CHO SUNG YONG (KR)
KIM DONG GIL (KR)
CHO SUNG YONG (KR)
GB1219383A | 1971-01-13 | |||
US4935500A | 1990-06-19 | |||
GB1194504A | 1970-06-10 | |||
US4607098A | 1986-08-19 |
1. | Dicyclic metal formazan derivatives represented by the below formula(l ): wherein A iiss benzene or naphthalene having 1 to 3 substituent groups and sulfo group(S03M) in orthoposition for Natom of hydrazone compound; B is strait or branchedchain alkyl group, phenyl group, naphthyl group or substituent heterocyclic group; C is benzene or naphthalene having from 1 to 3 substituent groups; D is benzene or naphthalene; M is hydrogen atom, alkali metal or alkaki earth metal; Me is metal ion of atomic number 27 to 29; Y is halogen; X is hydrogen atom or sulfo group, carboxyl group, phosphonic group providing solubility for water; R is strait or branchedchain alkyl group; Q is or Sθ2CH2CH2L(L is a group which may be substituted by alkali); and l,m,n are independently an intenger from 0 to 3. |
2. | Dicyclic metal formazan derivatives according to Claim 1 represented by the below formula(6): (6) . |
3. | Dicyclic metal formazan derivatives according to Claim 2 represented by the below formula(6' ): . |
4. | Dicyclic metal formazan derivatives according to Claim 3 represented by the below formula(6")' . |
5. | Dicyclic metal formazan derivatives according to Claim 1 represented by the below formula, wherein M is hydrogen, R is methyl group and Q is SO2CH2CH2OSO3H: . |
6. | Dicyclic metal formazan derivatives according to Claim 4 represented by the below formula, wherein M is hydrogen, R is ethyl group and Q is SO2CH2CH2OSO3H: . |
7. | Dicyclic metal formazan derivatives according to Claim 4 represented by the below formula, wherein M is hydrogen, R is hydroxyethyl group and Q is SO2CH2CH2OSO3H: . |
8. | Dicyclic metal formazan derivatives according to Claim 4 represented by the below formula, wherein M is hydrogen, R is ethylcarboxylamide group and Q is SO2CH2CH2OSO3H: . |
9. | A process for producing dicyclic formazan derivatives of the formula(l ) by firstly condensing formazan compound of the below formula(2) with 1,3,5trihalogenostriazine to give formazan compound of the below formulaO), and secondly condensing the obtained formazan compound of the formulaO) with amine compound of the below formula(4): R HN D Q (4) . |
10. | A process for producing dicyclic formazan derivatives according to Claim 9, wherein the first condensation is conducted at pH 2 to 4 and temperature of 5 to 20 *C , and the second condensation is conducted at pH 4 to 8 and temperature of 20 to 5 701 . |
11. | A process for producing dicyclic formazan derivatives according to Claim 10, wherein the first condensation is conducted at pH 3 to 4 and temperature of 0 to 10*0 , and the second condensation is conducted at pH 4 to 6 and temperature of 30 to 10 601C . |
12. | A process for producing dicyclic formazan derivatives, wherein 1,3,5trihalogenostriazine is condensed with the amine compound of the formula(4) to give a compound of the below formulaO), and then the obtained compound of the formulaO) is 15 condensed with formazan derivatives of the formulaO): . |
13. | A process for producing dicyclic formazan derivatives according to Claim 12, wherein the first condensation is conducted at pH 2 to 4 and temperature of 5 to 20 " , and the second condensation is conducted at pH 4 to 8 and temperature of 20 to 70t . |
14. | A process for producing dicyclic formazan derivatives according to Claim 13, wherein the first condensation is conducted at pH 3 to 4 and temperature of 0 to 10 "C , and the second condensation is conducted at pH 4 to 6 and temperature of 30 to . |
15. | Dicyclic metal formazan derivatives represented by the below formulaO): wherein A is benzene or naphthalene having 1 to 3 substituent groups and sulfo group(SOsM) in orthoposition for Natom of hydrazone compound; B is strait or branchedchain alkyl group, phenyl group, naphthyl group or substituent heterocyclic group; C is benzene or naphthalene having from 1 to 3 substituent groups.' M is hydrogen atom, alkali metal or alkaki earth metal; Me is metal ion of atomic number 27 to 29; Y is halogen; or sulfo group, carboxyl group, phosphonic group providing solubility for water; and l,m,n are independently an intenger from 0 to 3. |
16. | A process for producing formazan derivatives of the formulaO), wherein an amine compound of the below formulaO) is diazotated to give a sulfone compound, the obtained sulfone compound is hydrolized in the presence of inorganic acid to give hydrazine compound, the obtained compound is reacted with aldehyde compound of the formulaO) to synthesize hydrazone compound, the obtained hydrazone compound is reacted with the compound of the below formulaO) to diazotate it, and then the obtained compound of the formulaO) is coupled in the presence of metal ion: X, NH, (7) *m B CHO (8) HO c n H2N O) . |
