CN1028372C - Fibre-reactive dyestuffs - Google Patents
Fibre-reactive dyestuffs Download PDFInfo
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- CN1028372C CN1028372C CN 89109292 CN89109292A CN1028372C CN 1028372 C CN1028372 C CN 1028372C CN 89109292 CN89109292 CN 89109292 CN 89109292 A CN89109292 A CN 89109292A CN 1028372 C CN1028372 C CN 1028372C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/20—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a pyrimidine ring
- C09B62/24—Azo dyes
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- Organic Chemistry (AREA)
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Abstract
The present invention relates to free acid or salt of a fiber reactive compound disclosed in the specification and a mixture thereof. In the formula, F<c> is a base group of non-metal or metal complex type water solubility azo, formazane phthalocyanine, azomethine, oxazine, thiazine, phenoxazine or triphenylmethane dye. The base group can contain other fiber reactive base groups, and other symbols are limited in the specification. The compound is used for dyeing or printing organic matrix which contains hydroxy or nitrogen. The compound is suitable for substrate, such as leather, raw material containing natural or synthetic polyamide, or natural or regenerated cellulose, or fiber material composed of the raw material. Products which contain cotton or full cotton are preferable. The performance, such as light resistance, moisture resistance, firmness, antioxidation, etc., of obtained dyed colors and printing is good.
Description
The present invention relates to chromophore compound that contains fiber-reactive groups and preparation method thereof.These compounds are suitable for being used as fibre-reactive dyes in any traditional dyeing and printing technology.
More particularly, the invention provides the free acid of formula I compound or the mixture of salt and formula I compound,
Fc is water-soluble azo, a first no metal or the metal complexes form in the formula
, phthalocyanine, azomethine, oxazine, thiazine, azophenlyene or triphenylmethane dye group, these groups can contain the additional fibers reactive group,
A independently represents 0 or 1 separately,
B is 1 or 2,
X independently represent separately direct key ,-CO-or-SO
2-,
R
1Independent separately expression hydrogen, unsubstituted C
1-4Alkyl or by hydroxyl, halogen ,-SO
3H ,-OSO
3H or-the mono-substituted C of COOH
1-4Alkyl,
Alk independently represents C separately
2-4Alkylidene group;
W is independently expression separately
M is 0 or 1 in the formula,
B
1Be C
2-6Alkylidene group, have-O-or-NR
1-C
2-6Alkylidene chain is by one or two hydroxyl or by the C of a carboxyl substituted
3-6Alkylidene group,
N is 0,1,2,3 or 4 in the formula,
R
2Be hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or-SO
3H.
Any alkyl, alkenyl, alkynyl or alkylidene group in the specification sheets as not indicating in addition, all are the straight or branched groups.Any that replace by hydroxyl, be connected in the alkyl or alkylidene group on the nitrogen-atoms, this hydroxyl preferably is connected on the carbon atom that directly is not connected on the nitrogen-atoms.Contain in the alkylidene group of two hydroxyls at all, these hydroxyls are connected on the best different carbon atom not adjacent to each other.Having-O-or-NR
1-and be connected in any alkylidene group on the nitrogen-atoms ,-O-or-NR
1-preferably be connected in not directly with carbon atom that nitrogen-atoms links to each other on.
Any halogen preferentially refers to fluorine, chlorine or bromine; Chlorine or bromine is better, and chlorine is best.
Fc does not preferably have the water soluble group of monoazo metal or that contain metal or disazo dyes, and when dyestuff was metal complexes, it is first preferably
1: 1 copper complex or 1: 2 chromic compound or 1: 2 cobalt complex form, the copper or the nickel complex of phthalocyanine or triphendioxazine dyestuff.
The preferably independent separately direct key of expression of X or-SO
2-.
The preferably independent separately expression C of Alk
2-3Alkylidene group.
R
1Any alkyl of expression preferably contains 1 or 2 carbon atom.
R
1The alkyl of any replacement of expression is C preferably
1-3Alkyl, and wherein preferably contain one be selected from hydroxyl ,-SO
3H ,-OSO
3H or-COOH(hydroxyl especially) substituting group.
All R
1Be R
1A is better, wherein R
1A independently represent separately hydrogen, methyl, ethyl, 2-hydroxyethyl ,-(CH
2)
r-SO
3H ,-(CH
2)
r-OSO
3H or-(CH
2)
q-COOH, wherein r is 1 or 2, and q is 1,2 or 3.
All R
1Be R
1bR better, wherein
1bIndependent separately expression hydrogen, methyl, ethyl or 2-hydroxyethyl.Best each R
1All be hydrogen.
All R
2Be R
2aBetter, R wherein
2aIndependent separately expression hydrogen, methyl, methoxyl group ,-COOH or-SO
3H.All R
2Be R
2bR better, wherein
2bIndependent separately expression hydrogen or-SO
3H.
All B
1Be B
1aBetter, B wherein
1aIndependent separately expression C
2-4Alkylidene group, C
2-3Alkylidene group-O-C
2-3Alkylidene group, C
2-3Alkylidene group
The C that alkylidene group, monohydroxy replace
3-4Alkylidene group,
N in the formula
1Be 0,1,2 or 3.
All B
1Be B
1bB better, wherein
1bIndependent separately expression C
2-3The C that alkylidene group, monohydroxy replace
3-4Alkylidene group,
N in the formula
2Be 0,1 or 2.
All B
1Be B
1cBest, B wherein
1cIndependent separately expression C
2-3The C that alkylidene group or monohydroxy replace
3-4Alkylidene group.
All W are W
1Better, W wherein
1Independent separately expression
All W are W
2Better, W
2Independent separately expression
All W are W
3Best, W wherein
3Independent separately expression-NH-B
1c-NH-.
The formula I compound that does not have metal or metal complexes form preferably is corresponding to the compound shown in the formula that limits below (1) to (7):
Compound (1)
DK is the group of benzene type or naphthalene type diazonium composition in the formula,
KK be benzene type, naphthalene type or heterocyclic type coupling composition or can be by the group of the CH-acidic cpd of enolization,
Z is
W as above limits in the formula,
B is 1 or 2,
One of them or two group Z pass through
Link on diazonium and/or the coupling composition.
Preferably b is 1.
In the compound (1):
DK is in the group (a) to (h) preferably, and each key that is marked with asterisk all links to each other with azo-group in these groups,
R in the formula
1And R
2Definition the same,
R
3Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, kharophen, benzamido ,-SO
3H or-COR
13,
R
4Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group or-COR
13,
R
13Be-OH ,-OC
1-4Alkyl or-NH
2,
Alk
1Be-C
2-3Alkylidene group,
R
5Be hydrogen ,-SO
3H, C
1-4Alkyl or C
2-4Hydroxyalkyl,
R
50Be hydrogen or-SO
3H,
R
51Be
N is 0,1,2,3 or 4,
P is 0,1 or 2,
Q be 1,2 or 3 and
R is 1 or 2;
KK is (K preferably
1)-(K
7One of) group, wherein be marked with the position of the carbon atom of asterisk for the generation coupling,
R in the formula
1Define the same,
R
6Be hydrogen, C
1-4Alkyl or C
1-4Alkoxyl group and
R
7Be hydrogen, halogen, C
1-4Alkyl, C
1-4The alcoxyl formula ,-NHCOC
1-4Alkyl or-NHCONH
2;
R in the formula
1Definition the same,
R
8Be hydrogen, halogen, C
1-4Alkyl or C
1-4Alkoxyl group,
R
9Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or SO
3H and
R
10Be hydrogen ,-SO
3H or-NH
1-(Z);
R in the formula
11Be-OH or-NH
2,
R
12Be C
1-4Alkyl or-COR
13,
R
13Definition the same,
Q
1Be hydrogen, C
1-4Alkyl or
R
8And R
9Definition the same and
R
14Be hydrogen, halogen, C
1-4Alkyl,
,
-SO
3H or-(B
3)
a-
-(Z)
R wherein
1The same with a definition, B
3It is divalent bridging group;
Q in the formula
2Be hydrogen, C
1-4Alkyl, C
5-6Cycloalkyl, phenyl or phenyl (C
1-4Alkyl) (wherein each phenyl ring is unsubstituted or is selected from C by 1-3
1-4Alkyl, C
1-4Alkoxyl group, halogen ,-COOH and-SO
3The substituting group of H replaces) ,-COR
13Or quilt-SO
3H ,-OSO
3H or-COR
13Mono-substituted C
1-4Alkyl, Q
3Be hydrogen ,-CN ,-SO
3H ,-COR
13, C
1-4Alkyl, quilt-OH, halogen ,-CN, C
1-4Alkoxyl group,
,-SO
3H ,-OSO
3H or-NH
2
Mono-substituted C
1-4Alkyl ,-SO
2NH
2,
R in the formula
15Be hydrogen, C
1-4Alkyl or C
2-4Hydroxyalkyl, and
An
-Be non-color development negatively charged ion,
Q
4Be hydrogen,
, C
1-6Alkyl, C
2-4Alkenyl, C
2-4Alkynyl, C
5-6Cycloalkyl, phenyl or phenyl
(C
1-4Alkyl) (wherein each phenyl ring is unsubstituted or is selected from halogen, C by 1-3
1-4Alkyl, C
1-4Alkoxyl group ,-SO
3H ,-COOH and-N-(Z) substituting group replaces), or-C
1-6Alkylidene group-Y, Y is-COOH in the formula ,-COOC
1-4Alkyl ,-SO
3H ,-OSO
3H ,-OH ,-CN, C
1-4Alkoxyl group ,-NH
2Or one can be protonated aliphatic series, cyclic aliphatic, aromatics or heterocyclic amino or quaternary ammonium group,
B
2Be C
2-6Alkylidene group, the C that monohydroxy replaces
3-6Alkylidene group, have between one-O-or-NR
1C
2-6Alkylidene chain,
-B
2-NR
1-(Z) be-C
2-4And R alkylidene group-N N-(Z),
1, R
9, R
10And R
13Define the same;
R in the formula
16Be C
1-4Alkyl, phenyl or be selected from halogen, C by 1-3
1-4Alkyl and C
1-4The phenyl that the substituting group of alkoxyl group replaces,
R
1, a and m definition is the same.
