CN102292399A - Ring fluorinated reactive dyes - Google Patents

Ring fluorinated reactive dyes Download PDF

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Publication number
CN102292399A
CN102292399A CN2009801550203A CN200980155020A CN102292399A CN 102292399 A CN102292399 A CN 102292399A CN 2009801550203 A CN2009801550203 A CN 2009801550203A CN 200980155020 A CN200980155020 A CN 200980155020A CN 102292399 A CN102292399 A CN 102292399A
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group
formula
alkyl
hydrogen
phenylene
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S·埃伦伯格
W·埃比尼泽
M·哈钦斯
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Dystar Textilfarben GmbH and Co Deutschland KG
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Dystar Colours Deutschland GmbH
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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
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411—Azo dyes
    • C09B62/4413—Non-metallized monoazo dyes
    • 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
    • C09B62/04—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 triazine ring
    • C09B62/043—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 triazine ring containing two or more triazine rings linked together by a non-chromophoric link
    • 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
    • C09B62/04—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 triazine ring
    • C09B62/08—Azo dyes
    • C09B62/085—Monoazo dyes
    • 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
    • C09B62/25—Disazo or polyazo dyes
    • 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
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/51—Monoazo dyes
    • 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
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

The present invention claims dyestuffs of the formula (I) wherein a, is 1 or 2; X1, X2, RG, R1, R2, R3, R4, a, b, c and M are defined as given in claim 1, a method for their preparation and their use.

Description

Ring is fluoridized reactive dyestuffs
(1) technical field
The present invention relates to the technical field of fiber reactive azo dyes.
(2) background technology
The dyes and dyestuffs that contains fluorine atom (with the form of trifluoromethyl) separately is known and is described in the literature.For example, GB732121 discloses the monoazo matching stain that contains a trifluoromethyl-Phenylsulfonic acid.Ring fluorizated monoazo aniline pigment is described in dyestuff and pigment 42 (1999) 159-172, discloses in GB 882,001 and contain the azoic dyestuff of fluoridizing the diazo composition.
Containing the fibre-active azoic dyestuff of fluoridizing the diazonium composition is described in EP 0043560A1.Further, the fibre-active three benzo dioxazine dyess that carry a fluorine atom on three benzo dioxazines chromophoric grouies are described at WO2007/077129A2.The azoic dyestuff that contains a diazo composition has also carried a fluorine atom except that two sulfonic groups, this dyestuff is known in EP 0167785A1.
(3) summary of the invention
Shockingly found the fibre-active dyestuff describe below, this dyestuff is obtained as the diazonium composition by ring fluorizated aniline sulfonic acid, when being applied to cotton reactively, it demonstrates the fastness data drawing list (profiles) that has superiority especially, particularly, demonstrate extraordinary lifting force (build up) level in addition about colour fastness to light, the colour fastness of anti-chlorine and color fastness to perspiration.And this dyestuff has been given the homogeneous hue with excellent contact colour fastness after eccysis.
Therefore, the invention provides the have formula dyestuff of (I)
Figure BDA0000077193380000011
Wherein
A is 1 or 2;
X 1Be the aryl or the heteroaryl of a divalence;
RG be one under dyeing condition can with amide-containing-and/or hydroxyl-material form the active group of covalent linkage, or one contains the group that can form the active group of covalent linkage under dyeing condition with Mierocrystalline cellulose, or hydrogen;
R 1Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, chlorine or a group with formula (II)
Figure BDA0000077193380000021
Wherein
X 2Be an aryl or heteroaryl;
R 3Be hydrogen or-SO 3M;
R 4Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, fluorine, chlorine ,-SO 2CH=CH 2Or-SO 2CH 2CH 2Z, wherein Z is-OSO 3M ,-OAc ,-OPO 3H 2Or chlorine;
B is 1 or 2;
C is 1,2 or 3;
R 2Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, sulfo group, hydroxyl or chlorine; And
M is a hydrogen, the Equivalent of a kind of basic metal or a kind of alkaline-earth metal;
Supplementary condition are if R 1Be not the group with formula (II), RG is not a hydrogen; And further supplementary condition are to get rid of the compound with formula (A),
B is hydrogen or phenyl in the formula (A), and M as above defines.
The preferred X that represents 1The aryl of divalence or heteroaryl for having formula (IIIa) to one of group of formula (IIIj)
Figure BDA0000077193380000023
Figure BDA0000077193380000031
Wherein
Ar is a phenylene or by, the phenylene that two or three substituting groups replace, and wherein substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, halogen and-SO 3M;
E 1Has one of definition of Ar; Perhaps E 1Be naphthyl or the naphthyl that replaced by one, two or three substituting groups, wherein substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group ,-SO 3M, amino, kharophen or hydroxyl; Or E 1Be a heterocycle residue with 5 or 6 ring structures, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur; Or E 1Be a heterocycle residue with 5 or 6 ring structures, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur, and this heterocyclic group is by one, two or three substituting groups replacements, and described substituting group is selected from (C 1-C 4)-alkyl and (C 1-C 4)-alkoxyl group;
E 2Be phenylene or naphthylidene, described phenylene and naphthylidene are not substituted or by one, two or three substituting groups replacements, described substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group ,-SO 3M, amino, kharophen or hydroxyl; Or E 2Be the heterocycle residue of 5 or 6 ring structures of a divalence, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur; Or E 2Be the heterocycle residue of 5 or 6 ring structures of a divalence, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur, and this heterocycle residue is by one, two or three substituting groups replacements, and substituting group is selected from (C 1-C 4)-alkyl and (C 1-C 4)-alkoxyl group; Or E 2It is a group with formula (IV)
Figure BDA0000077193380000032
Wherein
R 7Be (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group ,-SO 3M or hydroxyl;
R 8And R 8' be hydrogen separately by oneself, (C 1-C 6)-alkyl, sulfo--(C 1-C 6)-alkyl, phenyl or quilt (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl ,-SO 3M, halogen ,-phenyl that COOM, kharophen or urea groups replace;
R 8aBe hydrogen or kharophen;
R 5Be (C 1-C 4)-alkyl or-COOM;
R 6Be hydrogen, CN or-CONH 2
L is 1,2-phenylene, 1, and 3-phenylene or 1, the 4-phenylene, described 1,2-phenylene, 1,3-phenylene and 1, the 4-phenylene is not substituted or quilt-SO 3M ,-COOM or R 8Replace; Or L is (C 2-C 6)-alkylidene group or (C 1-C 4)-alkylidene group-phenylene, described (C 2-C 6)-alkylidene group and (C 1-C 4)-alkylidene group-phenylene is not substituted or by R 8Replace;
The definition of M as mentioned above; And
*Represent this key to be connected with the RG group.
Represent E 1To contain one or two heteroatomic example with heterocycle residue of 5 or 6 ring structures be pyridone, pyrazolone and diamino-pyridine.
Similarly, represent E 2Pyrrolidone residue, pyrrolinone residue and the diamino-pyridine residue that to contain one or two heteroatomic example with heterocycle residue of 5 or 6 ring structures be divalence of divalence.
The particularly preferred X that represents 1The aryl or the heteroaryl of divalence be to have the group of formula (IIIm) to formula (IIIu)
Figure BDA0000077193380000041
Figure BDA0000077193380000051
Wherein, *Represent this key to be connected with the RG group and the definition of M as above.
