WO1986004080A1 - Improvements in or relating to organic compounds - Google Patents
Improvements in or relating to organic compounds Download PDFInfo
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- WO1986004080A1 WO1986004080A1 PCT/EP1985/000745 EP8500745W WO8604080A1 WO 1986004080 A1 WO1986004080 A1 WO 1986004080A1 EP 8500745 W EP8500745 W EP 8500745W WO 8604080 A1 WO8604080 A1 WO 8604080A1
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- alkyl
- substituted
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- XDTMQSROBMDMFD-UHFFFAOYSA-N C1CCCCC1 Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 0 CC1NC(NC(C=C2*)=C(*)C[C@]2N=NC)NC(*)N1 Chemical compound CC1NC(NC(C=C2*)=C(*)C[C@]2N=NC)NC(*)N1 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N C1CC=CCC1 Chemical compound C1CC=CCC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- CGKWPEZACKOGIO-UHFFFAOYSA-N CNC(C(C(N1)F)Cl)NC1F Chemical compound CNC(C(C(N1)F)Cl)NC1F CGKWPEZACKOGIO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Definitions
- the invention relates to water-soluble compounds containing a fibre-reactive group which compounds are suitable as dyestuffs in conventional dyeing and printing processes. Their dyeings and prints are resistant to any oxidative influences.
- each of F 1 and F 2 is independently a water-soluble organic dyestuff radical
- each Y is independently -O- or
- each B is independently a divalent bridge member
- m is independently 0 or 1
- each R is independently hydrogen, alky! or substituted alkyl
- n is 0, 1 or 2
- each Q is independently hydrogen, alkyl, substituted alkyl or a cellulose fibre-reactive group, provided that at least one of the two possible groups Q is a cellulose fibre- reactive group;
- B is a divalent bridge member
- R 1 is alkyl or substituted alkyl, p is 0 or 1,
- B 2 is a tri- or tetravalent bridge member, Q a i s a cellulose fibre-reactive group, r is 1 or 2, q is 0 or 1, whereby n + q is at least 1, and q is 0 if n is 1 or 2, provided that a compound of formula I contains at least one of the groups listed below,
- F 1 and F 2 are preferably an organic dyestuff radical of the metal-free or metallised mono-, dis- or polyazo, anthraquinone, phthalocyanine, oxazine, dioxazine, nitro or formazan series which contains water-solubilising groups.
- Particularly preferred are dyestuff radicals belonging to the metal-free or metallised mono- or disazo series.
- Any fibre-reactive group as A or Q a is preferably one of the following groups Q 1 to Q 5 : -
- the group Q 1 is most preferred.
- any hydroxysubstituted alkyl group which is attached to a nitrogen atom the hydroxy group is bound to a carbon atom other than to the C 1 -atom.
- Any alkyl as R is preferably linear or branched C 1-4 alkyl. More preferably it is methyl or ethyl, especially methyl.
- Any substituted alkyl as R is preferably a monohydroxysubstituted C 2 -8 alkyl group, a dihydroxysubstituted C 3 - 8 alkyl group, or More preferably it is a monohydroxysubstituted C 2-4 alkyl group, dihydroxysubstituted Chalkyl or -CH 2 CH 2 OCH 2 CH 2 OH. Most preferably it is 2-hydroxyethyl or 2,3-dihydroxypropyl.
- R is preferably R a , where R a is hydrogen, methyl, ethyl, monohydroxy-C 2-8 alkyl, dihydroxy-C 3-8 alkyl, or More preferably R is R b , where R b is hydrogen, methyl, monohydroxy-C 2-4 alkyl, dihydroxy-C 3-4 alkyl or
- R c is hydrogen, -CH 2 CH 2 OH, or -CH 2 CH 2 OCH 2 CH 2 OH.
- R d is hydrogen or -CH 2 CH 2 OH.
- Y is preferably -O- , -NH- or ; especially -NH-.