Compound (2)
R in the formula
6, R
7, R
1It is the same with the Z definition,
T is 2 or 3,
R
6XHas R independently
6A kind of in the implication and
R
7XHas R independently
7A kind of in the implication.
Compound (2) is R wherein preferably
6, R
6XAnd R
7XRespectively the do for oneself compound of hydrogen.
The compound that provides (3) is for based on following no metallic compound (3a) or metal complexes (3b), is preferably 1: 1 copper complex and 1: 2 chromic compound or 1: 2 cobalt complex,
R in the formula
1, Z and m definition is the same,
A is
In the formula m and q the definition the same,
R
17Be hydrogen, halogen, nitro, C
1-4Alkyl, C
1-4Alkoxyl group ,-COR
13,-SO
3H or-NHCOCH
3,
R
22Be OH, OCH
3Or NH
2And
R
13Define the same.
In 1: 2 chromic compound or 1: 2 cobalt complex, two azo-compounds can be identical or different, and promptly it is symmetric or asymmetric 1: 2 metal complexes.
Good especially 1: 1 copper complex that is based on compound (3a), wherein A is the group of benzene type diazonium composition, and the group of naphthalene type coupling composition is shown below,
In addition, also have 1: 1 copper complex corresponding to following formula (3c)-(3e):
R wherein
50Be hydrogen or SO
3H,
R
1, Z and r definition is the same;
R in the formula
52Be hydrogen, C
1-4Alkyl or C
1-4Alkoxyl group,
M is 0 or 1, and r is 1 or 2,
M+r is 2 or 3,
R
1, R
2, R
50The same with the Z definition;
D in the formula
3Be
R wherein
29Be hydrogen, COOH or SO
3H,
R
30Be hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group or-O-Alk
1-OR
5, and t, R
5And Alk
1Define the same,
R
1, R
52The same with the Z definition.
Compound (4)
D in the formula
1And D
2Independent separately expression contains the group of the diazonium composition of the amino-benzene of sulfo group, sulfonamido or a carboxyl or amino naphthalenes series at least,
Each m is 0 or 1, is 1 but require at least one m,
R
1, z and n definition is the same.
D
1Be D
1aBetter, D
1aBe formula (ax) or (cx) group,
R in the formula
18Be sulfo group, sulfonamido or-COR
13,
R
19Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-NHCOCH
3Or SO
3H,
R
13, m and p definition is the same,
M+p is 1 or 2.
D
2Be D
2aBetter, D
2aBe formula (dx) group,
R in the formula
4And R
18Define the same, being keyed on the azo-group of asterisk, another free linkage is received on the active group.
Better, (dx) R in the group
182 (azo-group is at 1), and the free linkage that is connected on the active group exists
4 or 5.
Compound (5)
X in the formula
1And X
2In one of be-O-, and another is a carboxyl,
R
20And R
21Independent separately expression hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COR
13Or-NHCO(C
1-4Alkyl),
R
1, R
13, Z and m definition is the same,
P independently represents 0,1 or 2 separately, and
M+2p is 2 at least.
Compound (6) and composition thereof
In the formula Q be-O-or-S-,
R
23Independent separately expression hydrogen or-SO
2CH
2CH
2OSO
3H,
M independently represents 0 or 1 separately,
X
3Independent separately expression-SO
2-,-NR
1-,-* CONR
1-, or-* SO
2NR
1, wherein the atom of asterisk is connected on the ring system carbon atom,
Alk
2Independent separately expression C
2-4Alkylidene group, and
R
1Independently represent above-mentioned definition separately with Z,
In a compound (6), two Z are preferably identical.
Compound (7) and composition thereof
C is 1,2 or 3 in the formula,
D is 0,1 or 2, but requires c+d to be not more than 3;
Pc is the phthalocyanine base,
Me is copper, nickel, cobalt, iron or aluminium,
R
24And R
25Independent separately expression hydrogen or C
1-6Alkyl, or-NR
24R
25Be can comprise again one-O-or
5 or 6 saturated element heterocycle, wherein R
31Be hydrogen, C
1-4Alkyl, 2-hydroxyethyl or 2-amino-ethyl, R
26Be hydrogen, halogen, hydroxyl, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or-SO
3H,
A is 0 or 1,
X
4Be randomly to contain
Aliphatic series, araliphatic or the heterocyclic bridged group of divalence,
Or-N=N-KK
2, KK wherein
2Be
R
9, R
11, R
12, Q
2,-B
2-,-B
3-and a definition is the same,
Each carbon atom that indicates asterisk is pointed out coupling position,
Q
3A is a hydrogen, CN ,-SO
3H ,-COR
13, C
1-4Alkyl, by hydroxyl, halogen ,-CN, C
1-4Alkoxyl group-SO
3H ,-OSO
3H or-NH
2; Mono-substituted C
1-4Alkyl ,-SO
2NH
2;
R wherein
9, R
13, R
15And An
-Define the same.
Fiber-reactive groups Z is better corresponding to the group of Za structure,
Z is that Zb is better, and wherein Zb is W
1Equal W
2The Za group.
Z is that Zc is best, and wherein Zc is W
1Equal W
3The Za group.
Formula (1) compound is the compound corresponding to formula (1a)～(1d) preferably: formula (1a) compound
Za definition is the same and be connected in DK in the formula
1Or KK
1On,
DK
1Be (a
1)～(f
1) one of group or group (h
1), the key that wherein indicates asterisk is connected on the azo-group:
P is 0,1 or 2 in the formula,
R
3aAnd R
4A independently represents hydrogen separately, chlorine, methyl, methoxyl group, oxyethyl group or-COOH;
T is 2 or 3,
R
5A is a hydrogen, methyl, ethyl ,-SO
3H or 2-hydroxyethyl;
R is 1 or 2,
M+r is 2 or 3;
R in the formula
1B, R
4A and p definition are the same;
R in the formula
1B and r definition are the same;
R in the formula
51A is
Or
R
50, R
1B, a and r definition are the same;
KK
1Be (the K that limits below
2A), (K
4A) with (K
5A) one of group shown in the or (K that limits above
3) group:
R
9A is a hydrogen, chlorine, methyl, methoxyl group ,-SO
3H or-COOH,
R
10A is a hydrogen ,-SO
3H or
(Za);
R
12A is a methyl ,-COOH or-CONH
2,
R
14A is a hydrogen, chlorine, methyl, ethyl ,-SO
3H or
(Za);
-COR
13,-CH
2SO
3H or-CH
2OSO
3H,
Q
3B is a hydrogen ,-CN ,-SO
3H ,-COR
13,
Methyl, ethyl ,-CH
2SO
3H or-CH
2NH
2,
Q
4A is a hydrogen,
Methyl, ethyl, cyclohexyl, phenyl or
Phenyl (C
1-2Alkyl), in the back in two groups, phenyl ring be unsubstituted or by 1 or 2 be selected from chlorine, methyl, methoxyl group ,-SO
3H ,-COOH ,-NH
2With
(Za) substituting group replaces, or-C
1-4Alkylidene group-Y
2,
B
2A is-C
2-4Alkylidene group, monohydroxy replaces-C
3-4Alkylidene group-,
,-C
1-2Alkylidene group
Or
Alkylidene group
Or B
2A and be attached thereto
(Za) form together
-C
2-3Alkylidene group
,-(Z
a),
Y
2Be-COOH-SO
3H ,-OSO
3H ,-OH ,-CN, methoxyl group or-NR
27R
28, R
27And R
28Independent separately expression hydrogen, unsubstituted C
1-4Alkyl is by hydroxyl, C
1-4Alkoxyl group ,-COOH ,-SO
3H ,-NH(C
1-4Alkyl) or N(C
1-4Alkyl)
2Mono-substituted C
1-4Alkyl, unsubstituted cyclohexyl is by 1-3 methyl substituted cyclohexyl, phenyl or phenyl (C
1-4Alkyl), wherein each phenyl ring is unsubstituted or is selected from halogen (preferably chlorine), C by 1 or 2
1-4Alkyl, C
1-4Alkoxyl group ,-SO
3H and-substituting group of COOH replaces, perhaps-NR
27R
28Be piperidines, morpholine or a piperazine ring, wherein each ring is unsubstituted or contains 1～3 methyl;
Formula (1b) compound,
M+r equals 2 or 3 in the formula,
R
6aBe hydrogen, methyl or methoxy,
R
7aBe hydrogen, chlorine, methyl, methoxyl group ,-NHCOCH
3Or-NHCONH
2; Formula (1c) compound,
DK in the formula
2Be the formula (a that limits above
1), (b
1) or (c
1) group; Formula (1d) compound,
Sulfo group is at 3 or 4 of naphthalene nucleus in the formula,
DK
3Be formula (a
2) or (c
2) group,
M+p equals 1 or 2 in the formula.