Preferred represent RG under dyeing condition can with amide-containing-and/or the active group of the material formation covalent linkage of hydroxyl be-SO 2-CH=CH 2,-SO 2-CH 2CH 2Z 1Or group with formula (IV)
-N(R 8)-A (IV)
Wherein
Z 1It is the separable group of alkali;
R 8Definition as above;
A has formula (Va), (Vb) or group (Vc)
Figure BDA0000077193380000052
V is a fluorine or chlorine;
U 1And U 2Be alone fluorine separately, chlorine or hydrogen; And
Q 1And Q 2Independent separately is chlorine, fluorine, cyanogen amino, hydroxyl, (C 1-C 6)-alkoxyl group, phenoxy group, sulfophenoxy, sulfydryl, (C 1-C 6)-alkyl thiol, pyrido, carboxyl pyridine also, formamyl pyrido or a group with formula (VI) or formula (VII)
Figure BDA0000077193380000061
Wherein
R 9Has R 1One of definition or R 9It is phenyl;
R 10And R 11Has R independently 1One of definition, or R 10And R 11Be phenyl, hydroxyl-(C independently 1-C 6)-alkyl, one have formula-(CH 2) 2-S-(CH 2) 2The group of-OH or R 10And R 11Has formula-(CH in conjunction with forming one 2) j-or formula-(CH 2) 2-B 1-(CH 2) 2-group, wherein j is 4 or 5, B 1Be oxygen, sulphur, alkylsulfonyl or-NR 9-, and R 9Be (C 1-C 6)-alkyl;
W is unsubstituted phenylene or the phenylene that replaced by one or two substituting group, and described substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, carboxyl, sulfo group, chlorine and bromine; Or W is (C 1-C 4)-alkylidene group phenylene, (C 2-C 6)-alkylidene group, wherein (C 2-C 6)-alkylidene group can be interrupted by oxygen, sulphur, alkylsulfonyl, amino, carbonyl or amide group; Or W is phenylene-CO-NH-phenylene unsubstituted or that replaced by one or two substituting group, and described substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, sulfo group, carboxyl, amino, urea groups and halogen; Or W is a naphthylidene unsubstituted or that replaced by one or two sulfo group; And
Z 2Be-CH=CH 2Or-CH 2CH 2Z 1
The active group that can form covalent linkage with Mierocrystalline cellulose under dyeing condition of the particularly preferred RG of representative is to have the group of formula (Vd) to formula (Vi)
-SO 2-CH＝CH 2(Vd) -SO 2-CH 2CH 2OSO 3M(Ve)
Wherein, R 8With the definition of M as above.
In the disclosed structural formula of specification sheets of the present invention, alkyl can be straight or branched, particularly methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.(C in addition 1-C 6)-alkyl can also be n-pentyl or n-hexyl.Preferably methyl and ethyl.Same logic is applicable to alkoxyl group and alkylidene group, so alkoxyl group preferably methoxyl group and oxyethyl group, and alkylidene group is ethylidene, propylidene and butylidene in particular.
Halogen is bromine preferably, chlorine and fluorine.
Basic metal M is lithium in particular, sodium or potassium; Alkaline-earth metal Equivalent M is the Equivalent of calcium in particular.M is hydrogen or sodium preferably.
Represent Z 1The example of the separable group of alkali be halogen, such as chlorine and bromine; The ester group of organic carboxyl acid and sulfonic acid, for example alkyl carboxylic acid, replacement or ester group, particularly (C unsubstituted benzene carboxylic acid and replacement or unsubstituted Phenylsulfonic acid 2-C 5)-alkanoyloxy is such as acetoxyl group, benzoyloxy, sulfosalicylic acid base, phenyl sulfonyloxy and tosyloxy; The acid ester group of mineral acid, as phosphoric acid, vitriolic and sodium byposulfite acid ester group (phosphoric acid salt, vitriol and thiosulphate group); And has (C separately 1-C 4The dialkyl amido of)-alkyl is such as dimethylamino and diethylamino.
Z 1Preferably chlorine, more preferably sulfato.
R 1Preferably hydrogen, methyl or a group with formula (II).
In a kind of preferred embodiment of the present invention, R 2Be hydrogen, and in the another kind of preferred embodiment of the present invention R 2It is sulfo group.
The preferred X that represents 2Aryl or heteroaryl be group with formula (IIIv)
Figure BDA0000077193380000081
Wherein
R 4' be SO 2CH=CH 2Or-SO 2CH 2CH 2OSO 3M; And
R 3With the definition of M as above.
Therefore, a group that preferably has formula (II) is the group with formula (IIa)
Figure BDA0000077193380000082
Wherein
R 4' be SO 2CH=CH 2Or-SO 2CH 2CH 2OSO 3M; And
R 3With the definition of M as above.
Particularly preferred group with formula (IIa) is to have the group of formula (IIa1) to formula (IIa4)
Wherein, the definition of M as above.
Preferred L is a hydrogen, sodium or potassium.
The dyestuff that preferably has formula (I) is to have the dyestuff of formula (Ia) to formula (In)
Figure BDA0000077193380000084
Figure BDA0000077193380000091
Wherein, X 1, X 2, R 3, R 4, R, G, b, the definition of c and M is as above.Particularly preferably be and have formula (Ia), (Ib), (Id), (Ie), (Ih) and dyestuff (In).
Other particularly preferred dyestuffs with formula (I) are to have the dyestuff of formula (Ia) to formula (In), wherein X 1, X 2, RG and M have as above preferably definition.
Therefore, particularly preferred example with dyestuff of formula (I) is to have the dyestuff of formula (Io) to formula (It)
Figure BDA0000077193380000092
Figure BDA0000077193380000101
Wherein
A 1Be to have formula (Vf), (Vg), (Vh) or group (Vi);
A 2Be to have formula (Vd) or group (Ve);
A 2' be to have formula (Vd) or group (Ve);
R 12Be methyl, methoxyl group or-SO 3M;
R 12' be methyl, methoxyl group or-SO 3M; And
The definition of M as above.
Dyestuff with formula (I) can prepare by synthesis step known to a person of ordinary skill in the art.
In a kind of preferable methods, make have formula (VI) compound diazotization and be coupled on the compound with formula (VII),
Figure BDA0000077193380000111
-X 1-RG(VII)
In the formula (VI), R 1, R 2, the definition of a and M as above, in the formula (VII), X 1With the definition of RG as above.
Compound with formula (VII) is known and can prepares by known method.
Compound with formula (VI) partly is known and can prepares by known method.For example, 4-amino-2-fluorobenzene sulfonic acid can be according to US 5,106, the method preparation of describing in 960,4-amino-3-fluorobenzene sulfonic acid can according to the method preparation of describing in the document [Helv.Chim.Acta 1982, (65), 546-550 page or leaf] and 2-amino-5-fluorobenzene sulfonic acid can [Helv.Chim.Acta 1983 according to document, (66), 68-75 page or leaf] the middle method preparation of describing.The compound with formula (VI) in addition is in document [Arzneimittelforschung/Drug Research, the 18th the 9th phase of volume, 1968, the 1220-1221 page or leaf] and document [J.Chem.Soc., Dalton Trans., the 1990th volume, 1990,3773-3779 page or leaf] in be disclosed.