17. | Dye composition comprising the below formula(l): wherein A is benzene or naphthalene having 1 to 3 substituent groups and sulfo group(SOsM) in orthoposition for Natom of hydrazone compound; B is strait or branchedchain alkyl group, phenyl group, naphthyl group or substituent heterocyclic group; C is benzene or naphthalene having from 1 to 3 substituent groups; D is benzene or naphthalene; M is hydrogen atom, alkali metal or alkaki earth metal; Me is metal ion of atomic number 27 to 29; Y is halogen; X is hydrogen atom or sulfo group, carboxyl group, phosphonic group providing solubility for water; R is strait or branchedchain alkyl group; Q is Sθ2CH=CH2, or S02CH2CH2L(L is a group which may be substituted by alkali); and l,m,n are independently an intenger from 0 to 3. |
18. | Process for dyeing fabrics by using dicyclic formazan derivatives represented by the formula(l ): wherein A is benzene or naphthalene having 1 to 3 substituent groups and sulfo group(S03M) in orthoposition for Natom of hydrazone compound; B is strait or branchedchain alkyl group, phenyl group, naphthyl group or substituent heterocyclic group; C is benzene or naphthalene having from 1 to 3 substituent groups; D is benzene or naphthalene; M is hydrogen atom, alkali metal or alkaki earth metal; Me is metal ion of atomic number 27 to 29; Y is halogen; X is hydrogen atom or sulfo group, carboxyl group, phosphonic group providing solubility for water; R is strait or branchedchain alkyl group; Q is S02CH=CH2, or Sθ2CH2CH2L(L is a group which may be substituted by alkali); and l,m,n are independently an intenger from 0 to 3. |
DICYCLIC METAL COMPLEX FORMAZAN DERIVATIVES-
PROCESS FOR PRODUCING THE SAME. COMPOSITION
CONTAINING THE SAME AND DYEING PROCESS
EMPLOYING THE SAME
Technical Field
The present invention relates to formazan derivatives useful
as reactive dye and a process for producing the derivatives. More
specifically, the present invention relates to a novel dicyclic metal
complex formazan derivatives used as a light blue dye and a
process for producing the derivatives.
Background Art
Generally, metal complex formazan derivatives are used as
complex salt of divalent or trivalent metal such as copper, nickel,
cobalt and chromee, have brighter colors than conventional azo
dyes, and have an excellent compatibility with the other color dyes
as compared with anthraquinone or dioxazine- based dyes.
Formazan derivatives as reacive dyes which have a form of
copper complex or have a vinylsulfone group or both of
vinylsulfone group and monochlorotriazine, have been developed
long time ago. The conventional formazan are mostly tricyclic.
Most of them are 2-carboxyl-5-sulfo-phenylhydrazine as hydrazine
compound. These tricyclic formazans are expensive in
manufactruing and poor in stability for alkali at the time of room
tepperature immersion (cold pad) dyeing.
Typical tricyclic formazan compounds have the following
formula:
Specifically, Japanese Patent Publication No.81-4783 describes a
compound represented by the below formula:
However, the said compound of Japanese Patent Publication
No.81 -4783 is not good in solubility, dyeing property and state of
remained bath. In addition, Japanese Patent Publication Sho
55-12187 and EP 0,099,721 disclose tricyclic formazan derivatives
as dye similiar to the compound of the Japanese Patent
Publication No.81-4783. But, these dyes are expensive in
manufacturing cost and are not good in fastness.
Further, United Kingdom Patent Publication 1,194,504 discloses
dicyclic formazan derivatives having the following formula-'
CH 3 S0 2 • S0 2 CH 2 CH 2 OS0 3 H
I I I
N.- C" N
^
The said dicyclic formazan derivatives is also not good in
fastness and dyeing property.
USP 4,607,098 discloses a compound of the following formula
which has more improved fastness than the said dicyclic formazan
derivatives:
BAD ORIGINAL
However, these formazan compounds known in USP 4,607,098 have
also somewhat problems in dyeing property and chlorine water.
Disclosure of the Invention
The inventors have made extensive and intensive sutdies with
a view to solving the above-described problems, and thereby have
obtained novel formazan derivatives represented by the below
formula(l):
wherein
A is benzene or naphthalene having 1 to 3 substituent groups
and sulfo group(-S03M) in ortho-position for N-atom of
hydrazone compound;
B is strait- or branched-chain alkyl group, phenyl group,
naphthyl group or substituent heterocyclic group;
C is benzene or naphthalene having from 1 to 3 substituent groups;
D is benzene or naphthalene;
M is hydrogen atom, alkali metal or alkaki earth metal;
Me is metal ion of atomic number 27 to 29;
Y is halogen;
X is hydrogen atom or sulfo group, carboxyl group, phosphonic
group providing solubility for water;
R is strait- or branched-chain alkyl group;
Q is -S0 2 CH=CH 2 , or -S0 2 CH 2 CH 2 L(L is a group which may be
substituted by alkali); and
l,m,n are independently an intenger from 0 to 3.