Compound (2) is corresponding to formula (2a) preferably,
R in the formula
7aDefine the samely, m+r equals 2 or 3.
Compound (3) is based on no metallic compound (3a preferably
1) or (3b
1) 1: 1 copper complex,
Wherein
R
17aBe hydrogen, chlorine, bromine, nitro, methyl, methoxyl group,
-SO
3H or-COOH,
R
22aBe OH or OCH
3, and
M+r equals 2 or 3;
R in the formula
22aDefine the same.
In addition, compound (3) also has corresponding to following general formula (3c preferably
1), (3d
1) and (3e
1) 1: 1 copper complex,
In the formula
R
50And R
2aDefine the same,
R
52aBe hydrogen, methyl or methoxy,
D
3a 
R in the formula
30aBe hydrogen, methyl or methoxy.
Compound (4) is formula (4a) compound preferably,
D in the formula
1a, R
4And R
18Define the same;
Be more preferably following formula (4a) compound: R wherein
4Be hydrogen, R
182 of phenyl, and
Formula (5) compound is R wherein preferably
20And R
21Respectively be R
20aAnd R
21aCompound, and R
20aAnd R
21aIndependent separately expression hydrogen, chlorine, methyl, methoxyl group ,-COOH or-NHCOCH
3
Compound (6) is following compound preferably:
Wherein Q is-O-,
X
3Independent separately expression
R
1Independent separately expression R
1b,
Alk
2Independent separately expression-C
2-3Alkylidene group-,
Z independently represents Za separately.
Better compound (6) is two identical compounds of group that contain Za wherein.
Compound (7) is that wherein Me is copper or nickel and R preferably
24And R
25Respectively be those compounds of hydrogen.
Better compound (7) is following compound:
Wherein Me is copper or nickel,
C is 2 or 3, and d is 0,
R
1Independent separately expression R
1B,
Z is Za,
R
26Be hydrogen ,-COOH or-SO
3H, and
A is 0, or
A is 1 and X
4Be-N=N-KK
2, KK wherein
2Be
Q in the formula
2a, Q
3bWith-B
2a-definition is the same.
In addition, good especially situation is in above-mentioned all good no metallic compounds and metal complexes
(1) Za is Zb;
(2) Za is Zc;
(3) Za is Zc, and R
1bBe hydrogen.
When formula I compound is the form of salt, not strict with sulfo group and any carboxyl bonded positively charged ion, can be any non-color development positively charged ion of those routines in the fibre-reactive dyes field, be water miscible but require corresponding salt.These cationic examples have alkali metal cation and ammonium ion unsubstituted and that replace, as lithium, sodium, and potassium, ammonium, one, two, three and tetramethyl-ammonium, triethyl ammonium and, two and the triethanol ammonium plasma.
Positively charged ion is alkali metal cation and ammonium ion preferably, and is best with sodium ion.
Can be identical or different in the formula I compound with sulfo group and any carboxyl bonded positively charged ion, for example above-mentioned positively charged ion can be mixed and use, this means that formula I compound can be the mixing salt form.
The present invention further provides the preparation method of formula I compound and composition thereof, comprised making formula II compound or its mixture at Y
3Be-during W-H and 5-cyano group-2,4, the reaction of 6-trichloropyrimidine is perhaps at Y
3When being chlorine and formula III compound (by formula II compound and 1: 1 mol ratio of formula III compound) reaction,
Y in the formula
3Be-W-H or chlorine Fc, X, R
1, Alk, a, b and W definition be the same,
The W definition is the same in the formula.
Y in the formula II compound
3Be-W-H is better.Formula II (Y
3Be-W-H) compound and 5-cyano group-2,4 that the condensation reaction of 6-trichloropyrimidine is suitable for carrying out under the condition of 0-40 ℃ and pH7-9.Usually be reaction medium with water, but when 5-cyano group-2,4, when the 6-trichloropyrimidine was dissolved in organic solvent such as the acetone, it also can use.
In addition, the tetrazo compound of formula (4) also can be by making formula IV compound diazotization and prepare with formula V compound alkaline coupling,
D in the formula
2, R
1, Z, m and n definition is the same,
D in the formula
1, R
1, Z, m and n definition is the same.
Formula I compound can be according to currently known methods, and for example Chang Gui use an alkali metal salt is saltoutd, filtered and dry (when needing vacuum available and improve temperature a little), separates.
According to reaction conditions and separation condition, the formula I compound that obtains be free acid or reasonable be contain one or more above-mentioned cationic salt for example form or or even mixing salt form.Can by ordinary method make its from free acid form change into salt or mixing salt form, perhaps press reverse direction and change, perhaps change the form of another kind of salt into from a kind of salt.
The initial compounds of formula II, III, IV and V or known substance, or can be according to currently known methods by known feedstock production.
Formula I compound and composition thereof can be used as fibre-reactive dyes hydroxyl or nitrogenous organic pollutant is dyeed or stamp.Matrix is leather or the filamentary material that contains following material or be made of described material preferably; Natural or synthesizing polyamides, particularly natural or regenerated cellulose is as cotton, viscose fiber and SPUN RAYON YARNS.Best matrix is the textile materials that contains cotton or be made of cotton.
Dyeing or stamp are to carry out according to fibre-reactive dyes field currently known methods commonly used.For formula I compound, in 30-80 ℃ of temperature range, use dip method.
The compounds of this invention can be compatible well with other fibre-reactive dyes; They can use separately, also can with the suitable allied fiber chemically-reactive dyes keying action with similar dyeing behavior, these performances comprise common dyefastness for example, by dye vat to dyeing capacity size of fiber or the like.The color fastness that dyes with this binding substances is good, and is comparable to the Color that obtains with homogencous dyes.
From their significant assembly ability, formula I compound has good dye uptake and degree of fixation.There is not that a part of dyestuff of set to take off from the matrix upper punch at an easy rate.Resulting dyeing and stamp show to have the good dry state and the light fastness of hygrometric state, and it is all fine also to have good moisture-proof fastness such as washable, water-fast, sea water resistance and a color fastness to perspiration.They also can anti-oxidantly influence, and for example can resist chloride water, hypo(chlorite)bleaching liquid and contain superoxide or the oxygenizement of the washings of perborate.
Further specify the present invention with following example.All umbers and per-cent all are by weight or volumeter in the example.Temperature is degree centigrade.
Example 1
In 18.3 parts in 500 parts of water (0.025 mole) formula B compounds, once add 6.1 parts of (20% is excessive) 5-cyano group-2,4,6-trichloropyrimidine acetone soln at 25 ℃.Continue to add 20% sodium carbonate solution, make the pH value of the spontaneous reduction of mixture remain on 7-7.5.It is 35 ℃ that the while heated mixt reaches outlet temperature.After 3-4 hour, TLC proves that this condensation reaction stops.
For reaction product isolated, with gained darker red orange solution be heated to 40 ℃ and with filter clay stir about 10 minutes.Filter then, in filtrate, add sodium-chlor (about 10% volume) while stirring.Leach thin throw out and in about 50 ℃ of vacuum-dryings.Dyestuff shown in the following formula of gained is dyed cotton products orange.Moisture-proof fastness ability that dyeing that obtains on cotton products by usual method and stamp show and good light fastness, in addition, they also have antioxygenation.