The compound with formula (VI) of other parts is new.Therefore, the present invention also provides the compound with formula (VIa)
Figure BDA0000077193380000112
Wherein
A is 1 or 2;
D is 1 or 2;
R 1aBe (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, fluorine, chlorine or a group with formula (II)
Figure BDA0000077193380000113
Wherein
X 2Be an aryl or heteroaryl;
R 3Be hydrogen or-SO 3M;
R 4Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, chlorine, SO 2CH=CH 2Or-SO 2CH 2CH 2Z, wherein Z is-OSO 3M ,-OAc ,-OPO 3H 2Or chlorine;
B is 1 or 2;
C is 1,2 or 3; And
M is a hydrogen, the Equivalent of a kind of basic metal or a kind of alkaline-earth metal;
Supplementary condition are to get rid of the compound with formula C and formula D,
Figure BDA0000077193380000121
Wherein the definition of M as above.
In the compound that preferably has formula (VIa), R 1aBe fluorine, methyl, methoxyl group or a group with formula (II).
The example that preferably has the compound of formula (VIa) is to have the compound of formula (VIa1) to formula (VIa9)
Figure BDA0000077193380000122
Figure BDA0000077193380000131
Wherein, Z 2Be-CH=CH 2Or-CH 2CH 2OSO 3M, the definition of M as above.
Compound with formula (VIa) can obtain by handling the compound with formula (VIII) with sulfonated reagent,
Figure BDA0000077193380000132
Wherein, R 1aDefinition as above.
Preferred sulfonated reagent is a chlorsulfonic acid, sulfuric acid and oleum.
Compound with formula (VIII) is known and can be by using known method preparation.
The dyestuff that the present invention has a formula (I) has the useful application performance and can be used to contain amide group-and/or the dyeing and the stamp of the material of oh group.Mentioned material can be for example flaky texture such as paper and leather, membrane structure such as polyamide membrane, or the form of varicosity composition (bulk composition), for example the varicosity composition of being made up of polymeric amide or Polyurethanes.But especially, they are that form with the fiber of mentioned material exists.
Therefore, the dyestuff of the present invention with formula (I) is used for the dyeing and the stamp of the cellulose fibre material of any kind of.Preferably, they are useful to the dyeing or the stamp of tynex or polymeric amide and BLENDED FABRIC cotton or that form with trevira also.
It also is feasible using dyestuff that the present invention has a formula (I) by ink-jetting process textiles or paper to be carried out stamp.
The dyestuff that therefore the present invention also provides the present invention to have formula (I) is used to contain the dyeing of amide group and/or oh group material and the purposes of stamp, or be used for the technology that method by a kind of routine makes these materials dyeing or stamp as the case may be, use among one or more the present invention in this ordinary method to have the dyestuff of formula (I) as tinting material.
Advantageously, the synthetic the present invention of institute has the solution of the dyestuff of formula (I), randomly after adding a kind of buffer substance, and randomly concentrate or dilution after, can directly be used for dyeing as a kind of flowing product.
At this mentioned filamentary material or fiber textile fibres in particular, can exist with woven fabrics, yarn or with the form of reeled yarn or winding bobbin yarn.
The example that contains the material of amide group is synthetic and natural polymeric amide and urethane, particularly with the form of fiber, and for example woollen and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
The material that contains hydroxyl is to have those materials natural or synthetic source, for example cellulose fibre material or their reconstituted product and polyvinyl alcohol.Cellulosic fibre material is preferably cotton, but also has the other plant fiber, such as flax, hemp, jute and ramee.Cellulosic regenerated fibre is, for example viscose staple fiber and viscose macrofiber.
The dyestuff that the present invention has formula (I) can be used for water misciblely by known, uses and anchors on the mentioned material especially for the application technique of fibre-active dyestuff, particularly anchors on the mentioned filamentary material.
Put in order (referring to for example H.Rath through no fulling milling or low fulling milling, Lehrbuch der Textilchemie, Springer-Verlag, the third edition (1972), 295-299 page or leaf, the particularly arrangement of carrying out according to the so-called He Kesaite wool shrinkproof method of the 298th page of record; J.Soc.Dyers and Colourists 1972,93-99 and 1975, woolen cloth 33-44) can be colored to having extraordinary fastness performance.At this, painted technology is to implement with a kind of method of routine from a kind of acidic medium on woolen cloth.For example, can in this dye bath, add acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or acetic acid and sodium acetate to obtain the pH value of an expectation.In order to obtain the dyeing of an acceptable equalization, the levelling agent that preferably adds a routine, for example based on a kind of levelling agent of the reaction product of the aniline sulfonic acid of cyanuryl chloride and 3 times of molar weights and/or napthylamine sulfonic acid, or based on a kind of levelling agent of the reaction product of for example stearylamide and oxyethane.For example, dyestuff of the present invention preferably stands to exhaust dyeing technique, it is big about 3.5 to 5.5 acid dye bath since control pH value that this exhausts dyeing technique, when being tending towards the terminal point of dyeing time that pH regulator is extremely neutral then, and alternatively with the weakly alkaline scope of pH regulator to the highest 8.5, especially in order to obtain very dark tone, between dyestuff of the present invention and fiber, to produce reactive bond completely.Simultaneously, partly be not removed by the dyestuff of active bonding.
Program described here also is used for by other neutral polymeric amide or by the painted generation on the filamentary material that synthesizing polyamides and urethane constituted.These materials can use describe in the document and (for example see H.-K.Rouette as normal dyeing and printing technology that those of ordinary skills know, Handbuch der Textilveredlung, Deutscher Fachverlag GmbH Frankfurt/Main) dyes.
Dye liquor and printing paste, the dyestuff that has formula (I) in addition can comprise other additive.Additive is, wetting agent for example, and antifoam, levelling agent and the reagent that influences the textile materials performance are such as tenderizer, be used for fire-resistant finish and antifouling, waterproof and grease proofing additive or water-softening chemicals.Printing paste can also comprise natural or the synthetic thickening material especially, such as alginates and ether of cellulose.Dyestuff content in dye bath and printing paste can change in a very wide scope according to the desired depth of shade that obtains.Usually, the content of dyestuff with formula (I) is at 0.01wt% to 15wt%, particularly at 0.1wt% to 10wt%, respectively based on treating painted material and based on printing paste.
By a high bath raio, use various acid binding agents and exhausting on the cellulosic fibre that the method for dying produces of neutral salt (for example sodium-chlor and sodium sulfate) randomly, dyeing has extraordinary tinctorial yield.Dyestuff is used preferably between pH value 3 to 7, for exhausting the method for dying particularly preferably between the pH value 4 to 6.Bath raio can be selected in a wide scope, such as between 3: 1 and 50: 1, preferably between 5: 1 and 30: 1.Dyeing is preferably carried out in the water-bath of a temperature between 40 to 105 ℃, is randomly carrying out under 130 ℃ the temperature at the most under reduced pressure, and is randomly carrying out in the presence of the normal dyeing auxiliary agent.In order to increase the moisture-proof colour fastness of coloring material, the dyestuff of set can not be removed in aftertreatment.This aftertreatment is carried out under 75 to 80 ℃ condition in pH value 8 to 9 and temperature especially.
Here a kind of possible program is that material is introduced in the temperature bath, and this body lotion is heated to temperature desired gradually and finishes dyeing course under this temperature.The neutral salt (if needs) that can quicken dye exhausting can also only just join in the dye bath after the dyeing temperature of reality reaches.
The pad dyeing method provides fabulous tinctorial yield and good color lifting force equally on cellulosic fibre, wherein dyestuff is to bank up by (for example up to about 60 ℃ under) at room temperature or under the elevated temperature, or by evaporating or by xeothermic and by set.
