \
U
z Jz T =
r r I. \ I r I ._ C~~U
Z Z .Z Z Z
U
I ~~ / I - \ I _ T
\ I \ I
b b c~
a>
N n., N N N

v as ~,r o0 W 7C ~ b a cV ~ N
C w sa U U U

ov N N
o _q _N H _a~ ~ ~ _a>
'8 r3' -3 ~' o ~~ ~' .b ~" c~ -c .fl R. ro. ~. o O O
\ ~ ~ ~ LLl Z
O O O pZ O O
U
C Z
p S Z

v \ ~ \ ~ \
w w O
,o / ~
/
\ ' / \ I / O
V v v~
O Z
Z
O Z Z Z rir 1 1=
.._.
\~ \~ \
O .
C
c~
c~
a~
N p, M ~t N N

U
m ~ ~N.. O~
X ~ .o a ~v~ o C w a y U U U
00 0, n o p N N N
b _O .~ ~ .~ 'v a) . ~' N O~ ~' ~f ~ b ~"
a. v. O c. sØ ~ 40.. R.
r U Z U Z r ~ r UO
U
Z
O
U r \ O O O
U
a ~ ~ ~~
\i r O Z~Z
w.
~.

Z
in O r O ~~ \
r I U
o z .I V Z .Z
O r r \
a N p, N N N

M
~ . ~ ~' ci5. ~ .b a~
~~ ., U U U

ONO OHO O
A N N M
b ~ _~ _N '~ _a) a4 '~
~' ~ Q. LZ. ~.~. Q.
O O
w w O O
O O U
O O U
w z z U
N
ctt o ~.
U
\ / \ / / I
a U Z
Cn / .
O ',. ~ / O Z ~ ~ ..~ Z
Z = Z. ~ v / ~ / ~ ~ ~ ..~ ~ z x 0 o wl a a N p"
o~ O .-a N M M

,.., ' o C' o p N ~ N CV ~ ~i Gr~ ~ \ ~ :3 C a.
~i U
U U o O
N M
b _a) a) N
w ø. ~ Q, O O
I
I ~ I I I ..
z z U ~~ ~ O O
t ~~~ _ _ x Z
O
N
N
O U-U .Z
x w° / I
I
U
z '" x I
I
I z z z z .z x x x x ~
I \ ( w N

y O
a y _ r y J C.
N M ~t a ~ Z M M M
N

C . ~ ~ ~a G~' ~ :v a c w t7 O
U U U
O N O
c~ . b N O N
b o ~~ o w yy ~~" .~''b °''~
G w a. w / ( I ~. ( U U
O O ~ ~ ~ O
U / ~ U /
I /

r ( .'' I r ~, w a ~ ~. ci .
I ( i z = ~r ~;, ~ ( = z I
I
z z .i i _z z z t 1 ~ I r I ( o 0 b a 'i N p., .
a~
' M M M

U
C' .
.O N
G N

O
a w, O
M
'a w N _N
U b w Q, O O
r.~ w U
r w g r ~ .
w i s O
z z x z C~ O
a a a~
N p"
a~
H ~z M