- Any alkyl as Q is straight chain or branched; any unsubstituted alkyl preferably contains 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms. Any substituted alkyl as Q is preferably monohydroxysubstituted C 2-4 alkyl, dihydroxysubstituted C 3-4 alkyl or -CH 2 CH 2 OCH 2 CH 2 OH.
- the group (Q a ) preferably signifies either the group , more preferably the group ,
- group -NH-Q a in which groups Q a is most preferably Q 1 ; or the group -NH-Q d , in which Q d is hydrogen, monohydroxy- C 2-4 alkyl, dihydroxy-C 3-4 alkyl or -CH 2 CH 2 OCH 2 CH 2 OH; more preferably Q d is hydrogen or -C H2 CH 2 OH.
- B is preferably a chain-type, linear or branched bridge member or a bridge member which is branched by a cycloaliphatic, aromatic or heteroaromatic ring system, which bridge members additionally contain at least one of the above-listed groups (a) to (d), especially a hydroxy or carbonyl group thereof.
- B is a chain-type bridge member, it preferably denotes mono- or dihydroxysubstituted C 3-6 alkylene or -CO(CH 2 ) 1-3 -; especially , or -COCH 2 -.
- Any branching in B preferably takes place through a heteroaromatic ring system, especially through triazine rings.
- Q b is hydrogen, alkyl, substituted alkyl or one of the groups Q 1 to Q 5 as defined above,
- R 2 is chlorine, or -OR 5 , each R 3 is independently hydrogen, alkyl or substituted alkyl,
- R 5 is monohydroxysubstituted C 2-6 alkyl, di- or polyhydroxy- substituted C 3-8 alkyl, or and
- R 4 is (i) monohydroxysubstituted C 2-6 alkylene or di- or polyhydroxysubstituted C 3-8 alkylene,
- R 2 is defined as .
- R 4 is a group as defined under (i) or (ii).
- R 1 is preferably monohydroxy-C 2-4 alkyl, dihydroxy-C 3-8 alkyl, more preferably, R 1 is -CH 2 CH 2 OH or -CH 2 CH(OH)CH 2 OH.
- B 1 is preferably a C 3-6 alkyleneamine group which is linear or branched and may be substituted by one or two hydroxy groups, or is -CO(CH 2 ) 1-5 NH-. Most preferably, B 1 is or -CO(CH 2 ) 1-5 NH-.
- B 2 is preferably a tri- or tetravalent, especially trivalent bridge member containing triazine rings.
- -B 2 -NH-Q a is a group of formula (a)
- R 2 , R 3 and R 4 are as defined above, and Q c is one of the groups Q 1 to Q 5 as defined above.
- B a is mono- or dihydroxysubstituted C 3 _ 6 alkylene or
- R is R a or
- R 2 , R 3 , R 4 and Q b are as defined above, and R 4 is more preferably a group as defined under (i) or (ii), provided that at least one of the two possible Q or Q b is a fibre-reactive group; and in which a) in the case where n is 1, F 1 -NH- has one of the following preferred significances: -
- t is 0 or 1 ;
- t is 0 or 1 , and subst. is H, CH 3 , OCH 3 or NHCOCH 3 ;
- each t is independently 0 or 1 , the sulpho group is in position 3 or 4;
- S 1 is H, CH 3 , OCH 3 , NHCOCH 3 or NHCONH 2
- S 2 is H or OCH 3 ;
- each of the -NH- groups is independently in the 4- or 5-position; in which compounds of formula la both groups may be the same or different and in particular, only one of both groups Q is a fibre-reactive group.
- R is preferably R b , and more preferably R c , and in the case where n is 1, as well as in the case where n is 2, the same definitions apply to F 1 as given for the compounds of formula la.
- R 2 , R 3 , R 4 and Q a are as defined above, and F 1 and F 2 have one of the following preferred significances: - a) F 1 -NH- is a group of the formula,
- F 2 -NH- is a group of the formula
- F 1 -NH- is a group of the formula
- F 2 -NH- is a group of the formul,
- each S 1 is independently H, CH 3 , OCH 3 , NHCOCH 3 or NHCONH 2
- each S 2 is independently H or OCH 3 .