Similarly, the printing method of the routine of cellulosic fibre, it can be undertaken by a step, for example with the printing paste stamp that contains sodium bicarbonate or some other acid binding agents, evaporated under 100 to 103 ℃ subsequently; Perhaps undertaken by two steps, for example use a kind of neutral or weakly acidic printing paste stamp, make printed material by containing of a heat of electrolytical alkaline bath or with the excessive pad dyeing of containing of a kind of alkalescence of electrolytical padding liquor then, subsequently the material of this alkalescence-excessive pad dyeing is banked up or evaporated or dry heat treatment makes the dyestuff set, produce firm have well-defined profile and white background colour printed clearly.The influence that the effect of stamp is changed by color fixing condition.
Xeothermic when carrying out fixation when utilizing according to the thermosetting method of routine, use 120 to 200 ℃ warm air.The steam under 101 to 103 ℃ except routine also might use superheated vapour and the highest 160 ℃ high pressure steam.
The acid binding agent that influences the set of dyestuff on cellulosic fibre is, for example water miscible inorganic or organic acid basic metal and the water-soluble alkaline salts of alkaline-earth metal similarly, or when heating, discharge the compound of alkali.Particularly suitable is alkali metal hydroxide and weak to medium inorganic or organic acid alkaline metal salt, and preferred alkali metal compound is the compound of sodium and potassium.This type of acid binding agent is, sodium hydroxide for example, and potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, sodium formiate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, Tricholroacetic Acid is received, water glass or tertiary sodium phosphate.
The distinguishing feature that the present invention has the dyestuff of formula (I) is to have hyperergy, good fixation ability, extraordinary load-carrying capacity and high fast light and colour fastness to perspiration.Therefore they can be applied in exhausting in the dyeing technique of low dyeing temperature, and only need very short evaporating the time in the technology in pad dyeing-evaporate.The fixation degree is very high and be not easy to eccysis by the part of set, and the difference that exhausts the degree of dying and set degree is very little, that is to say that the loss of soaping is very low.They are for stamp, and particularly the stamp on cotton is particularly useful, and for nitrogen-containing fiber, for example woollen or silk contain woolen cloth or the stamp of the BLENDED FABRIC of silk also particularly useful.
The distinguishing feature that the present invention has a dyestuff of formula (I) is not to be easy to eccysis on the fibre behind the dying operation by the part dyestuff of set, does not exist in the washing operation to be stained by the dyestuff of eccysis or pollute and the white point that forms.This is favourable for dying operation, washs in this dying operation and can circulate, and therefore can save cost.
Dyeing and stamp that the dyestuff that uses the present invention to have formula (I) generates all have high colour intensity and high fiber-dyestuff combination stability in acid range and alkaline range, and have good colour fastness to light and a good moisture-proof colour fastness performance, such as wash resistant, water-fast, sea water resistance, the dyeing of anti-intersection and colour fastness to perspiration, also have good anti-pleating, heat-resisting pressure and colour fastness to rubbing.
The present invention also provides the printing ink that is used for digital textile printing by ink ejecting method, and this printing ink comprises the dyestuff that the present invention has formula (I).
Printing ink of the present invention comprises the dyestuff that one or more the present invention have formula (I), and for example its content is 0.1wt% to 50wt% based on the gross weight of printing ink, is preferably 1wt% to 30wt% and 1wt% to 15wt% more preferably.For the printing ink that is used to the Continuous Flow process, can by add a kind of ionogen set specific conductivity 0.5 to 2.5mS/m.Useful ionogen comprises, for example lithium nitrate and saltpetre.Printing ink of the present invention can comprise total content at 1-50wt%, is preferably the organic solvent of 5-30wt%.
Appropriate organic solvent is an alcohols for example, methyl alcohol for example, ethanol, 1-propyl alcohol, Virahol, 1-butanols, uncle-butanols, amylalcohol, polyalcohols be for example: 1,1,2,3-glycerol, butyleneglycol, 1, the 3-butyleneglycol, 1,4-butyleneglycol, 1,2-propylene glycol, 2, ammediol, pentanediol, 1,4-pentanediol, 1,5-pentanediol, hexylene glycol, D, L-1, the 2-hexylene glycol, 1,6-hexylene glycol, 1,2,6-hexylene glycol, 1,2-ethohexadiol, polyalkylene glycols, for example: polyoxyethylene glycol, polypropylene glycol has the aklylene glycol class of 2 to 8 alkylidene groups, for example: monoethylene glycol, Diethylene Glycol, triethylene glycol, Tetraglycol 99, the sulfo-glycol, sulfo-glycol ether, butyl triglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol
The low alkyl ether of polyvalent alcohol, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diglycol monotertiary hexyl ether, triethylene glycol monomethyl ether, triethylene glycol butyl ether, tripropylene glycol monomethyl ether, Tetraglycol 99 monomethyl ether, the Tetraglycol 99 monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, the tripropylene glycol isopropyl ether, the polyalkylene glycol ethers class is for example as poly glycol monomethyl ether, Polypropylene Glycol Glycerin Ether, the polyoxyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether
Amine, for example as methylamine, ethamine, triethylamine, diethylamine, dimethylamine, Trimethylamine 99, dibutylamine, diethanolamine, trolamine, N-formyl thanomin, quadrol,
The derivative of urea, for example as urea, thiocarbamide, the N-methylurea, N, N '-ε-Dimethylurea, ethylidene-urea, 1,1,3, the 3-tetramethyl-urea, the N-acetyl ethanolamine,
Amides, for example as dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethanamide, ketone or ketols, for example as acetone, Pyranton,
The ring-type ethers, such as picture: tetrahydrofuran (THF), three ethane, TriMethylolPropane(TMP), butoxy ethanol, benzylalcohol, butoxy ethanol, gamma-butyrolactone, ε-Ji Neixianan,
Other tetramethylene sulfone, dimethylsulfolane, methyl sulfolane, 2, the 4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, methyl-sulphoxide, dibutyl sulfoxide, N-cyclohexyl pyrrolidone, the N-N-methyl-2-2-pyrrolidone N-, N-ethyl pyrrolidone, 2-Pyrrolidone, 1-(2-hydroxyethyl)-2-Pyrrolidone, 1-(3-hydroxypropyl)-2-Pyrrolidone, 1,3-dimethyl-2-imidazolone, 1,3-dimethyl-2-imidazolone, 1,3-dimethoxy-methyl imidazolone, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, 2-(2-butoxy oxyethyl group) ethanol, 2-(2-propoxy-oxyethyl group) ethanol, pyridine, piperidines, butyrolactone, trimethyl propane, 1, the 2-Propanal dimethyl acetal, dioxan, ethyl acetate, edetate, ethyl pentyl group ether, 1,2-Propanal dimethyl acetal and trimethyl propane.
Printing ink of the present invention can further comprise conventional additive, and viscosity moderator for example is in order to be set in viscosity 1.5 to 40.0mPas scope in 20 to 50 ℃ temperature range.Preferred printing ink has 1.5 to 20mPas viscosity and particularly preferred printing ink and has 1.5 to 15mPas viscosity.
Useful viscosity moderator comprises rheological additives, polyethylene hexanolactam for example, polyvinylpyrrolidone and their multipolymer polyether glycol, the associative thickener class, polyureas, urethane, sodium alginate, the polygalactomannan class of modification, polyethers urea, urethane and nonionic cellulose ether class.
As other additive, printing ink of the present invention can comprise surfactant, setting surface tension 20 to 65mN/m, can (if necessary) along with the variation of using method (heat or pressure techniques) makes this surface tension suitable.Useful surfactant comprises, for example all tensio-active agents, preferred nonionic surfactants, butyl Diethylene Glycol and 1,2-hexylene glycol.