Formazan derivatives represented by the above formula(l ) are
produced by firstly condensing formazan compound of the below
formula(2) with 1,3,5-trihalogeno-s-triazine to give formazan
compound of the below formulaO), and secondly condensing the
obtained formazan compound of the formula(3) with amine
compound of the below formula(4):
R
H -N -D-Q (4)
Alternatively, formazan derivatives of the formula( l ) are
produced by reacting 1 ,3,5-trihalogeno-s-triazine with the amine
compound of the formula(4) to give a compound of the below
formula(5), and then reacting the obtained compound • of the
formula(5) with formazan derivatives of the formula(2):
R • Y-τ^ ^f N-D-
(5)
The definitions in the compounds of the above formula(2) and
(3) are same as in the compound of the formula(l). However, the
substituents of benzene or naphthalene ring in definitions A and C
are preparably halogen, nitro, C1 -C4 alkyl group, C1 -C4 alkoxy
group, sulfamoyl group, N-mono or N,N-dialkyl(Cι -C4)sulfamoyl,
C1 -C4 alkylsulfonyl group, phenylsulfonyl group, more preferably
chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, sulfamoyl
or N,N -dimethylsulfamoyl group.
If B is a strait or branched chain, it is preferably Ci -Cβ,
more preferably C2-C8.
If B is a benzene or naphthalene, the substituent is preferably
halogen, hydroxy group, nitro group, C1-C4 alkyl, C1-C4 alkoxy
group, d -C4 carboalkoxy group.
If B is heterocyclic ring, the substituent is preferably furan,
thiophen, pyrrol, imidazole, indol, pyrazole, pyridine, pyrimidine,
quinoline, benzimidazole and the like. Hydrogen atom bonded to
the ring-membered carbon consisting of heterocyclic ring may be
substituted with chloro, phenyl, methyl, ethyl, methoxy or ethoxy,
and hydrogen atom bonded to hetero atom of the heterocyclic ring
may be substituted with methyl, ethyl or benzyl.
Me as metalic atom is preferably a compound of atomic
number 27 to 29, more preferably atomic number 29, Cu.
In the compounds of the above formula(l),(3) and (5), halogen
of definition Y is preferably fluorine, chlorine or bromine atom,
more preferably fluorine or chlorine atom.
X group providing solubility for water, is preferably sulfonic
acid, carboxylic acid or phosphonic acid, more preferably sulfonic
acid, which may be bonded to ring-membered carbon atom
consisting of ring or to aliphatic carbon atom linked to ring.
In the compounds of the above formula(l ), (4) and (5), if D is
phenyl, it may be substituted with halogen, C1 -C4 alkyl group or
C 1 -C 4 alkoxy group, preferably methyl, ethyl, methoxy, ethoxy,
chlorine or bromine. And if D is naphthalene, it is preferably
unsubstituted or substituted with sulfonic group.
Further, in the compounds of the formulaO ), (4) and (5), if R
is alkyl group, it is preferably low alkyl groups such as methyl,
ethyl, propyl and butyl, more preferably methyl, ethyl, carbamoyl,
ethyl, hydroxyethyl, n-propyl, isopropyl and the like, which may
be substituted with hydroxyl, carboxyl, sulfo, carbamoyl, methoxy
carbonyl group and the like.
l,m and n indenpendently, are preferably 2 or 3.
In the compounds of the above formula(l ),(4) and (5), if Q is
-SO2CH2CH2L, L is preferably ester group, -OPO3H2, -SSO3H2,
more preferably -OSO3H of organic carboxylic acid or sulfonic
acid comprising chlorine, bromine atom or acetyloxy group,
benzoyloxy group, benzene sulfonyloxy group and low alkane oxy
group.
Accordingly, Q can be represented by -SO2CH2CH2OSO3H,
wherein a part of these elements may be removed by alkali to
give a form of -S02CH=CH2.
A group of the below formula(5' ) in the formula(l ) may be
linked to any one of phenyl, naphthyl, alkyl, alkenyl, phenylene,
naphthalene, heterocycle or carbon atom of branched-chain,
preferably phenyl group:
( 5 ' )
Formazan derivatives of the formula(l) according to the above
preferable definitions are represented by the below formula(6):
wherein D,R,Q and Y are same as defined in the formula(l ),(3),(4)
and (5), p,q and r are indenpendently 0 or 1, provided that the
total amount of them is an intenger of 3 or less.
More preferable formazan derivatives is represented by the
below formula(6' ):
Most preferable formazan derivatives is represented by the
below formula(6"):
Formazan derivatives of the formula(l ) according to the
present invention are produced by reacting a formazan compound
of the above formula(2) with 1,3,5-trihalogeno-s-triazine to give a
formazan compound of the below formula(3), and condensing the
obtained formazan compound of the formula(3) with an amine
compound of the above formula(4); or by reacting
1,3,5-trihalogeno-s-triazine with the amine compound of the
formula(4) to give a compound of the below formula(5), and then
reacting the obtained compound of the formula(5) with formazan
derivatives of the formula(2) .
Reaction conditions and order in this process are not
specifically limited, the condensation reaction are conducted
generally at pH 2 to 8 and temperature of -5 to 70 TC , preferably
pH 3 to 6 and temperature of 0 to 60 T. .
More specifically, the reaction condition in the first
condensation may depend on physical properties of the reactants or
intermediates to be produced, but is relatively low pH and reaction
temperature. That is to say, the first condensation reaction is
conducted at pH 2 to 4 and temperature of -5 to 201 , preferably
pH 3 to 4 and temperature of 0 to ICC .