The preparation of initial compounds B
A) with 9.6 parts of 2-amino naphthalenes-3,6, the 8-trisulfonic acid is dissolved in 60 parts of water of the pH12 that adds 4.3 part of 30% sodium hydroxide solution.In this solution, drip 11 part of 30% hydrochloric acid, obtain a kind of suspension, it is fully stirred.Add after 25 parts of ice, add 6.5 parts of 4N sodium nitrite solutions at 0-5 ° and carry out diazotization reaction.This diazonium salt solution was added in 30 minutes in 3-7 ℃ the suspension of being made up of in 25 portions of frozen water 3.9 parts of 3-aminophenyl ureas.In the reinforced process, add 22 part of 20% sodium carbonate solution, make pH remain on 5.0.The aminoazo-compound that contains formula A in the red solution that forms.
B) with 30 minutes 5.1 parts of cyanuryl chlorides stirrings are joined in 30 portions of frozen water.In 5 minutes, add a) step gained dye solution then, add 8 part of 20% sodium carbonate solution, carry out condensation reaction at pH6.0.Be added in the reddish orange solution that obtains contain in 50 portions of frozen water 3.3 parts of 1, add 8 part of 30% hydrochloric acid and its pH transferred to 6.0 solution.In 1 hour, the temperature of this reaction mixture slowly is raised to 48-50 ℃.Simultaneously, adding 20 part of 20% sodium carbonate solution makes mixture pH remain on 6.0.Before this orange dye that separates formation, add 100 parts of sodium-chlor, make its precipitation.So just obtain formula B compound.
Example 2-200
According to the similar method of example 1 described method, with suitable initial compounds to form required color development part Fc, the no metallic compound shown in the listed formula I of table 1-11 below can further making.Top at all these tables has all provided the corresponding structure formula, the symbol in the formula as the table defined in.
Example 2-200 compound can be used to the matrix that contains cellulosic fibre or be made of cellulosic fibre according to the dip method of routine or printing technology, especially for the textile materials that is made of cotton yarn, obtains specifying the dyeing and the stamp of tone.Light fastness that dyeing that obtains on cotton products and stamp show and moisture-proof fastness ability, and oxygenizement had resistance.
In table 1 and each table thereafter-divalent group that the W-hurdle limits can be asymmetric diamino group.Usually, the connection between the pyrimidine carbon atom of Yi Bian triazine carbon atom and the other side is by in sequence given.But when the condensation product of pyrimidine compound and diamines was used as initial compounds, according to the preparation method of initial compounds, this connection order also may promptly become pyrimidine/triazine ring mode conversely.
Dyestuff with example 176-200 dyes and stamp to cotton products respectively, presents orange.
Example 201
Dyestuff shown in 15.6 parts of (0.02mol) following formulas is dissolved in the water of 300 parts of pH8.5-9.
Add small amount of hydrochloric acid and transfer pH to 6.0.Under 10-15 ℃ and agitation condition, in this solution, add 3.9 parts of (0.02mol+5%) cyanuryl chlorides, and be 5.5-6.5 by adding sodium hydroxide solution maintenance pH.Afterreaction was finished in about 1 hour.
In this reaction mixture (0.02mol), add 1.6 parts of (0.02mol+10%) 1.Carry out condensation at 40-50 ℃, add sodium hydroxide solution pH is remained on 5.5-6.5.Afterreaction was finished in about 2 hours.
In the thin dye suspensions (0.02mol) that obtains, add 4.6 parts of (0.02mol+10%) 5-cyano group-2,4, the 6-trichloropyrimidine.React with pH8.5-9.0 at 15-20 ℃.Isolate dyestuff by the saltouing of routine, filtration and drying means corresponding to following formula,
It dyes blueness with cotton products.The color of these cotton products has high fast light and moisture resistance properties, and can antioxygenation.
Example 202-291
According to example 201 described similar approach, make required color development part Fc with suitable initial compounds, further make the containing metal compound of the listed formula I of following table 12-17.Provide the corresponding structure formula at the top of each table, the symbol in the formula limits in table.
Adopt conventional dip method or printing technology, the metal complexes of example 202-291 will contain cellulosic fibre or the matrix (especially cotton-spinning fabric) that is made of cellulosic fibre is dyed specified tone.So dyeing and the stamp on the cotton products that form has high fast light or moisture resistance properties, and can antioxygenation.
The dyestuff of example 269-291 is dyed blueness with cotton products.
Example 292
45.3 parts are dissolved in 700 parts of water according to the monoazo-dyes shown in the following formula of currently known methods preparation,
Descend with 30 minutes toward wherein adding 18.5 parts of solid cyanuryl chlorides at 20-25 ℃.Stir the mixture at pH6.0-6.5, until no longer detecting free amine group.Then, add 11.1 parts of 1, reaction mixture was stirred 2 hours, add rare sodium carbonate solution simultaneously and keep pH7.0.Add sodium-chlor, make condensation product saltout out, filter.The wet mashed prod that obtains is dissolved in 900 parts of water.In this solution, add 24.9 parts of 5-cyano group-2,4, the 6-trichloropyrimidine, and 0-5 ℃ of stirring 2 hours.Make pH remain on 8-9 by adding rare sodium carbonate solution in the reaction process.Make the gained dye precipitated with sodium-chlor, separate.It is corresponding to following structural formula
This dyestuff is the garnet powder after the drying, presents redness when it is water-soluble, cotton products can be dyed scarlet.These colors that dye have good fast light and moisture resistance properties, and can antioxygenation.
Example 293-319
According to example 292 described similar approach,, can make other formula I compounds with suitable initial compounds.They are corresponding to structural formula (T18)
Symbol wherein provides definition in the following Table 18.The color that dyes on cotton products with the dyestuff of example 293-319 has good fast light and moisture resistance properties, and can antioxygenation.
In the end provided the dyeing on each comfortable cotton products in the hurdle I, wherein d is orange, and k is a scarlet.
Instance number R
3R
4-W-l
293 OC
2H
5H
k
294 OCH
3SO
3H do. k
295 -OC
2H
4OH H do. k
296 OCH
3H
k
297 do. SO
3H do. k
298 -OC
2H
4OH H do. k
299 OCH
3H
k
Example 320
In the mixture of 10 parts of water and 20 parts of ice, 5 parts of cyanuryl chlorides are stirred into unit for uniform suspension.The neutral solution that adds the pH7 of tetra-na salt in 160 parts of water of 30 parts of following formula dyestuffs in this suspension,
Under 5 ℃ and pH5.5-6.0 condition, stir, up to no longer detecting free amine group.At pH6.5-7.0 temperature slowly is raised to 15 ℃, adds 3.25 parts then, 1.Adding hydrochloric acid makes pH remain on 6.0.Mixture reacts completely after this section period 50 ℃ of heating 3 hours.Add 70 parts of sodium-chlor again, filter this red suspension.With 500 part of 20% sodium chloride solution filter wash cake.The gained mashed prod is placed 500 parts of water, add 4.5 parts of 5-cyano group-2,4, the 6-trichloropyrimidine.Stirred 12 hours at 20 °,, add 80 parts of sodium-chlor then until reacting completely.The dyestuff that obtains is precipitated and filter; It is corresponding to following structural formula:
After this dyestuff drying is the garnet powder, shows red when water-soluble, and it is blue red that the cotton products that dye are.The total fastness ability of the color that dyes on cotton products is fine.
Example 321-416
With the similar approach described in the example 320,, also made other listed formula I compound among the following table 19-22 with suitable initial compounds.At the top of each table, provided the corresponding structure formula, symbol wherein provides definition in showing below.Dyestuff dip method routinely with example 321-416 can be with cellulosic fibre, especially cotton products dyeing.The all colours that dyes all is blue red, and fastness is strong.
Example 417
212 parts of cyanuryl chlorides were stirred 45 minutes in 560 parts of ice and 200 parts of water.Toward wherein adding by 190 part 2 in 920 parts of water and 112 part of 30% sodium hydroxide solution, the solution that 4-diaminobenzene-1-sulfonic acid constitutes stirs this mixture 6 hours under the ice bath cooling.Subsequently with this white suspension indirect diazotization.
, press currently known methods therebetween with 140 parts of 4-benzaminic acid diazotization, and under the acid-reaction condition with 320 parts of 1-amino-8-hydroxyl naphthalene-3, the coupling of 6-disulfonic acid.In this red suspension, add above-mentioned diazo solution, carry out alkaline coupling.
In the blue solution that obtains, add 120 parts of 1.Condensation reaction was carried out 2 hours.Use sodium-chlor (25% volume) that reaction mixture is saltoutd then, filter.Blue filter cake is dissolved in again in the water of 10 times of amounts.