This printing ink can further comprise conventional additive, for example suppresses the antiseptic-germicide of fungi and bacterial growth, and its content is 0.01wt% to 1wt% based on total ink.
Printing ink of the present invention can adopt ordinary method by each component mixture in water is made.
Printing ink of the present invention is specially adapted in ink-jet printed technology diversified material previously treated be carried out stamp, and these material previously treateds are, for example the cellulosic fibre material of silk, leather, woolen cloth, any kind of, urethane and tynex.Printing inks of the present invention also is suitable for pretreated hydroxyl and/or contains fiber (for example cotton, silk, the mixture of woolen cloth and the long and slender dimension of polyester or tynex) amino, that exist with mixture carrying out stamp.
Compare with the textile printing (wherein printing paste has comprised all the fixation chemical and the thickening material that are used for reactive dyestuffs) of routine, these auxiliary agents must be applied on this fabric substrate in an independent pre-treatment step in ink-jet printed.
The pre-treatment of fabric substrate (for example Mierocrystalline cellulose and regenerated cellulosic fibre and silk and woollen) is by finishing with a kind of aqueous alkaline liquid before stamp.For the set reactive dyestuffs, alkaline agent is existed a kind of needs, described alkaline agent is, yellow soda ash for example, sodium bicarbonate, sodium-acetate, tertiary sodium phosphate, water glass, sodium hydroxide, the donor of alkali is (for example as sodium chloroacetate, sodium formiate), hydroaropic substance (for example as urea), reduction inhibitor agent (for example nitrobenzene sodium sulfonate), and also have prevention colour image mobile thickening material when applying this printing inks (for example polygalactomannan of the polyacrylic ester of sodium alginate, modification or height etherificate).
These pretreating reagents are by using suitable coating machine (for example using the padding machine of a kind of 2-or 3-roller), the spray technique of non-contact-point, in the mode of foam application or use suitable evenly being coated on the fabric substrate, be dried subsequently through the value of adaptive ink-jet technology according to expectation.
After stamp, fabric fiber material is dry under 120 to 150 ℃, subsequently by fixation.
Ink-jet printed fixation with the reactive dyestuffs preparation can at room temperature or with saturated steam, superheated vapour, warm air, microwave, ir radiation, laser or electron beam or with other transmission ofenergy technology that are fit to realize.
One has a difference mutually and between the two-phase color-fixing method: in a phase fixation, necessary fixation chemical has been on the fabric substrate.In the two-phase fixation, this pre-treatment is unnecessary.Fixation only needs alkaline agent, and it is dry in the middle of not needing after ink-jet printed, applied before the fixation process.Other additive such as urea or thickening material are unwanted.
What follow after the fixation is the stamp aftertreatment, and it is good colour fastness, high brightness and the prerequisite of a flawless white background.
Use the stamp of printing ink production of the present invention all to have high colour intensity and high fiber-dye bond stability at acid range and alkaline range, also have good colour fastness to light and extraordinary moisture-proof colour fastness characteristic, for example washable, water-fast, sea water resistance, the dyeing of anti-intersection and colour fastness to perspiration, and also have good anti-pleating, heat-resisting pressure and colour fastness to rubbing.
(4) embodiment
The compound of describing in example with regard to chemical formula, is to point out with the form of free acid, is produced and separates even they generally are forms (the preferably salt of sodium or potassium) with their salt, and be used for dyeing with their form of salt.All λ max values are all measured in water in the following embodiments.
Embodiment 1
A) preparation of 2-amino-4-fluorobenzene sulfonic acid
140.5ml the vitriol oil join in the three-necked flask that the O/H agitator is housed of a 1000ml, in ice bath, cool off, add 65% the oleum of 110ml then, added in 15 minutes, obtain 25% oleum solution.Mixture is cooled to 10 ℃, dropwise adds the 3-fluoroaniline of 48.5ml then, added in 10 minutes, make 55 ℃＜T＜40 ℃ by exterior cooling in the dropping process.In case all reactants all add, reduce ice bath, stirring reaction and cool to room temperature.Reaction mixture is flooded 1080g blend in the ice, make T＜15 ℃ by the cooling of outside ice bath.The gained mixture is heated to room temperature and kept 1 hour then, leaches solid then, with 50ml saturated common salt water washing three times, drains and obtains thick product.
The thick product of gained being suspended in obtaining the pH value in the 2N NaOH solution of 200ml is 13.7, heating and add less water.All substances are all dissolved in the time of 70 ℃, and being cooled to room temperature then and being acidified to the pH value with dense HCl in ice bath is 1.5.The solid of separating out leaches, and is dry in a fan baking oven then.Solid HPLC result shows that product purity 98%, 2% is a para-isomeride.Obtain the crystalline solid of 49.0g lightpink behind the solid abrasive, one of HPLC demonstration is unimodal.Data analysis is consistent with the structure of suggestion.
B) preparation of dyestuff
(1.74g 0.0082mol) under agitation joins in the 50ml water 2-amino-4-fluorobenzene sulfonic acid, and the pH value to 6.5 of the sodium hydrogen carbonate solution regulator solution with 10% obtains solution.(0.57g 0.0082mol) joins in this solution, stirs that solution is dropwise joined in ice (50g) and dense HCl (10mls) mixture after being mixed after 10 minutes, uses exterior cooling to guarantee that temperature maintenance is at＜5 ℃ with Sodium Nitrite.After 30 minutes, diazotization reaction finishes, and excessive nitrite adds thionamic acid and removes.Monoazo-dyes (7.08g according to prior art for preparing with formula (IIIb1), 0.0082mol) in water-soluble (100ml), then diazonium salt is added in this solution in batches, add in 15 minutes, and keep pH value of solution between 5.0-6.0 by the sodium carbonate solution that adds 2N.Stirring is spent the night, and reaction mixture reduces volume through evaporation, and adds the dark solid product (10.55g) that methylated spirit is separated out expectation, and the analytical data that this solid shows is consistent with the structure with formula (Ia1) of expection.λmax?598nm，εmax?44800。
Figure BDA0000077193380000191
Figure BDA0000077193380000201
Embodiment 2
A) (10.0g 0.047mol) under agitation joins in the water (100ml), and with the pH value to 6.0 of sodium hydrogen carbonate solution regulator solution, obtains solution according to the 2-amino-4-fluorobenzene sulfonic acid of embodiment 1a preparation.(3.25g 0.047mol) joins in this solution, stirs that this solution is dropwise joined in ice (25g), water (25g) and dense HCl (15ml) mixture after being mixed after 10 minutes, uses exterior cooling to guarantee that temperature maintenance is at＜5 ℃ with Sodium Nitrite.After 30 minutes, diazotization reaction finishes, and excessive nitrite adds thionamic acid to be removed, add then H-acid (17.2g, 0.045mol) and stir and spend the night, during the pH value while reaction mixture that descends rise to envrionment temperature.Add the product that methylated spirit is separated out expectation then in mixture, this product is dark red solid (23.53g), and the analytical data that this solid analysis obtains is consistent with desired results.λmax?524nm?εmax?24000.