- B 1 is NH- or -CO(CH 2 ) 1 _ 5 NH-
- R 1 is monohydroxysubstituted C 2-4 alkyl, dihydroxysubstituted C 3-8 alkyl, i s a group of the formula
- each t is independently 0 or 1 and the sulpho group is in the 3- or 4-position
- S 3 is H or CH 3 and S 4 is -O-B 1 -R 1 or
- S 3 is -NH-B 1 -R 1 and S 4 is H.
- the fibre- reactive group is Q 1 .
- the cation of any sulpho and carboxy groups is not critical and may be any of those non-chromophoric cations conventional in the field of reactive dyestuffs provided that the corresponding salts as obtained are water-soluble.
- examples of such cations are alkali metal cations and unsubstituted or substituted ammonium cations, e.g., lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, triethyl-ammonium, mono-, di- and tri-ethanolammonium.
- the preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.
- a compound of formula I the cations of any sulpho and carboxy groups can be the same or different, i.e. they can also be a mixture of the above mentioned cations meaning that the compound of formula I can be in a mixed salt form.
- the present invention further provides a process for the preparation of the compounds of formula I comprising reacting a compound of formula II,
- R x is hydrogen, alkyl or substituted alkyl, and each n' is independently 0 or 1 , with a compound of formula II I ,
- Q a Hal III in which Q a is a cellulose fibre-reactive group
- Hal is halogen
- This condensation may be effected in accordance with conventional methods.
- the compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali metal salts, filtering and drying in vacuo.
- a compound of formula I containing sulpho and/or carboxy groups is obtained in free acid or preferably salt form or even mixed salt form containing, for example, one or more of the above-mentioned cations. It may be converted from free acid form to a salt form or mixtureof salt forms or vice versa or from one salt form to another by conventional means.
- the starting compounds of formula II are known with regard to their chromophoric part.
- various ways of preparation may be used. All these methods concern processes known per se which therefore are analogous preparation processes.
- step (1a) may be prepared using in step (1a), instead of cyanuric chloride, the condensation product consisting of two cyanuric chloride radicals linked together by a bridge; the process is otherwise effected in analogous manner.
- S is a protecting group, either with a bifunctional chlorohydrin such as epichloro hydrin, or with an ⁇ -chloro-acid chloride such as chloroacetic acid chloride;
- the compounds of formula I and mixtures thereof are useful as fibre-reactive dyestuffs for dyeing or printing hydroxy group or nitrogen containing organic substrates.
- Preferred substrates are leather and fibre materials containing or consisting of natural or synthetic polyamides and, particularly, of natural or regenerated cellulose such as cotton, viscose and spun rayon.
- the most preferred substrate is textile material containing or consisting of cotton.
- Dyeing or printing is effected in accordance with known methods conventional in the reactive dyestuff field. Especially preferred is the exhaust dyeing method.
- the most favourable and therefore preferred dyeing temperature is within the cold-dyeing range of from 30 to 60°C.
- the compounds of this invention are well compatible with other reactive dyes; they may be applied per se or in combination with appropriate fibre-reactive dyestuffs of the same class having analogous dyeing properties, e.g., concerning common fastness properties, extent of ability to exhaust from the dyebath onto the fibre etc.
- the dyeings obtained with such combination mixtures have good fastness properties and are comparable to those obtained with a single dyestuff.
- the compounds of formula I give high exhaust and fixation yields.
- the dyeings and prints obtained show particularly good light fastness, but also good wet fastness properties such as fastness to washing, water, sea water and sweat.
- the present dyestuffs give dyeings and prints which show good resistance to any oxidative influences, e.g., chlorinated water, hypochlorite bleach and peroxide or perborate containing wash liquors.
- the dyestuff thus obtained is salted out using an appropriate amount of sodium chloride, and is filtered off. 13.5 Parts of 5-chloro-2,4,6-trifluoropyrimidine are added to the dye paste which is dissolved in 900 parts of water. Stirring is effected for two hours at 30-40°, and the pH is kept at 5-6 by adding dilute sodium carbonate solution.