Materials used (amine/coupler) Example 14: 2,5-di(4'-aminophenyl)-3,4-oxadiazole/ 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene Example 15: 2,5-di(4'-aminophenyl)-3,4-oxadiazole/ 2-hydroxy-3,6-bis(3'-nitrophenylaminocarbonyl)naphthalene Example 16: 2,5-di(4'-aminophenyl)-3,4-oxadiazole/ 2-hydroxy-3,6-bis(2'-ethylphenylaminocarbonyl)naphthalene Example 17: 2,5-di(4'-aminophenyl)-3,4-oxadiazole/ 2-hydroxy-3,6-bis(2'-chlorophenylaminocarbonyl)naphthalene Example 18: 2,5-di(4'-aminophenyl)-3,4-oxadiazole/ 2-hydroxy-3,6-bis(2'-chlorophenylureidocarbonyl)naphthalene Example 19: 2,7-diamino-9-fluorenone/ 2-hydroxy-3,6-bis(2'-nitrophenylaminocarbonyl)naphthalene Example 20: 2,7-diamino-9-fluorenone/ 2-hydroxy-3,6-bis(2'-ethylphenylaminocarbonyl)naphthalene Example 21: 2,7-diamino-9-fluorenone/ 2-hydroxy-3,6-bis(2'-chlorophenylaminocarbonyl)naphthalene Example 22: 2,7-diamino-9-fluorenone/ 2-hydroxy-3,6-bis(2'-chlorophenylureidocarbonyl)naphthalene Example 23: 2-(4'-aminophenyl)-6-aminobenz-1,3-oxazole/ 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene Example 24: 2-(4'-aminophenyl)-6-aminobenz-1,3-oxazole/ 2-hydroxy-3,6-bis(3'-nitrophenylaminocarbonyl)napht halene Example 25: 2-(4'-aminophenyl)~-6-aminobenz-1,3-oxazole/ 2-hydroxy-3,6-bis(2'-ethylphenylaminocarbonyl)naphthalene Example 26: 2-(4'-aminophenyl)-6-aminobenz-1,3-oxazole/ 2-hydroxy-3,6-bis(2'-chlorophenylaminocarbonyl)naphthalene Example 27: 2-(4'-aminophenyl)-6-aminobenz-1,3-oxazole/ 2-hydroxy-3,6-bis(2'-chloropher~ylureidocarbonyl)naphthalene Example 28: 2-(4'-aminophenyl)-~6-aminobenz-1,2,3-triazole/ 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene Example 2g: 2-(4'-aminophenyl)-6-aminobenz-1,2,3-triazole/ 2-hydroxy-3,6-bis(3'-nitrophenylaminocarbonyl)naphthalene Example 30: 2-(4'-aminophenyl)-6-aminobenz-1,2,3-triazole/ 2-hydraxy-3,6-bis(2'-ethylphenylaminocarbonyl)naphthalene Example 31: 4,4'-diamino-a-cyanostilbene/ 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene Example 32: 4,4'-diamino-a-cyanostilbene/ 2-hydroxy-3,6-bis(3'-nitrophenylaminocarbonyl)naphthalene Example 33: 4,4'-diaminoazobenzene/ 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene Example 34: 4,4'-diaminoazobenzene/ 2-hydroxy-3,6-bis(3'-nitrophenylaminocarbonyl)naphthalene Example 35: 4,4=diaminodiphenyl sulfide/ 2-hydroxy-3,6-bis(3'-nitrophenylaminocarbonyl)naphthalene Example 36:4,4=diaminodiphenyl sulfide/ 2-hydroxy-3,6-bis(2°-chlorophenylaminocarbonyl)naphthalene Example 37:4,4'-diaminodiphenyl disulfide/ 2-hydroxy-3,6-bisphenylaminocarbonylnaphthalene Example 38: 4,4=diaminodiphenyl disutfidc/2-hydroxy-3,6-bis(3'-nitrophenylaminocarbonyl)naphthalene Example 39 S;rnthesis of~alcium salt of 1,4-bis~~'-by lroxv-3',6'-dih~rs2.x~;~r onvlna htR h1'-"yla7.~ol y / \ ~N / \
2 Cap' \ / \ /
OOC COp J
In 30 g of water, 1.1 g of p-phenylenediamine was dispersed, and dissolved by adding 5.2 g of 35% hydrochloric acid. Diazotization is then conducted by adding dropwise a solution of 1.7 g of sodium nitrite dissolved in 1C) g of water, while maintaining the temperature at 0°C. On the other hand, 4.6 g of 2-hydroxy-3,6-dihydroxycarbonylnaphthalene was suspended in 10 g of water, dissolved by adding 28.0 g of 10% aqueous sodium hydroxide and 13.5 g of 5% resin solution, and then maintained at 13(~2)°C. To this solution, the above diazo solution was added dropwise over about 30 minutes, and further stirred for 9CI minutes. After adjusting the pH of the reaction mixture to 9.0-9.5, a solution of 4.4 g of calcium chloride dehydrate dissolved in 40 g of water was added dropwise in order to form a lake. After one hour, the mixture was brought to 70°C, left for about 30 minutes, and then cooled gradually to room temperature. To this, 200 g of water was added, and filtered with aspirating. The product was washed with water, and dried to give 1.94 g of a dark bluish purple powder calcium salt of 1,4-bis(2'-hydroxy-3',6'-dihydroxycarbonylnaphth-l.'-ylazo)benzene3 (melting/decomposition point:
412.1°C
(decomposition)).
An IR spectrum of this compound (KBr method) is shown in Eig. 4.
Examples 40-44 According to the same manner as described in Example 39 with the exception that as diamine compunents, amines shown beiowv Tabl~ 3 were substituted for p-phenylenediamine in Example 39, as coupler components, couplers shown below Table 3 were substituted for 2-hydroxy-3,Ei-dihydroxycarbonylnaphthalene, and l.l-1.2 equivalents of calcium chloride d.ihydrate was used, azo compounds were synthesized.
Melting/decomposition points of the synthesized a-r_o compounds are shown in Table 3.