But, the second dondensation reaction depends on physical
prorerties of reactants and formazan derivatives to be produced,
and is conducted at relatively high pH, for example pH 4 to 8 and
relatively high temperature of 20 to 70 "C , preferably pH 4 to 6 and
relatively high temperature of 30 to 601 .
Formazan derivatives of the formual(2) can be produced by
diazotating an amine compound of the below formula(7) to give a
sulfone compound, hydrolizing the obtained sulfone compound in
the presence of inorganic acid to give hydrazine compound,
reacting the obtained compound with aldehyde compound of the
formula(8) to synthesize hydrazone compound, reacting the
obtained hydrazone compound with the compound of the below
formulaO) to diazotate it, and then coupling them in the presence
of metal ion:
X.
NH„
(7)
X HO m B -C
(8)
If the above obtained compound is not amine compound of the
formula(2) but compound of the below formula(lθ) having nitro or
acetylamino group, the compound of the formula(2) can be easily
produced by reduction of nitro group or hydrolysis of acetylamino
group:
( 10) wherein T is nitro group or acetylamino group, and definition for
the other symbols are same as these of the above formula(l).
Metal ion used in this process are sulfate, carbonate,
acetate, salisilate, tartarate or chloride which concerns in the
reaction.
Examples of the compound represented by the forumla(7)
are aniline-2-sulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-
disulfonic acid, 4-methylaniline-2-sulfonic acid, 5-methylaniline
-2-sulfonic acid, 2,4-dimethylaniline-2-sulfonic acid, 4,5-
dimethylaniline-2-sulfonic acid, 2-methylaniline-4,6-disulfonic acid,
4-methylaniline-2,5-disulfonic acid, 4-methoxyaniline-2-sulfonic
acid, 5-methoxyaniline-2- sulfonic acid, 4-methoxy-5-chloroaniline-
2-sulfonic acid, 4,5-dim ethoxy aniline-2- sulfonic acid, 4-
ethoxyaniline-2- sulfonic acid, 5-ethoxyaniline-2- sulfonic acid, 4-
hydroxyaniline-2- sulfonic acid, 5-hydroxyaniline-2- sulfonic acid,
5-hydroxyaniline-2,4-disulfonic acid, 4-carboxylaniline- 2- sulfonic
acid, 5-carboxylaniline-2-sulfonic acid, 4-hydroxy-3-carboxylaniline
-2- sulfonic acid, 4-nitroaniline~2- sulfonic acid, 5-nitroaniline-2-
sulfonic acid, 2,4-dinitroaniline-6-sulfonic acid, 5-nitro-4-
chloroaniline-2- sulfonic acid, 4-fluoroaniline-2- sulfonic acid,
3-chloroaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid,
5-chloroaniline-2-sulfonic acid, 4,5-dichloroaniline-2-sulfonic acid,
2,4-dichloroaniline-6-sulfonic acid, 2,4,5-trichloroaniline-2-sulfonic
acid, 4-chloro-5-carboxylaniline-2-sulfonic acid, 2,5-dichloro-4-
nitroaniline-6- sulfonic acid, 4-bromoaniline-2- sulfonic acid,
5-bromoaniline-2-sulfonic acid, 2,4-dibromoaniline-6- sulfonic acid,
3,4-dibromoaniline-6- sulfonic acid, 4-iodoaniline-2-sulfonic acid,
5-iodoaniline-2-sulfonic acid, 4-acetaminoaniline-2-sulfonic acid,
5-acetaminoaniline-2- sulfonic acid, l ,4-phenylenediamine-2,5-
disulfonic acid, l,3-phenylenediamine-4,6-disulfonic acid, 1 -
naphthylamine-2-sulfonic acid, 2-naphthylamine-l -sulfonic acid,
l -naphthylamine-2,4-disulfonic acid, l-naphthylamine-2,5-disulfonic
acid, 2-naphthylamine-l,5-disulfonic acid, 2-naphthylamine- l,7-
disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-
naphthy lamine-3,7-disulfonic acid, 1 -naphthy lamine-2,4,7-trisulfonic
acid, 2-naphthylamine-3,6,8-trisulfonic acid, 2-naphthylamine- 1,5,7-
trisulfonic acid.