Figure BDA0000077193380000202
B) (6.1g 0.009mol) is dissolved in the 100ml water red monoazo product that a) prepares according to above-mentioned steps, obtains the solution of pH5; Add the cold suspension of the diazonium salt of 2-sulfo group-4-sulfato ethylsulfonyl aniline (0.01mol) in the gained solution in batches, get back to 5.0 with manganese hydrogen sodium regulating solution pH then.Again with this mixture heating up to envrionment temperature and keep pH=5.0 to spend the night.Regulator solution pH to 3.5 separates out product by controlledly adding methylated spirit then.Solid by filtration is separated also dry in one 40 ℃ fan baking oven, (Ia2) dyestuff that obtains having formula, and this dyestuff is dark solid (8.09g), the analytical data that this dyestuff shows is consistent with the structure of expection.λmax600nm，εmax?42500.
Figure BDA0000077193380000203
Embodiment 3
A) the red monoazo compound that obtains according to top embodiment 2b is separated, detects its intensity by combustion analysis then.
B) mixture of being made up of the compound of following two formulas is to make 2,4 according to prior art, 6-trifluoro pyrimidine and 2, and the condensation of 4-diamino benzene sulfonic acid makes, and the ratio of following positional isomers is approximate 2: 1 in this mixture.
Figure BDA0000077193380000211
C) (7.65g 0.01mol) is dissolved in the 60ml water mixture that obtains according to top step b), makes pH 6.0 by adding 10% sodium bicarbonate aqueous solution.(0.69g 0.01mol) and with mixture stirred 10 minutes to add Sodium Nitrite in this solution.This solution dropwise joins in ice (25g) and dense HCl (10ml) mixture after being mixed more then, use exterior cooling guarantee temperature remain on＜5 ℃.After 30 minutes, diazotization reaction finishes, and excessive nitrite is removed by adding thionamic acid, adds the solid chemical compound (6.78g for preparing according to top step a) then, 0.01mol) and stir, during pH risen and remain on 6.5 by adding sodium bicarbonate.Stir under the envrionment temperature and spend the night, the solution evaporation solvent gets enriched material, separates out product by controlledly adding methylated spirit then.Filtering separation obtains product, then at one 40 ℃ fan baking oven inner drying, and obtain the having formula dark solid (13.04g) of (Ia3), the analytical data that this solid shows is consistent with the isometry mixture of products of expection.λmax607nm，εmax?49000.
Figure BDA0000077193380000212
Dyestuff among the following embodiment 4 to 112 can obtain according to the method for describing among the embodiment 1 to 3:
Figure BDA0000077193380000213
Figure BDA0000077193380000221
Figure BDA0000077193380000231
Figure BDA0000077193380000251
Figure BDA0000077193380000261
Figure BDA0000077193380000271
Figure BDA0000077193380000291
Figure BDA0000077193380000321
Figure BDA0000077193380000331
Figure BDA0000077193380000341
Figure BDA0000077193380000351
Figure BDA0000077193380000361
Figure BDA0000077193380000371
Figure BDA0000077193380000381
Figure BDA0000077193380000401
Figure BDA0000077193380000411
Embodiment 113: have the 2-amino-4 of formula (VIa1), the preparation of 5-difluoro Phenylsulfonic acid
The vitriol oil (70.25ml) joins in the three-necked flask that the O/H agitator is housed of a 500ml, and ice bath cools off, and adds 65% oleum (55ml) then, adds in 15 minutes, obtains 25% oleum solution.Dropwise add 3 then, 4-phenyl-difluoride amine (24.79ml) uses exterior cooling so that T＜56 ℃ in the process.In case temperature stops to rise, reduce ice bath and be arranged on reacting by heating 3.5h in 95 ℃ the hot oil bath in advance at one.Reaction mixture is submerged in blends in the ice (approximately 400g), make T＜30 ℃, obtain the peach solid suspension of separating out by outside ice bath cooling.This solid leaches, and uses the saturated aqueous common salt of 80ml to wash on suction filter 3 times, then decompress filter.Again with solid suspension in acetone, filter, drain, dry in 40 ℃ of fan baking ovens then.With lightpink solid abrasive powdered (39.72g), one of HPLC demonstration is unimodal.Analytical data is consistent with the structure that is proposed.
Embodiment 114: the preparation with 2-amino-4-fluoro-5-toluene sulfonic acide of formula (VIa3)
The vitriol oil (70.25ml) joins in the there-necked flask of a 500ml that the O/H agitator is housed, and the ice bath cooling adds 65% oleum (56ml) then, adds in 10 minutes, obtains 25% oleum, it is cooled to about 10 ℃ again.Heating makes 3-fluoro-4-monomethylaniline, and (28.9ml, 0.25mol) fusing and directly pipette with transfer pipet joins in the reaction mixture, adds to guarantee that temperature of reaction is no more than 50 ℃ in 10 minutes.Then the brown reaction mixture of this viscosity is removed ice bath, and be cooled to room temperature.Reaction mixture is submerged in the 470g trash ice, cools off in the ice-water bath by the outside.The solid of separating out leaches, and decompress filter is with the saturated common salt water washing of 40ml.Wet cake is dried overnight in one 40 ℃ fan baking oven.Obtain the white powder (69.18g) of slight viscosity behind the solid abrasive, one of HPLC demonstration is unimodal.Analytical data is consistent with the structure that is proposed.
Embodiment 115: have the 4-amino-2 of formula (VIa2), the preparation of 5-difluoro Phenylsulfonic acid.
The method of describing among the preparation of this compound and the embodiment 114 is similar.
Embodiment 116: 2-amino-4-fluoro-5-[4-(2-sulfonic acid oxygen-ethylsulfonyl)-phenylazo-with formula (VIa4)]-preparation of Phenylsulfonic acid
(28.85g, 0.1mol) in the water of stirring suspension at 400ml, and adding 10% yellow soda ash, to regulate pH be 7 to sulfuric acid list-[2-(4-amino-benzenesulfonyl)-ethyl] ester, obtains solution.Sodium nitrite solution (the 22ml that in this solution, adds 5M; 0.11mol).Then this solution is joined in ice (150g) and concentrated hydrochloric acid (70ml) mixture after being mixed, add in 1 hour, continue again to stir 1 hour.Excessive nitrite is removed by adding thionamic acid.Stir down 2-amino-5-fluorobenzene sulfonic acid (19.0g, 0.09mol) all join in the diazonium salt, add the back and regulate the pH to 4 of mixture, be to regulate pH to 4 at first by adding solid sodium bicarbonate, keep this pH value by adding 10% yellow soda ash then, under room temperature, pH=4 condition, stir again and spend the night.Add 20ml concentrated hydrochloric acid and 10g 1,3 in reaction mixture, the 6-naphthalene trisulfonic acid is heated to 45 ℃ of reactions 5 hours then.The salt that adds 10%w/v filters and collects the solid that generates, and at one 40 ℃ fan baking oven inner drying, obtains brown solid (31.5g) then, and analytical data is consistent with the structure that is proposed.
Embodiment 117: the preparation with 2-amino-4-fluoro-5-methoxy benzenesulfonic acid of formula (VIa6)
(5.0g 35.42mmol) joins in the three-necked flask of a 250ml who is equipped with overhead type agitator, condenser, thermometer and dropping funnel 3-fluoro-4-anisidine.Add 1,2-dichlorobenzene (100ml) stirs.(4.25g 35.42mmol), dropwised in 20 minutes, generated the precipitation of purple dropwise to add chlorsulfonic acid in this solution.Solution slowly is heated to reflux temperature, refluxed 4 hours.Solution is cooled to envrionment temperature, and the purple solid leaches and uses washed with dichloromethane.Solid is dissolved in the water of 100ml and regulates pH=7, use the dichloromethane extraction 3 times of 50ml then with the NaOH of 2N.With dense HCl solution is acidified to pH=1, generates light grey precipitation.Solid leaches and use washing with acetone, and is dry in one 40 ℃ fan baking oven then, obtains product (7.09g).The analytical data that shows is consistent with the structure of expection.