- the obtained dyestuff is salted out with sodium chloride and isolated in conventional manner, it corresponds, in free acid form, to the formula
- the dyestuff when dried is a dark-red powder which dissolves in water in a red colour.
- This dyestuff dyes cotton a red shade.
- the dyeings obtained show good light and wet fastness properties, especially they are stable to any oxidative influences.
- Cellulose fibres may be dyed with the dyestuffs listed in the tables, in particular using the conventional exhaust dyeing method.
- column I of each of the Tables 1 to 4 the shade of the dyeing on cotton is given, whereby a is greenish-yellow h is bluish-red b is yellow i is ruby c is golden-yellow j is violet d is orange k is blue e is red-orange l is greenish-blue f is scarlet m is turquoise g is red n is navy.
- the cotton dyeings obtained with the compounds of Table 5 are all reddish-yellow.
- the resultant cotton dyeings have good light and wet fastness properties, they are especially resistant to any oxidative influences.
- X is -NHCH 2 CH 2 OH; for Example 136, X is each of them dyes cotton a navy shade.
- the dyestuffs of Examples 1 to 137 are obtained in the sodium salt form. They may, depending on the reaction/isolation conditions or by reacting the sodium salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms containing one or more cations indicated in the description above.
- the dyeing is soaped at the boil for 15 minutes in 500 parts of demineralised water and 0.25 parts of sodium lauryl sulphonate. After rinsing with running hot water (for 3 minutes) and centrifuging, the dyeing is dried in a cabinet dryer at ca. 70°. A red (navy) cotton dyeing is obtained which shows good light fastness and wet fastness properties and which is resistant to any oxidative influences.
- a printing paste consisting of
- the printed fabric is dried and fixed in steam at 105° for one minute. It is then rinsed in hot water, soaped at the boil (according to the method described in Application Example A) and dried. A red (red-orange) print is obtained which has good general fastness properties and is stable to any oxidative influences.
- the dyestuffs of the other examples or mixtures of the dyestuffs of Examples 1 to 137 may be employed to dye or print cotton in accordance with the method given for Application Examples A and B.
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Abstract
New water-soluble, fibre-reactive compounds correspond to formula (I) in which the symbols are as defined in Claim 1, provided that a compound of formula (I) contains at least one of the following groups: (a) hydroxy groups, (b) ether groupings, (c) carbonyl groups, (d) carboxy groups, which group(s) is (are) in the compounds of formula (II) and/or in R. These compounds are prepared in conventional manner by condensation of a compound Qa-Hal with an appropriate starting compound containing a primary or secondary amine group. The compounds of formula (I) are suitable as fibre-reactive dyes for dyeing or printing hydroxy group or nitrogen containing organic substrates, especially cotton. The preferred dyeing temperature is in the cold-dyeing range. The dyeings and prints obtained have good general fastness properties and are stable to any oxidative influences.
Description
IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
The invention relates to water-soluble compounds containing a fibre-reactive group which compounds are suitable as dyestuffs in conventional dyeing and printing processes. Their dyeings and prints are resistant to any oxidative influences.
According to the invention there is provided a compound corresponding to formula I
in which each of F1 and F2 is independently a water-soluble organic dyestuff radical, each Y is independently -O- or ,
each B is independently a divalent bridge member, m is independently 0 or 1 , each R is independently hydrogen, alky! or substituted alkyl,
n is 0, 1 or 2, each Q is independently hydrogen, alkyl, substituted alkyl or a cellulose fibre-reactive group, provided that at least one of the two possible groups Q is a cellulose fibre- reactive group;
B is a divalent bridge member,
R1 is alkyl or substituted alkyl, p is 0 or 1,
B2 is a tri- or tetravalent bridge member, Qa i s a cellulose fibre-reactive group, r is 1 or 2, q is 0 or 1, whereby n + q is at least 1, and q is 0 if n is 1 or 2, provided that a compound of formula I contains at least one of the groups listed below,
(a) hydroxy groups
(b) ether groupings
(c) carbonyl groups
(d) carboxy groups which is present in one of the groups -Y-B- ; -Y-B1-R1 ;
and R, respectively, and salts of a compound of formula I.