In two hours, add in this aqueous solution and in 350 parts of water and 150 parts of ice, stir 175 parts of 5-cyano group-2,4 of 45 minutes, the suspension of 6-trichloropyrimidine.The pH of this reaction mixture was kept 3 hours 9.Add sodium-chlor (10% volume) and make products therefrom saltout out, filter, filter cake is 40 ℃ of vacuum-dryings.This dyestuff has following structural formula,
This dyestuff is dyed navy with cellulosic fibre, particularly cotton products.This look has good fastness ability, as fast light and moisture resistance properties, and can antioxygenation.
Example 418-456
According to example 417 described similar approach, with suitable initial compounds, can make other formula I compound, they are corresponding to compound shown in the formula (T23),
Symbol in the formula provides definition in the following Table 23.Adopt conventional dip method, this example 418-456 dyestuff is dyed navy with cellulosic fibre, particularly cotton products.These dyeing have good various conventional fastness ability.
Example 457
65.9 parts of following formula dyestuffs by the currently known methods preparation are dissolved in 1200 parts of water.At 20-25 ° with adding 37 parts of solid cyanuryl chlorides in 30 minutes.By add dilute sodium carbonate solution continuously in mixture, maintenance pH is 6.0-6.5, stirs 1 hour.Add 22.2 parts of 1, stirred 2 hours, add dilute sodium carbonate solution simultaneously, keep pH7.0 at 40-50 ℃.Make condensation product saltout out with sodium-chlor, filter.The gained mashed prod is dissolved in 1400 parts of water.Add 49.5 parts of 5-cyano group-2,4 in this solution, the 6-trichloropyrimidine stirred 2 hours at 5-10 ℃.Adding dilute sodium carbonate solution in reaction process makes pH remain on 8-9.Add sodium-chlor the gained dye salt is separated out, separate.It is corresponding to following structural formula, and dry back is a black powder, is mazarine after water-soluble, and this dyestuff is dyed mazarine with cotton products.This dyeing has good fast light and moisture-proof fastness.
Example 458-472
Can make other formula I compound according to example 457 described similar approach.They are corresponding to structural formula (T24).
Symbol in the formula provides definition in the following Table 24.The dyestuff of example 458-472 is dyed mazarine with cotton products.These dyeing have good fast light and moisture resistance properties.
Table 24/ formula (T24) compound
Example 473
25.7 parts of (0.025mol) dyestuffs (press currently known methods with the copper phthalocyanine chlorosulphonation, then with 1,3-diaminobenzene-4-sulfonic acid reaction makes, and on average contains 2.5 carbonyldioxies and 1 sulfonamido in each molecule approximately) are dissolved in the water of 200 parts of pH6.5-7.0.Add after 150 parts of ice, add 4.6 parts of cyanuryl chlorides, stirred two hours at pH6.0-6.5 at 0-5 ℃.Add 2.8 parts of 1 then, after 1 hour, make temperature in two hours, be raised to 30-35 ℃, add 20% sodium carbonate solution pH is transferred to 7.5-8.0 0-5 ° of stirring.To separate out also with 70 parts of sodium chloride salts, filtering reaction product be dissolved in 250 parts of water again.Add 6.3 parts of 5-cyano group 2,4 at 0-5 ℃, the 6-trichloropyrimidine stirred the mixture under this temperature 3 hours.By adding yellow soda ash pH is remained on 8-8.5 simultaneously.After condensation reaction is finished, make mixture salt plate with 45 parts of sodium-chlor.Suction filtration goes out sedimentary dyestuff and 35 ℃ of dryings.The dyestuff that obtains is corresponding to following structural formula,
It dyes cellulosic fibre, especially cotton products bright-coloured dark green.These dyeing have good light fastness and fabulous moisture-proof fastness ability.
Example 474
According to example 473 described methods, with 25.7 parts of copper phthalocyaine dyes of nickel phthalocyanine dye (i.e. 25.5 parts (0.025mol)) replacement of equivalent.Obtain corresponding [NiPc] dyestuff (its structural formula is similar to the formula that example 473 is given), it dyes blue-greenish colour with cotton products.This dyeing has good fastness ability.
Example 475-480
According to being similar to example 473 and 474 described methods, can make the other phthalocyanine pigment.They are corresponding to following structural formula,
The definition of the symbol in the formula provides in the following Table 25.
In the end provided the tone of separately cotton products being dyed in the hurdle I, wherein e is bright dark green, and f is a blue-greenish colour.
These dyeing have good fastness ability.
Table 25/ formula (T25) compound
Example 481
25.5 parts of dyestuffs (press currently known methods with the nickel phthalocyanine chlorosulphonation, then with 1,3-diaminobenzene-4-sulfonic acid reaction makes, and on average contains 2.5 sulfonic groups and 1 sulfonamido in each molecule approximately) are stirred with 1.8 parts of Sodium Nitrites in 150 parts of water.This solution is chilled to 0-2 °, is added drop-wise in 100 parts of mixture of ice and water and 12 part of 30% hydrochloric acid.Then the gained diazonium salt suspension is added to by 5.9 parts of 1-(3 '-methylamino propyl group)-solution that 6-hydroxy-4-methyl pyridone-(2) constitute in 300 parts of ice/water in, maintain the temperature at 0-5 ℃ simultaneously.In the coupled reaction process, make mixture pH remain on 9-9.5 by adding 30% sodium hydroxide solution.By being similar to the method described in the example 473, make gained green solution priority and cyanuryl chloride, 1 and 5-cyano group-2,4, the reaction of 6-trichloropyrimidine obtains the dyestuff shown in the following formula,
By example 473 described similar approach it is separated.This dyestuff is dyed emerald green with cellulosic fibre, especially cotton products.These dyeing have high light fastness and fabulous moisture-proof fastness.
Example 482-519
Can make the other phthalocyanine pigment according to example 481 described similar approach.They have following structural formula,
Symbol in the formula provides definition in the table 26 and 27 below.
The dyestuff of example 482-519 is dyed green with cotton, and when using nickel phthalocyanine, color is more bright-coloured.These dyeing have well fast light and moisture-proof fastness.
Example 520
According to example 481 described similar approach, with suitable initial compounds, can make and isolate the dyestuff shown in the following formula,
It dyes bright-coloured green with cotton products.The color that is dyed has good fast light and moisture-proof fastness.
According to described method, can obtain the sodium-salt form of example 1-520 dyestuff.According to different reaction/separation conditions, or by currently known methods this sodium salt is reacted, also can obtain their free acid form or other salt form, for example those contain one or more above-mentioned cationic salt.
The application of explanation The compounds of this invention in the example below.
Application example A
The dyestuff of 0.3 part of example 1 is dissolved in 300 parts of softening waters, adds 15 parts of saltcake (baking).Dye vat is heated to 40 °, adds 10 parts of cotton fabrics of bleaching then.40 ° keep 30 minutes after, in cylinder, add 6 parts of yellow soda ash (baking) in batches, added once every 10 minutes, added amount is followed successively by 0.2,0.6,1.2 and last 4.0 parts.In adding the process of yellow soda ash, temperature remains on 40 °.Dyed again 1 hour at 40 ° then.
The cotton fabric that will dye is with cold flowing water rinsing 3 minutes, the flowing water rinsing of reusable heat afterwards 3 minutes then.Fabric boiling washing after in containing 500 parts of softening waters of 0.25 part of commercially available anion active washing composition, will dying 15 minutes.After mobile hot water rinsing 3 minutes and centrifugal treating, the fabric that dyed is dry in about 70 ℃ desiccator cabinet.The orange fast light and moisture-proof fastness that shows of the cotton fabric that obtains, and can antioxygenation.
Application example B
In the dye vat that fills 300 parts of softening waters, add 10 parts of saltcake (baking), 10 parts of cotton fabrics (bleaching).In 10 minutes, dye vat is heated to 40 ℃, adds the dyestuff of 0.5 part of example 1.Add 3 parts of baked yellow soda ash at 40 ℃ after keeping 30 minutes again, continued again to dye 45 minutes at 40 ℃.
The method that the fabric that dyed provides by application example A is successively used cold flow water and hot-fluid water rinse, and boiling washing.After rinsing and the drying, the cotton fabric that obtains orange has the same good fastness ability of pointing out with application example 1.
Application example C
Method described in the application example A is done some change, use the dyestuff of 0.3 part of example 481, only with 2 parts of baked yellow soda ash and once adding, the yellow soda ash that the total amount that replacement adds is 6 parts in batches.40 ℃ of starting temperatures are brought up to 60 ℃, and the dyeing course of back carried out 1 hour at 60 ℃.In others, adopt the described method of application example A similarly.The cotton fabric dyeing process that obtains is bright-coloured green, and pile-on properties is good, and shows good light fastness.