Embodiment 118: the preparation with 2-amino-4-fluoro-5-toluene sulfonic acide of formula (VIa3)
(12.52g 100mmol) joins in the there-necked flask of a 250ml who is equipped with overhead type agitator, condenser, thermometer and dropping funnel 3-fluoro-4-monomethylaniline.Add 1 of 50ml, 2-dichloro benzo stirs.(12.01g 100mmol), dropwised in 20 minutes, generated gray precipitate dropwise to add chlorsulfonic acid in gained solution.This solution slowly is heated to reflux temperature, and refluxes 4 hours.Then solution is cooled to room temperature, solid leaches and uses washed with dichloromethane.Be dissolved in solid in the 100ml water and usefulness 2N NaOH adjusting pH=7, use the 50ml dichloromethane extraction then 3 times.With dense HCl gained solution is acidified to pH=1, generates grayish precipitation.Solid leaches and use washing with acetone, and is dry in one 40 ℃ fan baking oven then, obtains product (14.94g), and the analytical data that this product shows is consistent with the structure of expection.
Embodiment 119: have the amino 4-fluoro-1 of 6-of formula (VIa7), the preparation of 3-Phenylsulfonic acid
The 3-fluoroaniline (28.06g, 0.25mol) dropwise joined at ambient temperature oleum after the stirring (25%, 125.3mls) in, make temperature inside remain on below 50 ℃.Kept 30 minutes with this mixture heating up to 90 ℃ and under this temperature then, be cooled to envrionment temperature again,, obtain yellow solution in 500g quenching on ice.The solution that adding KCl obtains 5%w/vol generates white precipitate.Solid filtering is also used washing with acetone, and is dry in one 40 ℃ fan baking oven then, obtains white solid (69.63g), and the analytical data that this solid shows is consistent with the structure of expection.
Embodiment 120: the preparation with 6-amino-2,4 difluorobenzene sulfonic acid of formula (VIa8).
The vitriol oil (28.1ml) is added in the three-necked flask of a 250ml that agitator is housed, and the ice bath cooling adds 65% oleum (22ml) then, adds in 15 minutes, obtains 25% oleum solution.Add 3,5-difluoroaniline (13.04g) also added in 40 minutes so that T＜45 ℃.In case temperature stops to rise, reacting by heating is 2 hours 20 minutes in the hot oil bath in advance of a design temperature at 60 ℃.Then mixture is cooled to envrionment temperature in an ice-water bath.Reaction mixture is flooded blending of 210g generate precipitation in the ice.This precipitation is sifted out and decompress filter.The solid suspension that obtains in 70ml water, is heated to 60 ℃ and alkalize to pH=10 with yellow soda ash, obtains limpid solution.Then with this solution with dense HCl acidifying and be cooled to envrionment temperature.The solid that generates leaches, and decompress filter is dry in one 40 ℃ fan baking oven then, obtains the solid (10.087g) of rice white, and the analytical data that this solid shows is consistent with the structure of expection.
Embodiment 121: have the 6-amino-2 of formula (VIa5), 4-two fluoro-1, the preparation of 3-Phenylsulfonic acid
The vitriol oil (26ml) is added in the three-necked flask of a 250ml that agitator is housed, and the ice bath cooling adds 65% oleum (22ml), adds in 25 minutes and obtains 25% oleum solution.Add 3,5-difluoroaniline (12.14g) and adding in 10 minutes makes T＜50 ℃.Along with this mixture is heated to 95 ℃ from 65 ℃, stirring reaction 6 hours, envrionment temperature is got back in cooling then.Mixture promptly is submerged in the 210g trash ice, handles to the precipitation of 7% formation white with salt.This solid leaches and decompress filter, and is dry in one 40 ℃ fan baking oven then.White solid obtains white powder (25.71g) through grinding, and the analytical data that this powder shows is consistent with the structure of expection.
Embodiment 122
The textile fabric that is made of mercerized cotton pads with the liquid of the low viscosity sodium alginate (6%) of the urea of the anhydrous sodium carbonate of a kind of 35g/l of containing, 100g/l and 150g/l, and is dry then.The fiber liquid absorption is 70%.The fabric that obtains of the pre-treatment ink-jet printed head that uses a drop on demand ink jet carries out stamp with a kind of water color ink that contains the dyestuff that makes among 2% the embodiment 1,20% tetramethylene sulfone, 0.01%Mergal K9N and 77.99% water thus.The stamp thorough drying.With saturation steam 102 ℃ of following fixation 8 minutes.The stamp warm water washing stands the fastness washing of 95 ℃ hot water subsequently, warm water washing, the stamp that dry then acquisition has fabulous fastness.

Claims (10)

1. the dyestuff that has formula (I)
Figure FDA0000077193370000011
Wherein
A is 1 or 2;
X 1Be the aryl or the heteroaryl of a divalence;
RG be one under dyeing condition can with amide-containing-and/or hydroxyl-material form the active group of covalent linkage, or one contains the group that can form the active group of covalent linkage under dyeing condition with Mierocrystalline cellulose, or hydrogen;
R 1Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, chlorine or a group with formula (II)
Figure FDA0000077193370000012
Wherein
X 2Be an aryl or heteroaryl;
R 3Be hydrogen or-SO 3M;
R 4Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, fluorine, chlorine ,-SO 2CH=CH 2Or-SO 2CH 2CH 2Z, wherein Z is-OSO 3M ,-OAc ,-OPO 3H 2Or chlorine;
B is 1 or 2;
C is 1,2 or 3;
R 2Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, sulfo group, hydroxyl or chlorine; And
M is a hydrogen, the Equivalent of a kind of basic metal or a kind of alkaline-earth metal;
Supplementary condition are if R 1Be not the group with formula (II), RG is not a hydrogen; And further supplementary condition are to get rid of the compound with formula (A),
B is hydrogen or phenyl in the formula (A), and M as above defines.
2. the dyestuff described in claim 1, wherein X 1Be to have formula (IIIa) to one of group of formula (IIIj):
Wherein
Ar is a phenylene or by 1,2 or 3 phenylenes that substituting group replaces, and wherein substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, halogen and-SO 3M;
E 1Has one of definition of Ar; Perhaps E 1Be naphthyl or the naphthyls that replaced by 1,2 or 3 substituting groups, wherein substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group ,-SO 3M, amino, kharophen or hydroxyl; Or E 1Be a heterocycle residue with 5 or 6 ring structures, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur; Or E 1Be a heterocycle residue with 5 or 6 ring structures, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur, and this heterocyclic group is by 1,2 or 3 substituting groups replacements, and described substituting group is selected from (C 1-C 4)-alkyl and (C 1-C 4)-alkoxyl group;
E 2Be phenylene or naphthylidene, described phenylene and naphthylidene are not substituted or by 1,2 or 3 substituting groups replacements, described substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group ,-SO 3M, amino, kharophen or hydroxyl; Or E 2Be the heterocycle residue of 5 or 6 ring structures of a divalence, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur; Or E 2Be the heterocycle residue of 5 or 6 ring structures of a divalence, this heterocycle residue contains one or two heteroatoms, and heteroatoms is selected from nitrogen, oxygen and sulphur, and this heterocycle residue is by one, two or three substituting groups replacements, and described substituting group is selected from (C 1-C 4)-alkyl and (C 1-C 4)-alkoxyl group; Or E 2It is a group with formula (IV)
Figure FDA0000077193370000031
Wherein
R 7Be (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group ,-SO 3M or hydroxyl;
R 8And R 8' be alone hydrogen separately, (C 1-C 6)-alkyl, sulfo--(C 1-C 6)-alkyl, phenyl or quilt (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl ,-SO 3M, halogen ,-phenyl that COOM, kharophen or urea groups replace;
R 8aBe hydrogen or kharophen;
R 5Be (C 1-C 4)-alkyl or-COOM;
R 6Be hydrogen, CN or-CONH 2
L is 1,2-phenylene, 1, and 3-phenylene or 1, the 4-phenylene, described 1,2-phenylene, 1,3-phenylene and 1, the 4-phenylene is not substituted or quilt-SO 3M ,-COOM or R 8Replace; Or L is (C 2-C 6)-alkylidene group or (C 1-C 4)-alkylidene group-phenylene, described (C 2-C 6)-alkylidene group and (C 1-C 4)-alkylidene group-phenylene is not substituted or by R 8Replace;
The definition of M as mentioned above; And
*Represent this key to be connected with the RG group.