Examples of the aldehyde compound represented by the
forumla(8) are benzaldehyde, 2-methoxybenzaldehyde, 3-methoxy
benzaldehyde, 4-methoxybenzaldehyde, 4-methoxybenzaldehyde-3-
sulfonic acid, 2-methylbenzaldehyde, 3-methylbenzaldehyde,
4-methoxy-3-chlorobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenz
aldehyde, 2-hydroxybenzaldehyde, 2-chlorobenzaldehyde, 4-
chlorobenzaldehyde, 2,4-dichlorobenzaldehyde, 2-chlorobenzaldehyde
-5-sulfonic acid, benzaldehyde-2- sulfonic acid, benzaldehyde-3-
sulfonic acid, benzaldehyde-4- sulfonic acid, benzaldehyde-2,4-
disulfonic acid, 2-acetylaminobenzaldehyde, 4-acetylaminobenz
aldehyde, 4-nitrobenzaldehyde-2- sulfonic acid, 3-methyl-2-
nitrobenzaldehyde, 3-methyl-β-nitrobenzaldehyde, 2-chloro~6-
nitrobenzaldehyde, 1 -naphthoaldehyde, 2-naphthoaldehyde, furan-2-
aldehyde, thiophene-2-aldehyde, pyrrol-2-aldehyde imidazole-2-
aldehyde, pyrazole-5-aldehyde, pyridine-2-aldehyde, pyridine-3-
aldehyde, pyridine-4-aldehyde, pyrimidine-5-aldehyde, quinoline-4-
aldehyde, benzimidazole-2-aldehyde, acetaldehyde, buthylaldehyde,
ethanealdehyde, acrylaldehyde, crotonaldehyde, phenacetaldehyde,
cinamaldehyde.
Examples of the amine compound represented by the
forumla(9) are 2-aminophenol, 4-methyl-2-aminophenol, 5-methyl-2
-aminophenol, 4-sulfo-2-aminophenol, 5-sulfo-2-aminophenol, 4-
methoxy-2-aminophenol, 5-methylsulfonyl-2-aminophenol, 4-methyl
sulfamoyl-2-aminophenol, 4-dimethylsulfamoyl-2-aminophenol, 5-
nitro-2-aminophenol, 4-bromo-2-aminophenol, 4,6-disulfo-2-
aminophenol, 2-acetylamino-6-aminophenol-4-sulfonic acid,
6-nitro-4-sulfo-2-aminophenol, 4-nitro-6-sulfo-2-aminophenol, 4-
acetylamino-6-sulfo-2-aminophenol,
4-chloro-6-sulfo-2-aminophenol, 6-chloro-4-sulfo-2-aminophenol,
4-methylsulfonyl-2-aminophenol, 4-buthylsulfonyl-2-aminophenol,
4-ethylsulfonyl-2-aminophenol, 4-sulfamoyl-2-aminophenol, 1 -
amino-2-hydroxynaphthalene-4,6-disulfonic acid, l-amino-2-
hydroxynaphthalene-6-chloronaphthalene-4- sulfonic acid, 4-
methylol-6-sulfo-2-aminophenol.
Aromatic amine represented by the above formula(4) can be
produced by alkylating aromatic amine of the below formula(ll ) in
the presence of alkylating agent such as alkylhalide, dialkylsulfate,
monosubstituted ethylene oxide:
Examples of alkylhalide are halides such as methylchloride,
ethylchloride, n-propylchloride, isopropylchloride, n-buthylchloride,
isobuthylchloride, sec-buthylchloride, methylbromide, ethylbromide,
n-propylbromide, isopropylbromide, n-buthylbromide, isobuthyl
bromide, and sec-buthylbromide; and examples of mono
substituted ethylene are acrylonitrile, acrylic acid, methylacrylate,
ethylacrylate, acrylamide, and binylsulfonic acid.
Examples of dialkylsulfate are dimethylsulfate, diethylsulfate
and dipropylsulfate; and examples of oxide are ethyleneoxide,
propyleneoxide, glycol, trimethyleneoxide, /3-buthyloxide, 2-methyl-
α-buthyleneoxide, 2-ethyl-3-methyleneoxide, methoxyethyleneoxide,
methoxyleneoxide and n-buthoxyyleneoxide.
Aromatic amine compound of the above formula(l l ) can be
produced by esterizing or halogenizing a compound of the below
formula(12):
H2N-D-SO2CH2CH2OH (12)
Examples of aromatic amine compound represented by the
above formula(l l ) which cna be produced by the said process, are
l -aminobenzene-2,3-/3-sulfatoethy lsulfone, l-aminobenzene-2,4-/3-
sulfatoethy lsulfone, 1 -aminobenzene-3-phosphatoethylbenzene,
l-amino-4-methylbenzene-3-#-sulfatoethylsulfone,
l-aminobenzene-3-0-phosphatoethylbenzens,
l -aminobenzene-4-methoxybenzens-3-/ϊ-sulfatoethy lsulfone,
l-amino-2,5-dimethylbenzene-4-jS-sulfatoethylsulfone,
l -amino-4-methoxybenzene-4-0-sulfatoethylsulfone,
l -amino-4-chlorobenzene-4-0-sulfatoethylsulfone,
l -amino-4-methoxybenzene-5-#-sulfatoethylsulfone,
2-aminonaphthalene-8-(5-sulfatoethylsulfone-6- sulfonic acid,
2-aminonaphthalene-8-/3-sulfatoethylsulfone,
l -amino-2,5-dimethoxybenzene-4- vinylsulfone,
l -amino-2-methoxy-5-methylbenzene-4-0-sulfatoethylsulfone,
2-aminonaphthalene-4,5,6-/J-sulfatoethylsulfone,