a V U U
°° oo so v p p N - ~ O
~ M N M
.a _O x O .Cy N _N
.sNe .~ ~., "~e .~ ~., ..sa .n -~ a o. ~ .n Q. ~ .a a.
U U U
N ~ N
u7 G ! i I
o O p 10 Io ~ fo O
o r. y .' y O o r ', o U O
I
V /.
/ \ p V I
O I Q
_c3 O
c0 ~ I ~-~ / I
U
Ip ~ z 2 x = x w I .-- 1 r t o Io I o to o. o t I
..
M py O ~ O O .-i N
H r~ z '~ ~ '" -a o_ U U

M
DD
s. .s~ _a~ .ct _N
'.~d .
fl A~ ~ .fl »
tC
U
U
Z
/ I U
I.
. t0 Z t0 Z ~.
°a. O . O O O
U
o r ~ U
U
I i z I
w I
n z z Z \ I
U I° = s O O V
IO = I
U
h ( . t ~ Z
I
b a~
.b M p"
N
H ~ z 'M~' Materials used (amine/coupler) Example 40: 2-chloro-1,4-phenylenediamine/ 2-hydroxy-3,6-bishydroxycarbonylnaphthalene Example 41: 1,5-phenylenediamine-2-sulfonic acid/ 2-hydroxy-3,6-bishydroxycarbonylnaphthalene Example 42: 1,5-naphthylenediamine/ 2-hydroxy-3,6-bishydroxycarbonylnaphthalene Example 43: 1,4-phenylenediamine/ 2-hydroxy-3-hydroxycarbonyl-6-phenylaminocarbonylnaphthalene Example 44: 1,4-phenylenediamine/ 2-hydroxy-3-hydroxycarbonyl-6-(5'-chloro-2,4'-dimethoxyphenyl)aminocarbonylnaphthalene For Examples 40, 41 and 43, printing inks were prepared according to JIS
IC5101, and extended. The obtained color data is shown in Table 4. As color data, the dominant wavelength ~l d, the excitation purity Pe, and the brightness Y as described in JIS 28701 are shown.
Table 4 Dominant wavelengthExcitation purityBrightness Y
,a. d Pe Example 652 nm ~ 12.5% . 6.6%
40 i ~

Example 614 nm 13.9% 4.8%
41 700 nm 10.1% ~. 5.5%
Example43 According to the same manner as described in Example 13 with the exception that as diamine components, diamines shown below Table 5 were substituted for 2,7-diamino-9-fluorenone, and as coupler components, couplers shown below Table ~~ were substituted for 2-hydroxy-3,6-bis(phenylaminocarbonyl)naphthalene, azo compounds were synthesized. Melting/decomposition point of the synthesil.ed azo compounds are shown in Table 5.

a 'N U
o V U
(V ~,.~ o a _ M
cV
'W.y. G. W .~. P.
N
O
I ' \ I .- i U z ~, ~ I
U
O O O
O D
b r \ U o o ~- \ U
U
o \ I / / I \ \ I
Z _ \ /
o Z
N .
c0 o / I / I
\ I
.g z z .- \ s ~- \
/ \
o \ I ~ o ~. I ~ o \ I .-. U
o z o ~~ ~.~, ''' \ I ~ ~ ~ I ~ I
r I' . .
H u~ z '~

t7 O
'~ U U U
~. ~ Wn ~q_ o .
M M M
_ _O .C ~ .C' O ~.~ _N
.~d .N ~. .~4 .~' .~4 '~ .a O. ~ .a C1. '~ ~ P.
O
/ \ / \ "~ ~ .~u ' '~ ' z=
'~ '~ \ / w z 0 o z z O O V i w V o O
-d i w V I i w V
I
o. p ~ _i z z y. I
a z Z
N
cOC ~
° .Z
o z x z z z , v ° .-w 1 ~ o o w L.~ v.
z z z . .~ z z~cn cry / \ ~ I
/ \ / z z z z b .b a>
R.
O ~ 00 O\ O
~t d~