Application example D
The dyestuff of 2.5 parts of examples 473 is dissolved in 2000 parts of water.Add 100 parts of cotton fabrics, in 10 minutes, the dye vat temperature is brought up to 80 ℃.Add 100 parts of baked saltcake, add 20 parts of baked yellow soda ash after 30 minutes.Continue dyeing 1 hour at 80 ℃.Then, the fabric that dyed with flowing cold water and the rinsing of mobile hot water and boiling washing successively of the method that provides according to application example A.After rinsing and the drying, the dyeing on the cotton fabric is bright-coloured dark green, has good fastness ability.
Similarly, the mixture of the dyestuff of all the other examples or the dyestuff of enumerating can be used for according to the described method of application example A-D cotton products being dyeed.
Application example E
With the printing paste with following ingredients routinely printing method with cotton fabric printing:
The dyestuff of 40 parts of examples 1
100 parts of urea
350 parts of water
50 part of 4% sodiun alginate thickening material
10 parts of sodium bicarbonates
1000 parts.
With the fabric drying behind the stamp and in 102-104 ℃ steam fixation 4-8 minute, according to the described method of application example A with it with cold water, reusable heat water rinse and boiling washing, and dry.The orange stamp that obtains has good various conventional fastness ability.
Similarly, the mixture of the dyestuff of example 2-520 or the dyestuff the enumerated method that can provide according to application example E is with the cotton products stamp.The fastness ability that all stamps that obtain all show.
Table 1(is continuous)
Instance number D
T1.R
1. R
9.-W-
10 do. H do.
11
H H
12 do. H SO
3H（3）
13 do. H SO
3H（2）
14
H H
15 do. H H -NHCH
2CH
2NH-
16 do. H SO
3H（3）
17
H H do.
18 do. CH
3H do.
19 do. H SO
3H（2） do.
In last table and later table, do.=is the same.
The dyeing and the stamp that carry out on cotton products with the dyestuff of example 2-19 have greenish-yellow tone.
Table 2/ formula (T2) compound
Instance number R
2. R
3. R
4. R
8. R
9. R
10.-W-
20 H H -SO
3H H H H -NHCH
2CH
2NH-
21 H H do. CH
3-SO
3H CH
3 
22 CH
3OCH
3H do. do. OCH
3do.
23 do. CH
3H do. do. do. do.
24 H H -SO
3H do. do. do.
25 CH
3OCH
3H -SO
3H H -SO
3H
The dyeing and the stamp that carry out on cotton products with the dyestuff of example 20-25 have greenish-yellow tone.
Table 3/ formula (T3) compound
Instance number-W-
28 -NHCH
2CH
2NH-
The dyeing and the stamp that carry out on cotton products with the dyestuff of example 26-29 have greenish-yellow tone.
Table 4/ formula (T4) compound
In the end provided the dyeing of separately cotton products being dyed in the hurdle I, wherein a is a green-yellow, and b is yellow.
The position of substitution
Instance number D
T4.R
12.R
13.-NH-.-W-.I
30
CH
3H 5
b
31 do. do. H 5
b
32
do. H 4 do. b
33 do. do. H 4 -NHCH
2CH
2NH- b
34 do. do. H 5
b
35
do. H 4 do. b
36
do. H 5 do. b
Table 4(is continuous)
The position of substitution
Instance number D
T4.R
12.R
13.-NH-.-W-.I
37
-SO
3H 5
a
38
do. do. 4
a
39
do. do. 5 do. a
40
do. do. 4 do. b
41 do. do. do. 4 -NHCH
2CH
2NH- b
Table 6/ formula (T6) compound
In the end provided the tone that presents after separately cotton products being dyeed in the hurdle I, wherein a is a green-yellow, and b is yellow.
The position of substitution the position of substitution
Instance number-W-.-CONH--N=N-R
3R
11R
12R
13R
14I
62 -NHCH
2CH
2NH- 3′ 3 4-SO
3H OH CH
3-SO
3H 4-SO
3H a
63 do. 4′ 4 3-SO
3H OH do. do. 5-SO
3H b
64 do. 3′ 4 do. NH
2do. H 4-SO
3H a
65
3′ 4 do. OH do. -SO
3H 5-SO
3H b
66 do. 4′ 3 4-SO
3H OH COOH CH
34-SO
3H a
67 do. 4′ 3 do. OH do. H do. a
68
3′ 4 3-SO
3H OH CH
3Cl do. b
69 do. 3′ 3 4-SO
3H NH
2do. Cl 5-SO
3H a
70 do. 4′ 4 3-SO
3H OH do. -SO
3H 4-SO
3H b
71 do. 4′ 4 do. OH COOH CH
3do. b
Table 7/ formula (T7) compound
Instance number R
3R
4Q
2Q
3Q
4-W-
72 -SO
3H H CH
3-SO
3H CH
3
73 do. H do. do. do.
74 do. -SO
3H do. -CONH
2do. do.
75 do. do. do. do. -CH
2CH
3do.
76 do. H do. -CH
2SO
3H do. -NHCH
2CH
2NH-
77 do. -SO
3H do. H do.
78 do. do. -COOH H H do.
79 do. H do. H H
80 H H -CH
2SO
3H H CH
3do.
81 -SO
3H H do. -CONH
2do.
82 do. H CH
3H -CH
2CH
2SO
3H
83 do. -SO
3H do. H -（CH
2）
3NHCH
3 
84 do. do. do. -CONH
2-CH
2CH
3 
Table 7(is continuous)
Instance number R
3R
4Q
2Q
3Q
4-W-
85 -SO
3H -SO
3H CH
3-CONH
2-CH
2CH
3 
86 do. H do. -CH
2SO
3H H
Various dyestuffs with example 72-86 dye cotton products and stamp, present greenish-yellow tone.
Table 8/ formula (T8) compound
The position of substitution
Instance number R
4Q
2Q
3Q
4-NH--W-
87 H CH
3-CH
2SO
3H H 3
88 H do. do. CH
34 do.
89 H do. do. -CH
2CH
33 do.
90 H -COOH H H 3 do.
91 H CH
3-SO
3H H 3 do.
92 -SO
3H do. -CH
2SO
3H H 4
93 do. do. -CONH
2-CH
2CH
34 do.
94 H do. -CH
2SO
3H do. 3 do.
Table 8(is continuous)
The position of substitution
Instance number R
4Q
2Q
3Q
4-NH--W-
95 H -CH
2SO
3H -CONH
2CH
33
96 -SO
3H CH
3H -CH
2CH
2SO
3H 4 do.
97 H -CH
2SO
3H -CH
2SO
3H CH
33
98 -SO
3H CH
3-CONH
2-CH
2CH
2SO
3H 4
99 H CH
3H -CH
2CH
34
Various dyestuffs with example 87-99 dye cotton products and stamp, present greenish-yellow tone.
Table 9/ formula (T9) compound
In the end provided the tone of separately cotton products being dyed in the hurdle I, wherein a is a green-yellow, and b is yellow.
All carbon atoms that are marked with asterisk are connected on the nitrogen-atoms of pyridone in the divalent radical that limits in-B-the hurdle.
D in the table 9
T9Can be the following formula group,
According to R
50And R
51Definition, corresponding group is expressed as DD
1To DD
12Provide DD below
1To DD
12The meaning of each group.
DD
1: R
51For
And R
50Be H
DD
2: R
51Be do. and R
50Be SO
3H
DD
3: R
51For
And R
50Be H
DD
4: R
51For
And R
50Be H
DD
5: R
51For
And R
50Be SO
3H
DD
6: R
51For
And R
50Be H
DD
7: R
51For
And R
50Be H
DD
8: R
51Be do. and R
50Be SO
3H
DD
9: R
51For
And R
50Be H
DD
10: R
51For
And R
50Be H
DD
11: R
51For
And R
50Be SO
3H
DD
12: R
51For
And R
50Be H.
In addition, D
T9Can be the following formula group,
At DD
13-DD
21In the corresponding group of expression, R
50And R
51Limit as follows:
DD
13: R
51For
And R
50Be H
DD
14: R
51For
And R
50Be SO
3H
DD
15: R
51For
And R
50Be H
DD
16: R
51For
And R
50Be H
DD
17: R
51For
And R
50Be H
DD
18: R
51For
And R
50Be H
DD
19: R
51For
And R
50Be SO
3H
DD
20: R
51For
And R
50Be SO
3H
DD
21: R
51For
And R
50Be H.
Table 9
Instance number D
T9Q
2Q
3-B--W-I
100
CH
3-CONH
2-
＊CH
2CH
2NH-
a
101
do. H
-NHCH
2CH
2NH- a
102
do. -CH
2SO
3H
a
103
do. -SO
3H
a
104
do. -CH
2SO
3H -
＊CH
2CH
2NH-
b
105
do. -CONH
2 
a
106
do. b
107
CH
3H -
＊CH
2CH
2NH- -NHCH
2CH
2NH- b
Table 10/ formula (T10) compound
In the end provided the tone of separately cotton products being dyed in the hurdle I, wherein b is yellow, and c is a yellowish-orange, and d is orange.