2-aminonaphthalene-4,5,7-/3-sulfatoethy lsulfone,
l -amino-2-bromobenzene-4- vinylsulfone,
2-amino-8-sulfonaphthalene-6-i3-sulfatoethylsulfone,
2-aminonaphthalene-8-)3-phosphatoethylsulfone-6- sulfonic acid,
2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid,
l-amino-2-methoxy-5-methylbenzene-4-0-chloroethy lsulfone,
l -aminobenzene-2,3- vinylsulfone, l-aminobenzene-2,4-vinylsulfone,
l-amino-2-methoxy-5-chlorobenzene-4-j3-chloroethylsulfone ,
l -amino-2-methoxy-5-chlorobenzene-4- vinylsulfone,
l-amino-2-ethoxy-5-chlorobenzene-4-iS-chloroethylsulfone,
l-amino-2-ethoxy-5-chlorobenzene-4-viny lsulfone,
2 -aminonaphthalene-8-0 - sulf atoethy lsulfone- 1 - sulfonic acid,
5-chloroaniline-2-/?-sulfatoethy lsulfone,
5-sulfoaniline-2-0-sulfatoethylsulfone,
aniline-2-ι3-thiosulfatoethylsulfone, 5-chloroaniline-2-(3-thiosulfato
ethylsulfone, 5-sulfoaniline-2-|3-thiosulfatoethylsulfone, aniline-2-i3
-phosphatoethylsulfone, 5-chloroaniline-2-/3-phosphatoethylsulfone,
5-sulfoaniline-2-β-phosphatoethylsulfone, 5-chloroaniline-2-
vinylsulfone, 5- sulfoaniline- 2 -vinylsulfone, aniline-2- β -chloro
ethylsulfone, 5-chloroaniline-2-|3-chloroethylsulfone and 5-
sulfoaniline-2- S-chloroethy lsulfone.
Best Mode for Conducting the Invention
Process for preparing formazan derivatives according to the
present invention is more specifically described in the following
examples, however the present invention is not intended to be
restricted to the examples.
Example 1
Phenylhydrazine-2,5-disulfonic acid is produced by diazotating
aniline- 2,5-disulfonic acid of the formula(7). 35.6 parts of
benzaldehyde phenylhydrazone-2,5- sulfonic acid is produced by
reacting the above obtained phenylhydrazine-2,5-disulfonic acid
with benzaldehyde of the formula(δ). 35.6 parts of
phenylhydrazone-2,5- sulfonic acid is dispersed in 200 parts of
water, and acidity of the dispersion is controled to pH 4 with a
solution of 10% sodium hydroxide. 24.6 parts of 3-acetylamino
-2-hydroxyaniline-5~sulfonic acid of the formulaO) is diazotated
and added to the said pH-controled solution with stirring. Aquous
solution obtained by solubilize 26.2 parts of copper sulfate to water
is added thereto. pH of the solution is controled in the range
from 3 to 5 with 20% sodium carbonate aquous solution obtained
by solubilizing sodium carbonate and reaction is conducted for one
hour. The reaction is conducted at elevated temperature of 40 to
50 "C for one hour to complete the reacition. The reaction solution
is cooled to the room temperatrue, and 20% of sodium chloride
based on the entire solution is added to this solution, and stirred
for one hour. The precipitate is filtered out to give formazan
derivatives. The formazan derivatives is added to a solution of
sodium hydroxide, hydro lized by heating at temperatureof 90 "C for
one hour to obtain the product. As a result, dicyclic formazan
derivatives represented by the below formula is obtained by
removing acetyl group from the product:
Example 2
Formazan derivatives obtained in Example 1 is acidified to pH
3 to 4 with concentrated hydrochloric acid, and 16.6 parts of
cyanuric chloride are added thereto with maintaining them at
temperature of 5t for one hour to give formazan derivatives
represented by the below formula(3):
Example 3
To a solution containing formazan derivatives obtained in
Example 2 are added 27.8 parts of l-N-ethylaminobenzene-3- 5-
sulfatoethy lsulfone produced by reacting l-aminobenzene-3-ιS-
sulfatoethylsulfone with diethylsulfate. The mixture is heated to
temperature of 40 * , and is maintained at pH 5 to 6 for 25 hours.
To the reaction -completed solution is added sodium chloride to
give preciitate which is filtered out to obtain blue(603 nm)
formazan derivatives of the below formula:
Examples 4 to 44
The procedures described in Example 3 are repeated in a
solution containing formazan derivatives obtained in Examples 1
and 2 by using the following compounds instead of compounds
used in Examples 1 and 2. As a result, blue(603 ± 2nm) formazan
derivatives are obtained.