3. as claim 1 and/or 2 described dyestuffs, wherein RG is-SO 2-CH=CH 2,-SO 2-CH 2CH 2Z 1Or group with formula (IV)
-N(R 8)-A (IV)
Wherein
Z 1It is the separable group of alkali;
R 8Definition as above;
A has formula (Va), (Vb) or group (Vc)
Figure FDA0000077193370000041
V is a fluorine or chlorine;
U 1And U 2Be alone fluorine separately, chlorine or hydrogen; And
Q 1And Q 2Independent separately is chlorine, fluorine, cyanogen amino, hydroxyl, (C 1-C 6)-alkoxyl group, phenoxy group, sulfophenoxy, sulfydryl, (C 1-C 6)-alkyl thiol, pyrido, carboxyl pyridine also, formamyl pyrido or a group with formula (VI) or formula (VII)
Figure FDA0000077193370000042
Wherein
R 9Has R 1One of definition or R 9It is phenyl;
R 10And R 11Has R independently 1One of definition, or R 10And R 11Be phenyl, hydroxyl-(C independently 1-C 6)-alkyl, one have formula-(CH 2) 2-S-(CH 2) 2The group of-OH or R 10And R 11Has formula-(CH in conjunction with forming one 2) j-or formula-(CH 2) 2-B 1-(CH 2) 2-group, wherein j is 4 or 5, B 1Be oxygen, sulphur, alkylsulfonyl or-NR 9-, and R 9Be (C 1-C 6)-alkyl;
W is unsubstituted phenylene or the phenylenes that replaced by 1 or 2 substituting groups, and described substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, carboxyl, sulfo group, chlorine and bromine; Or W is (C 1-C 4)-alkylidene group phenylene, (C 2-C 6)-alkylidene group, wherein (C 2-C 6)-alkylidene group can be interrupted by oxygen, sulphur, alkylsulfonyl, amino, carbonyl or amide group; Or W is unsubstituted or by 1 or 2 phenylene-CO-NH-phenylenes that substituting group replaces, described substituting group is selected from (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, sulfo group, carboxyl, amino, urea groups and halogen; Or W is naphthylidenes unsubstituted or that replaced by 1 or 2 sulfo groups; And
Z 2Be-CH=CH 2Or-CH 2CH 2Z 1
4. as one in the claim 1 to 3 or multinomial described dyestuff, it is to have formula (Ia) to one of dyestuff of formula (In):
Figure FDA0000077193370000051
Figure FDA0000077193370000061
Wherein, X 1, X 2, R 3, R 4, R, G, b, the definition of c and M is with claim 1.
5. as one in the claim 1 to 4 or multinomial described dyestuff, it is to have formula (Io) to one of dyestuff of formula (It):
Figure FDA0000077193370000062
Figure FDA0000077193370000071
Wherein
A 1Be to have formula (Vf), (Vg), (Vh) or group (Vi);
A 2Be to have formula (Vd) or group (Ve);
A 2' be to have formula (Vd) or group (Ve);
R 12Be methyl, methoxyl group or-SO 3M;
R 12' be methyl, methoxyl group or-SO 3M; And
The definition of M according to claim 1.
6. prepare the method with dyestuff of formula (I) as claimed in claim 1, wherein make compound diazotization and be coupled on the have formula compound of (VII) with formula (VI),
Figure FDA0000077193370000081
-X 1-RG (VII)
In the formula (VI), R 1, R 2, the definition of a and M according to claim 1; In the formula (VII), X 1With the definition of RG according to claim 1.
7. the dyestuff with formula (I) as claimed in claim 1 is in amide-containing-and/or the dyeing of the material of hydroxyl and purposes in the stamp.
8. a printing ink that is used for being undertaken by ink-jetting process the textiles digit printing comprises dyestuff as claimed in claim 1.
9. the compound that has formula (VIa)
Figure FDA0000077193370000082
Wherein
A is 1 or 2;
D is 1 or 2;
R 1aBe (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, fluorine, chlorine or a group with formula (II)
Figure FDA0000077193370000083
Wherein
X 2Be an aryl or heteroaryl;
R 3Be hydrogen or-SO 3M;
R 4Be hydrogen, (C 1-C 4)-alkyl, (C 1-C 4)-alkoxyl group, hydroxyl, chlorine, SO 2CH=CH 2Or-SO 2CH 2CH 2Z, wherein Z is-OSO 3M ,-OAc ,-OPO 3H 2Or chlorine;
B is 1 or 2;
C is 1,2 or 3; And
M is a hydrogen, the Equivalent of a kind of basic metal or a kind of alkaline-earth metal;
Supplementary condition are to get rid of the compound with formula C and formula D,
Figure FDA0000077193370000091
Wherein the definition of M as above.
10. the compound described in claim 9, it is to have formula (VIa1) to one of compound of formula (VIa9):
Figure FDA0000077193370000092
Figure FDA0000077193370000101
Z wherein 2Be-CH=CH 2Or-CH 2CH 2OSO 3M, the definition of M is as described in the claim 9.
CN2009801550203A 2008-11-20 2009-11-13 Ring fluorinated reactive dyes Pending CN102292399A (en)

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CN102876079A (en) * 2012-09-20 2013-01-16 天津德凯化工股份有限公司 Black reactive dye and preparation method thereof
CN104968732A (en) * 2012-06-18 2015-10-07 德司达染料分销有限公司 Metal free reactive dyes, process for the production thereof and their use
CN105603776A (en) * 2015-10-30 2016-05-25 无锡市长安曙光手套厂 Formula of reactive dye
CN105745282A (en) * 2013-08-29 2016-07-06 德司达染料分销有限公司 Dye mixtures of reactive dyes, production and use
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CN104968732B (en) * 2012-06-18 2017-08-08 德司达染料分销有限公司 Metal-free reactive dye, and its preparation method and application
CN102876079A (en) * 2012-09-20 2013-01-16 天津德凯化工股份有限公司 Black reactive dye and preparation method thereof
CN105745282A (en) * 2013-08-29 2016-07-06 德司达染料分销有限公司 Dye mixtures of reactive dyes, production and use
CN105745282B (en) * 2013-08-29 2017-06-23 德司达染料分销有限公司 Reactive dye mixture, and its preparation method and application
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CN105603776A (en) * 2015-10-30 2016-05-25 无锡市长安曙光手套厂 Formula of reactive dye

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