Materials used (amine/coupler) Example 45: p-phenylenediamine:/ 2-hydroxy-3-methaxycarbonyl-6-(3'-nitrophenyl)amirrocarbanylnapht halene Example 46: p-phenylenediamine:/ 2-hydraxy-3-methoxycarbonyl-6-benzyloxycarbonylnaphthalene Example 47: p-phenylenediamine/ 2-hydroxy-3,Ci-bis(phenoxycarbonyl)naphthalene Example 48: p-phenylenediamine/ 2-hydroxy-3,6-bis(benzothiazol-2'-ylaminocarbonyl)naphthalene Example 49: 2-vitro-1,4-phenylenediamine/ 2-hydraxy-3,6-bis(4',5'-dicyanoimidazol-2'-ylaminocarbonyl)naphthalene Example 50: p-phenylenediamine/ 2-methoxy-3-(bcnzimidazolon-5'-ylaminocarbonyl)-6-phenylaminocarbonylnaphthalene:
Industrial Applicability The bisazo compounds of the invention are navel and are useful as pigments having excellent resistance to water, chemical agents, salvents, heat and the like.
Brief Description of Drawings Fig. 1 is an IR spectrum of the bisaza compound obtained v~ f:xample 1.
Fig. 2 shows a spectral property of the bisaza compound ok>tained in Example 5.
Fig. 3 shows a spectral property of the biSBZC) compound obtained in Example 7.
Fig. 4 is an IR spectrurr~ of the bisazo compound obtained ixr Example 39.

Claims (14)

Claims

1. A bisazo compound represented by the following general formula [I]:
A-N=N-E-N=N-A' [I]
[wherein, A and A' may be the same or different, and represent the following general formula [II]:
(wherein, Y is -(CONH)n-X or -COR, Y' is -(CONH)n-X' or -COR', and 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), n represents an integer of 1 or 2, R and R' may be the same or different, and represent a hydroxy group, an optionally branched alkoxy group having 1-6 carbon atoms, a benzyloxy group, a phenoxy group, or a phenacyloxy group, R2 represents a hydrogen atom, an optionally branched alkyl group having 1-6 carbon atoms, an acyl group having 1-6 carbon atoms or a phenylalkyl group;
Q represents an optionally branched alkyl group having 1-6 carbon atoms, an optionally branched alkoxy group having 1-6 carbon atoms, a halogen atom, a nitro group or a nitroso group, and m represents an integer from 0 to 3, and when one of R and R' represents a hydroxy group, it may optionally form an acceptable salt;
E represents a cyclic group having a conjugated double bond.]

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

3. The bisazo compound according to claim 1 in which E is a group selected from a group consisting of arylene groups, the general formulas [III] and [V]:
-Ar-M-Ar'- [III]
(wherein, Ar and Ar' each independently represent an optionally substituted aryl or heterocyclic group having a conjugated double bond, M represents a group selected from a group consisting of a single bond, -CH2-, -CH=C(E')- (in which E' is a hydrogen, a halogen atom, a lower alkyl group, or a cyano group), -O-, -S-, -S-S-, -CO-, -COO-, -SO2-, -N(T)-(in which T is an optionally substituted phenyl or a lower alkyl group), -N=N-, -CH=CH-.PHI.-CH=CH- (in which .PHI. is an arylene group), and a formula (IV]:
(in which G represents -O-, -S-, or -NH-)];
(wherein, L represents >N-CH3, >C=O, or >C=S].

4. Use of a bisazo compound of any one of claims 1 to 3, as a pigment.

5. Use of a bisazo compound of any one of claim 1 to 3, to manufacture a printing ink.

6. Use of a bisazo compound of any one of claims 1 to 3, to manufacture a paint.

7. Use of a bisazo compound of any one of claims 1 to 3, as a colouring agent for plastics.

8. Use of a bisazo compound of any one of claims 1 to 3, as an organic photoconductor.

9. A pigment comprising the bisazo compound set forth in any one of claims 1 to 3.

10. A printing ink comprising the bisazo compound set forth in any one of claims 1 to 3.

11. A paint comprising the bisazo compound set forth in any one of claims 1 to 3.

12. A colouring agent for plastics comprising the bisazo compound set forth in any one of claims 1 to 3.

13. An organic photoconducter comprising the bisazo compound set forth in any one of claims 1 to 3.

14. A process for producing the bisazo compound set forth in claim 1 which comprises diazotizing a compound represented by the general formula [VI]:
H2N-E-NH2 [VI]
(wherein, E represents a cyclic group having a conjugated double bond], and coupling the obtained bisdiazonium compound with a compound represented by the general formula [VII]:
[wherein, Y is -(CONH)n-X or -COR, Y' is -(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, n represents an integer of 1 or 2, R and R' may be the same or different, and represent a hydroxy group, an optionally branched alkoxy group having 1-6 carbon atoms, a benzyloxy group, a phenoxy group, or a phenacyloxy group, R2 represents a hydrogen atom, an optionally branched alkyl group having 1-6 carbon atoms, an acyl group having 1-6 carbon atoms or a phenylalkyl group;
Q represents an optionally branched alkyl group having 1-6 carbon atoms, an optionally branched alkoxy group having 1-6 carbon atoms, a halogen atom, a nitro group or a nitroso group, and m represents an integer from 0 to 3], and optionally, when R or R' is a hydroxy group, it may further be converted to a lake.