Example No. Used compounds
4 l-N-ethylaminobenzene-4- β -sulfatoethy lsulfone
5 l-N-ethylaminobenzene-2- β -sulfatoethy lsulfone
6 l-N-methylamino-4-methoxybenzene-3- β -sulfatoethylsulfone
7 l-N-methylaminobenzene-3- β -sulfatoethylsulfone
8 l-N-methylaminobenzene-4- β -sulfatoethylsulfone
9 l-N -methylaminobenzene-2- β -sulfatoethylsulfone
10 l-N-methylamino-4-methoxybenzene-3- β -sulfatoethylsulfone
11 1 -N- β -carbamoylethylaminobenzene-3- β -sulfatoethylsulfone
12 1 -N- β -carbamoylethylaminobenzene-4- β -sulfatoethylsulfone
13 1 -N- β -carbamoylethylaminobenzene-2- β -sulfatoethylsulfone
14 1 -N - yff -carbamoylmethylamino-4-methoxybenzene-3-
β -sulfatoethylsulfone
15 l -N -n-propylaminobenzene-3- ? -sulfatoethylsulfone
16 l-N-n-propylaminobenzene-4- β -sulfatoethylsulfone
17 l-N-n-propylaminobenzene-2- £ -sulfatoethylsulfone
18 1 -N-n-propylamino-4-methoxybenzene-3- β - sulfatoethylsulfone
19 1 -N- β -cyanoethylaminobenzene-3- β - sulfatoethylsulfone
20 1 -N- β -cyanoethylaminobenzene-4- β -sulfatoethylsulfone
21 1 -N- β -cyanoethylaminobenzene-2- β -sulfatoethylsulfone
22 1-N- β -cyanoethylamino-4-methoxybenzene-3- β -
sulfatoethylsulfone
3 1 -N- β -hydroxyethylaminobenzene-3- β -sulfatoethylsulfone
4 1-N- β -hydroxyethylaminobenzene-4- β -sulfatoethylsulfone
5 1-N- β -hydroxyethylaminobenzene-2- β -sulfatoethylsulfone
6 1-N- /5 -hydroxyethylaminobenzene-4-methoxybenzene
-3- β -sulfatoethylsulfone
27 1 -N- β -sulfatoethylaminobenzene-3- β -sulfatoethylsulfone
28 1-N- β -methoxycarbonylethylaminobenzene-3- β -
sulfatoethylsulfone
29 l-N-ethylamino-2-rnethoxybenzene-5- β -sulfatoethylsulfone
30 l-N-ethylamino-2,4-dirnethylbenzene-5- ^ -sulfatoethylsιιlfone
31 l-N-ethylamino-2-methoxy-5-methylbenzene-3- β -
sulfatoethylsulfone
32 l -N-ethylaminonaphthalene-6- β -sulfatoethylsulfone
33 1 -N-ethylamino-8-sulfonaphthalene-6- β -sulfatoethylsulfone
34 l-N-methylaminonaphthalene-8- β -sulfatoethylsulfone
35 l -aminobenzene-4- β -sulfatoethylsulfone
36 l-aminobenzene-2- 9 -sulfatoethylsulfone
37 l-aminobenzene-3- # -sulfatoethylsulfone
38 l-amino-4-methoxybenzene-3- /3 -sulfatoethylsulfone
39 l -amino-2-methoxybenzene-5- /9 -sulfatoethylsulfone
40 l-amino-2-methoxy-5-methylbenzene-5- β -sulfatoethylsulfone
41 1 -amino-2,4-dimethylbenzene-5- β -sulfatoethylsulfone
42 l -aminonaphthalene-6- β -sulfatoethylsulfone
43 l -amino-8-sulfonaphthalene-6- β -sulfatoethylsulfone
44 l -aminonaphthalene-8- β -sulfatoethylsulfone
Examples 45
The reaction is conducted at the same condition and procedure
as those of Example 1, except that phenylhydrazine-2.4-disulfonic
acid as a starting material is used instead of phenylhydrazine
-2.5-disulfonic acid to give formazan derivatives represented by
the below formula.
Examples 46
The reaction between formazan derivatives produced from
Example 45 and cyanurilchloride of Example 2 is conducted at the
same reaction condition to give formazan derivatives represented
by the below formula:
Examples 47
Formazan derivatives produced in Example 46 is reacted with
the same compounds and process as those of Example 3 to give a
blue(606 nm) formazan derivatives:
Examples 48 to 88
Formazan derivatives produced in Example 46 is reacted with
the same compounds and process as those of Example 3, except
that the following compounds are used instead of 1 -N-
ethylaminobenzene-3-ø-sulfatoethylsulfone. As a result, blue(606±
2nm) formazan derivatives are obtained.