Example the position of substitution m R
6R
7-W-I
Number-N=N-(the position of substitution)
147 2 1（3） H -NHCONH
2 
d
148 2 1（4） H do. do. d
149 1 1（3） H do. do. d
150 2 0 H CH
3do. b
151 2 1（4） H do. do. b
152 1 1（3） H do. do. b
153 2 1（3） H H do. b
154 2 0 H H do. b
155 2 1（3） CH
3CH
3do. b
156 2 1（4） OCH
3H do. b
157 2 1（3） H -NHCOCH
3do. c
158 1 1（3） H do. do. c
159 1 1（3） H -NHCONH
2 
d
160 2 0 H do. do. d
161 2 1（4） H do. do. d
162 2 1（3） H H do. b
Table 10(is continuous)
Example the position of substitution m R
6R
7-W-I
Number-N=N-(the position of substitution)
163 2 1（3） H -NHCOCH
3 
c
164 1 1（3） H do. do. c
165 2 0 H do. do. c
166 2 1（3） H CH
3do. b
167 2 1（3） OCH
3H do. b
168 2 1（3） H -NHCONH
2-NHCH
2CH
2NH- d
169 2 1（4） H do. do. d
170 1 1（3） H do. do. d
171 2 1（3） H CH
3do. b
172 2 1（3） H H do. b
173 2 1（3） H -NHCONH
2 
d
174 2 1（4） H CH
3do. b
175 2 1（3） H -NHCONH
2 
d
Table 11/ formula (T11) compound
m
Example (the position of substitution) R
7-W-
Number
176 1（4） CH
3 
177 1（4） -CH
2CH
3do.
178 0 CH
3do.
179 1（3） do. do.
180 1（4） do.
181 1（4） -CH
2CH
3do.
182 0 do. do.
183 0 CH
3do.
184 1（3） -CH
2CH
3do.
185 1（4） CH
3-NHCH
2CH
2NH-
186 1（3） do. do.
187 0 do. do.
188 1（4） do.
189 1（4） do.
190 1（3） -CH
2CH
3do.
191 0 CH
3 
192 1（3） H
193 1（4） H do.
Table 11(is continuous)
m
Example (the position of substitution) R
7-W-
Number
194 1（3） -NHCOCH
3-NH（CH
2）
3NH-
195 1（3） do.
196 1（3） -NHCONH
2do.
197 1（4） do. do.
198 1（3） H do.
199 1（3） -NHCONH
2 
200 1（3） do. -NH（CH
2）
3NH-
Table 12/ formula (T12) compound
Instance number D
T12R
52-W-
202
CH
3-NHCH
2CH
2NH-
203 do. do.
204 do. do.
205
H
206
H do.
207
CH
3
208
do. do.
209 do. H
Table 12(is continuous)
Instance number D
T12R
52-W-
210
H
211 do. CH
3-NHCH
2CH
2NH-
212
do.
213
do.
214
H do.
The various dyestuffs of example 202-214 are dyed blueness with cotton products.
Table 13/ formula (T13) compound
Table 13
The position of substitution
Instance number R
2R
29R
52-NH--W-q(the position of substitution)
215 H H H 4 -NHCH
2CH
2NH- 2（3，6）
216 2-OCH
33-SO
3H CH
35
2（3，8）
217 H do. H 5 do. 3（3，6，8）
218 2-OCH
3H CH
34
do.
219 2-CH
3H H 5 do. 2（4，6）
220 H 2-SO
3H H 4 -NH（CH
2）
3NH- 2（3，8）
221 H do. H 4
do.
222 H do. CH
35 do. 2（3，6）
223 H do. H 4 do. 3（3，6，8）
224 2-OCH
33-SO
3H H 5 do. do.
225 do. do. H 5
do.
226 do. do. H 5 -NHCH
2CH
2NH- do.
The dyestuff of example 215-226 is dyed blueness with cotton products.
Table 14/ formula (T14) compound
Table 14
The position of substitution
Instance number SO
3H R
17R
1-W-
227 4 H H
228 4 H CH
3do.
229 6 H H do.
230 4 6-Cl H do.
231 4 do. CH
3do.
232 6 4-Cl H do.
233 4 6-COOH H do.
234 4 6-SO
3H H do.
235 4 do. CH
3do.
236 4 H H
237 6 H H do.
238 6 4-CH
3H do.
239 4 6-Cl H do.
240 4 6-SO
3H H do.
241 4 do. H -NHCH
2CH
2NH-
242 4 H H do.
243 4 6-NO
2H do.
244 4 6-Cl H do.
245 6 4-Cl H do.
246 4 H H -NH（CH
2）
3NH-
247 4 6-Cl H do.
248 4 6-SO
3H H do.
249 4 do. H
250 4 do. H
The dyestuff of example 227-250 is dyed Ruby red with cotton products.
Table 15/ formula (T15) compound
Instance number-W-
251 -NHCH
2CH
2NH-
252
253 -NH（CH
2）
3NH-
The dyestuff of example 251-256 is dyed mazarine with cotton products.
Table 16/ formula (T16) compound
Last hurdle I has provided cotton products colour tone separately in the table, and wherein g is a Ruby red, and h is a purple.
Table 16
The position of substitution
Instance number R
50-NH--W-r(the position of substitution) I
257 5-SO
3H 3 -NHCH
2CH
2NH- 1（6） g
258 do. 3
do. g
259 3-SO
3H 5 do. do. g
260 do. 5
do. g
261 5-SO
3H 3 do. do. g
262 do. 3
do. g
263 H 4 do. 2（6，8） h
264 H 4
do. h
265 H 5 do. do. h
266 H 4 -NHCH
2CH
2NH- do. h
267 H 4 -NH（CH
2）
3NH- do. h
268 H 4
do. h
Table 18(is continuous)
Instance number R
3R
4-W-I
300 OCH
3SO
3H -NHCH
2CH
2NH- k
301 OC
2H
5H do. k
302 -OC
2H
4OH H do. k
303 OCH
3H -NH（CH
2）
3NH- k
304 do. SO
3H do. k
305 -OC
2H
4OH H do. k
306 OC
2H5 H
k
307 OCH
3H
k
308 do. SO
3H do. k
309 -OC
2H
4OH H do. k
310 -OC
2H
4OC
2H
4OH H do. k
311 do. H -NHCH
2CH
2NH- k
312 do. H -NH（CH
2）
3NH- k
313 do. H
k
314 do. H
k
315 CH
3SO
3H do. d
316 do. do.
d
317 do. do. -NHCH
2CH
2NH- d
318 do. do.
d
319 do. H do. d
Example 320
In the mixture of 10 parts of water and 20 parts of ice, 5 parts of cyanuryl chlorides are stirred into unit for uniform suspension.The tetra-na salt that adds 30 parts of following formula dyestuffs in this suspension is in 160 parts of water
Table 19/ formula (T19) compound
Example m SO
3The H base-W-
Number the position of substitution
321 0 1
322 0 1
323 1 1，5 do.
324 1 3，6 do.
325 0 1
326 1 1，5 do.
327 0 1 -NHCH
2CH
2NH-
328 1 1，5 do.
329 1 4，8 do.
330 0 1 -NH（CH
2）
3NH-
331 1 1，5 do.
332 0 1
333 1 1，5 do.
334 1 3，6 do.
335 1 4，8 do.
336 0 1
337 1 4，8
Table 20/ formula (T20) compound
Example m(SO
3H gets R
3R
4-W-
Number subrogate and to put)
338 1（2） H H
339 do. 5-SO
3H H do.
340 do. do. 4-CH
3do.
341 do. do. 4-OCH
3do.
342 do. H 4-CH
3do.
343 do. H 4-OCH
3do.
344 do. 4-SO
3H H do.
345 do. H H
346 do. H 4-OCH
3do.
347 do. 5-SO
3H H do.
348 do. H 4-CH
3
349 do. H 4-OCH
3do.
350 do. H H do.
351 do. 5-SO
3H H do.
352 do. 4-SO
3H H do.
353 0 2-COOH H do.
354 0 3-COOH H do.
355 0 4-COOH H do.
356 1（2） 5-SO
3H 4-OCH
3 
357 do. H H do.
358 do. H 4-CH
3do.
Table 20(is continuous)
Example m(SO
3H gets R
3R
4-W-
Number subrogate and to put)
359 1（2） H 4-OCH
3 
360 do. 4-SO
3H H do.
361 0 3-COOH H do.
362 1（2） H H
363 do. 5-SO
3H H do.
364 do. do. 4-CH
3do.
365 do. 4-SO
3H H do.
366 0 2-COOH H do.
367 0 3-COOH H do.
368 0 4-COOH H do.