Example No Used compounds
48 l-N-ethylaminobenzene-4- β -sulfatoethylsulfone
49 l-N-ethylaminobenzene-2- β -sulfatoethylsulfone
50 1 -N-etJιylammo-4-methoxybenzene-3- β -sulfatoethylsulfone
51 l-N-methylaminobenzene-3- β -sulfatoethylsulfone
52 l-N-methylaminobenzene-4- β -sulfatoethylsulfone
53 l-N-methylaminobenzene-2- β -sulfatoethylsulfone
54 l-N-methylamino-4-methoxybenzene-3- β -sulfatoethylsulfone
55 1 -N- β -carbaπrøylethylaminobenzene-3- β -sulfatoethylsulfone
56 1 -N- β -carbamoylethylaminobenzene-4- β -sulfatoethylsulfone
57 1 -N- β -carbamoylethylaminobenzene-2- β -sulfatoethylsulfone
58 1 -N- yS -carbamoylmethylamino-4-methoxybenzene-3-
β -sulfatoethylsulfone
59 l -N-n-propylaminobenzene-3- β -sulfatoethylsulfone
60 l-N-n-propylaminobenzene-4- ? -sulfatoethylsulfone
61 l-N-n-propylaminobenzene-2- # -sulfatoethylsulfone
62 1 -N-n-propy lamino-4-methoxybenzene-3- β - sulfatoethylsulfone
63 1-N- β -cyanoethylaminobenzene-3- β -sulfatoethylsulfone
64 1-N- β -cyanoethylaminobenzene-4- β -sulfatoethylsulfone
65 1-N- β -cyanoethylaminobenzene-2- β -sulfatoethylsulfone
66 1-N- β -cyanomethylamino-4-methoxybenzene-3- β -
sulfatoethylsulfone
67 1 -N- β -hydroxyethylaminobenzene-3- β -sulfatoethylsulfone
68 1-N- β -hydroxyethylaιrrinobenzene-4- β -sulfatoethylsulfone
69 1-N- β -hydroxyethylaminobenzene-2- β -sulfatoethylsulfone
70 1-N- β -hydroxyethylaminobenzene-4-methoxybenzene-3- β -
sulfatoethylsulfone
71 1 -N- β -sulf atoethylaminobenzene-3- β -sulfatoethylsulfone
72 1-N- β -methoxycarbonylethylaminobenzene-3- β -
sulfatoethylsulfone
73 l-N-methylamino-2-methoxybenzene-5- β -sulfatoethylsulfone
74 l-N-e ylamino-2,4-dimethylbenzene-5- β -sulfatoethylsulfone
75 l-N-ethylamino-2-methoxy-5-methylbenzene-3- £ -
sulfatoethylsulfone
76 l-N-ethylaminonaphthalene-6- β -sulfatoethylsulfone
77 l-N-ethylaιrano-8-sulfonaphthalene-6- tf -sulfatoethylsulfone
78 l -N -methylaminonaphthalene-8- β -sulfatoethylsulfone
79 l-aminobenzene-4- β -sulfatoethylsulfone
80 l-aminobenzene-2- β -sulfatoethylsulfone
81 l-aminobenzene-3- β -sulfatoethylsulfone
82 l -amino-4-methoxybenzene-3- # -sulfatoethylsulfone
83 l -amino-2-methoxybenzene-5- # -sulfatoethylsulfone
84 1 -amino-2-methoxy-5-methylbenzene-5- β -sulfatoethylsulfone
85 1 -amino-2,4-dimethylbenzene-5- β -sulfatoethylsulfone
86 l-aminonaphthalene-6- # -sulfatoethylsulfone
87 l-amino-8-sulfonaphthalene-6- # -sulfatoethylsulfone
88 l-aminonaphthalene-8- β -sulfatoethylsulfone
Experiments for dyeing property for formazan derivatives of
the present invention are conducted.
Experiment 1
0.1 part of metal formazan derivatives having the below
formula described in EP 0,099,721 and 0.1 part of metal formazan
derivatives produced in Example 3 are separately melted in 200
parts of water to give a dyeing solution.
10 parts of sodium sulfate are added to the solution and then 10
parts of cotton cloth are added thereto. The solution is heated to
temperature of 60 * C . At this temperature, 4 parts of sodium
hydrogen carbonate are added thereto and stirred for one hour.
Dyed cloth is washed by water, washed again by boiled soup
water for 10 minutes, then washed by water to remove soup
water, and dried. Dyeing property and remained concentration
after washing soup water are compared and the results are
shown in the below table.
Experiment 2
The procedure described in Experiment 1 is repeated, except
that metal formazan compound of EP 0,099,721 and 0.2 part of
metal formazan compound produced in Example 3 are solubilized in
200 parts of water to form a dyeing solution. Dyeing property
and remained concentration after washing soup water are
compared and the results are shown in the below table.
Experiment 3
The procedure described in Experiment 1 is repeated, except
that metal formazan compound of EP 0,099,721 and 0.4 part of
metal formazan compound produced in Example 3 are solubilized in
200 parts of water to form a dyeing solution. Dyeing property
and remained concentration after washing soup water are
compared and the results are shown in the below table.
Sunlight fastness and washing fastness for the dried cloth
used in the experiments of the dyeing property are determined
according to JIS L 0841 and JIS L 0844, and chlorine fastness in
20 ppm solution of sodium hypochloride is determined. The
results are shown in Table.
TABLE
EP The Present 0,099,721 Invention
Dyeing Property 100 104.41
Experiment 1 Remained Concentration After Washing of Soup Water 100 76.64
Dyeing Property 100 105.63
Experiment 2 Remained Concentration After Washing of Soup Water 100 71.38
Dyeing Property 100 105.59
Remained Concentration After Washing of Soup Water 100 73.35
Experiment 3 Sunlight Fastness 5 < 5-6
Washing Fastness 4 5
Chlorine Fastness 4 4
As seen from the above table, dicyclic metal formazan
compound has excellent dyeing property as compared with the
conventional tricyclic metal formazan compound. Further, the dye
stuff withstand removing from fiber after washing the dyed cloth
with soup water as well as has excellent post-dyeing sunlight and
washing fastness.
Dicyclic metal formazan compound of the formula(l) can be
also used as reactive dye in fiber having dydroxy group or amido
group.