369 1（2） H H -NHCH
2CH
2NH-
370 do. H 4-OCH
3do.
371 0 2-COOH H do.
372 1（2） 5-SO
3H H -NH（CH
2）
3NH-
Table 21/ formula (T21) compound
Example-W-R
16
Number
373-NHCH
2CH
2The NH-methyl
374 do. ethyls
375 do. phenyl
Table 21(is continuous)
Instance number-W-R
16
376
Phenyl
377 do. methyl
378 do. ethyls
379
Methyl
380 do. phenyl
381
do.
382 do. ethyls
383
Methyl
384-NH(CH
2)
3The NH-phenyl
Table 22/ formula (T22) compound
Table 22
The position of substitution the position of substitution
Instance number D
T22SO
3H-NH--W-
385
3 3 -NHCH
2CH
2NH-
386 do. 3 4 do.
387 do. 3 3
388 do. 3 3
389 do. 3 3
390 do. 3 3
391 do. 4 3 do.
392
3 4 do.
393 do. 4 3 do.
394 do. 3 3 do.
395
3 4 do.
396 do. 3 3 do.
397 do. 4 4 do.
398 do. 3 3
Table 22(is continuous)
The position of substitution the position of substitution
Instance number D
T22SO
3H-NH--W-
399
3 4
400 do. 3 3 -NHCH
2CH
2NH-
401 do. 3 3
402 do. 3 4
403
3 3
404 do. 3 4
405 do. 4 4 do.
406
3 4 do.
407 do. 3 3 -NHCH
2CH
2NH-
408
3 3 do.
409 do. 4 3 do.
410 do. 3 4
411 do. 3 3
412
3 4 do.
Table 22(is continuous)
The position of substitution the position of substitution
Instance number D
T22SO
3H-NH--W-
413
3 4
414
3 3 do.
415 do. 4 4 -NH（CH
2）
3NH-
416 do. 3 4
Table 23/ formula (T23) compound
Instance number R
3R
4The position of substitution R
5-W-
-NH-
418 4-SO
3H H 5 SO
3H
419 3-COOH H 4 do. do.
420 4-COOH H 4 COOH do.
421 do. H 4 SO
3H
422 3-SO
3H H 5 do. do.
423 5-COOH 2-Cl 4 do. do.
424 do. do. 5 do. do.
425 do. do. 4 COOH do.
426 3-COOH H 5 SO
3H do.
427 4-SO
3H H 4 COOH do.
428 2-SO
3H 4-Cl 4 do. do.
429 4-SO
3H H 4 SO
3H do.
430 2-SO
3H 4-Cl 4 do. do.
431 4-SO
3H H 5 do. do.
432 2-SO
3H 4-Cl 5 do. do.
433 5-COOH 2-Cl 5 do.
434 4-COOH H 5 do. do.
435 4-SO
3H H 5 do. do.
436 3-COOH H 5 do. do.
437 3-COOH H 4 do. do.
438 3-SO
3H H 4 do. do.
439 do. H 4 COOH do.
440 do. H 5 SO
3H -NHCH
2CH
2NH-
441 5-COOH 2-Cl 5 do. do.
442 5-SO
3H do. 5 do. do.
443 3-COOH H 5 do. do.
444 2-SO
3H 4-Cl 5 do. -NH（CH
2）
3NH-
Table 23(is continuous)
Instance number R
3R
4The position of substitution R
5-W-
-NH-
445 5-SO
3H 2-Cl 4 SO
3H -NH（CH
2）
3NH-
446 4-COOH H 4 COOH
447 5-SO
3H 2-Cl 5 SO
3H do.
448 4-COOH H 5 do. do.
449 5-COOH 2-Cl 5 do. do.
450 3-COOH H 4 COOH
451 3-SO
3H H 4 do. do.
452 do. H 5 SO
3H do.
453 5-COOH 2-Cl 4 COOH do.
454 4-COOH H 5 SO
3H
455 5-SO
3H 2-Cl 4 COOH do.
456 2-SO
3H 4-Cl 4 do. do.
Claims (5)
1, the method for the mixture of the free acid of compound or salt shown in the preparation formula I and formula I compound,
Fc is water-soluble azo, the first of no metal or metal complexes form in the formula
, phthalocyanine, azomethine, oxazine, thiazine, azophenlyene or triphenylmethane dye group,
A independently represents 0 or 1 separately,
B is 1 or 2,
X independently represent separately direct key ,-CO-or-SO
2-,
R
1Independently represent hydrogen separately, do not replace C
1-4Alkyl or by hydroxyl, halogen ,-SO
3H, OSO
3H or-the mono-substituted C of COOH
1-4Alkyl,
Alk independently represents C separately
2-4Alkylidene group;
W is independently expression separately
M is 0 or 1 in the formula,
B
1Be C
2-6Alkylidene group, have-O-or-NR
1-C
2-6Alkylidene chain is by one or two hydroxyl or by the C of a carboxyl substituted
3-6Alkylidene group,
N is 0,1,2,3 or 4 in the formula,
R
2Be hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-COOH or-SO
3H,
Comprise that the mixture that makes formula II compound or formula II compound is at Y
3Be-during W-H and 5-cyano group-2,4,6-trichloropyrimidine or at Y
3When being chlorine and formula III compound reaction, the mol ratio of formula II and formula III compound is 1: 1,
Y in the formula
3Be-W-H or chlorine,
2,, comprise making Y according to the method for claim 1
3Be-the formula II compound of W-H participates in reaction.
3, according to the method for claim 1, preparation has the no metallic compound (1) of following formula,
DK relates to the group of the diazonium composition of benzene or naphthalene in the formula,
KK relate to benzene, naphthalene or heterocyclic coupling composition group or can be by the group of the CH-acidic cpd of enolization, Z is
Wherein
B is 1, and this moment, Z passed through
Be bonded on diazonium or the coupling composition.
4, according to the method for claim 1, preparation has the free acid or the salt of the no metallic compound of following formula,
Z is in the formula
T is 2 or 3,
R
6Be hydrogen, C
1-4Alkyl or C
1-4Alkoxyl group,
R
7Be hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group ,-NHCOC
1-4Alkyl or-NHCONH
2,
R
6XHas R independently
6One of definition and
R
7XHas R independently
7One of definition.
5, according to the method for claim 1, prepare based on no metallic compound (3a) or the metal complexes (3b) shown in the following formula,
A is
M independently represents 0 or 1 separately,
Q is 1,2 or 3,
R
17Be hydrogen, halogen, nitro, C
1-4Alkyl, C
1-4Alkoxyl group ,-COR
13,-SO
3H or-NHCOCH
3,
R
22Be OH, OCH
3Or NH
2And
R
13Be OH ,-OC
1-4Alkyl or NH
2,
This metal complexes is free acid form or salt form, and is 1: 1 copper complex or a kind of symmetric or asymmetric 1: 2 chromic compound or 1: 2 cobalt complex.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19883835724 DE3835724A1 (en) | 1988-10-20 | 1988-10-20 | New reactive azo dyes |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94105676A Division CN1056635C (en) | 1988-06-14 | 1994-05-13 | Fibre-reactive dyestuffs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052493A CN1052493A (en) | 1991-06-26 |
| CN1028372C true CN1028372C (en) | 1995-05-10 |
Family
ID=6365534
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109347 Pending CN1052492A (en) | 1988-10-20 | 1989-12-14 | fiber-reactive azo dyes |
| CN 89109292 Expired - Fee Related CN1028372C (en) | 1988-10-20 | 1989-12-14 | Fibre-reactive dyestuffs |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109347 Pending CN1052492A (en) | 1988-10-20 | 1989-12-14 | fiber-reactive azo dyes |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN1052492A (en) |
| DE (1) | DE3835724A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047607C (en) * | 1994-12-29 | 1999-12-22 | 大连理工大学 | Water-soluble fluorescent dye |
| DE60139949D1 (en) * | 2000-10-10 | 2009-10-29 | Clariant Finance Bvi Ltd | FIBER-REACTIVE COPPER COMPLEXES OF MONOAZO DYES |
| CN106398299A (en) * | 2016-08-30 | 2017-02-15 | 江苏德美科化工有限公司 | Active yellow-dye compound containing fluorine and preparation method thereof |
| CN110903680B (en) * | 2019-12-23 | 2021-09-03 | 上海染料研究所有限公司 | Low-salt purification method of edible colorant |
-
1988
- 1988-10-20 DE DE19883835724 patent/DE3835724A1/en not_active Withdrawn
-
1989
- 1989-12-14 CN CN 89109347 patent/CN1052492A/en active Pending
- 1989-12-14 CN CN 89109292 patent/CN1028372C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3835724A1 (en) | 1990-04-26 |
| CN1052493A (en) | 1991-06-26 |
| CN1052492A (en) | 1991-06-26 |
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