F1 and F2 are preferably an organic dyestuff radical of the metal-free or metallised mono-, dis- or polyazo, anthraquinone, phthalocyanine, oxazine, dioxazine, nitro or formazan series which contains water-solubilising groups. Particularly preferred are dyestuff radicals belonging to the metal-free or metallised mono- or disazo series.
Any fibre-reactive group as A or Qa is preferably one of the following groups Q1 to Q5 : -
The group Q1 is most preferred.
In the specification, in any hydroxysubstituted alkyl group which is attached to a nitrogen atom, the hydroxy group is bound to a carbon atom other than to the C1-atom.
Any alkyl as R is preferably linear or branched C1-4alkyl. More preferably it is methyl or ethyl, especially methyl.
Any substituted alkyl as R is preferably a monohydroxysubstituted C2 -8alkyl group, a dihydroxysubstituted C3-8alkyl group, or More
preferably it is a monohydroxysubstituted C2-4alkyl group, dihydroxysubstituted Chalkyl or -CH2CH2OCH2CH2OH. Most preferably it is 2-hydroxyethyl or 2,3-dihydroxypropyl.
R is preferably Ra, where Ra is hydrogen, methyl, ethyl,
monohydroxy-C2-8alkyl, dihydroxy-C3-8alkyl,
or More preferably R is Rb, where Rb is hydrogen,
methyl, monohydroxy-C2-4alkyl, dihydroxy-C3-4alkyl or
-CH2CH2OCH2CH2OH. Even more preferably it is Rc, where Rc is hydrogen, -CH2CH2OH, or -CH2CH2OCH2CH2OH. Most pre
ferably, R is Rd, where Rd is hydrogen or -CH2CH2OH.
Any alkyl as Q is straight chain or branched; any unsubstituted alkyl preferably contains 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms. Any substituted alkyl as Q is preferably monohydroxysubstituted C2-4alkyl, dihydroxysubstituted C3-4alkyl or -CH2CH2OCH2CH2OH.
especially the group -NH-Qa, in which groups Qa is most preferably Q1; or the group -NH-Qd, in which Qd is hydrogen, monohydroxy- C2-4alkyl, dihydroxy-C3-4alkyl or -CH2CH2OCH2CH2OH; more preferably Qd is hydrogen or -CH2CH2OH.
B is preferably a chain-type, linear or branched bridge member or a bridge member which is branched by a cycloaliphatic, aromatic or heteroaromatic ring system, which bridge members additionally contain at least one of the above-listed groups (a)
to (d), especially a hydroxy or carbonyl group thereof.
If B is a chain-type bridge member, it preferably denotes mono- or dihydroxysubstituted C3-6alkylene or -CO(CH2)1-3-; especially , or -COCH2-.
Any branching in B preferably takes place through a heteroaromatic ring system, especially through triazine rings.
in which
Qb is hydrogen, alkyl, substituted alkyl or one of the groups Q1 to Q5 as defined above,
R4 is (i) monohydroxysubstituted C2-6alkylene or di- or polyhydroxysubstituted C3-8alkylene,
(ii) C2-6alkylene or,
(iii) together with the groups -NR3-(wherein R3 is
hydrogen) to which R4 is attached, forms a piperazine ring,
More preferably R4 is a group as defined under (i) or (ii). R1 is preferably monohydroxy-C2-4alkyl, dihydroxy-C3-8alkyl, more preferably, R1 is
-CH2CH2OH or -CH2CH(OH)CH2OH.
B1 is preferably a C3-6alkyleneamine group which is linear or branched and may be substituted by one or two hydroxy groups, or is -CO(CH2)1-5 NH-. Most preferably, B 1 is or -CO(CH2)1-5NH-.
B2 is preferably a tri- or tetravalent, especially trivalent bridge member containing triazine rings. Particularly, -B2-NH-Qa is a group of formula (a),
in which R2, R3 and R4 are as defined above, and Qc is one of the groups Q1 to Q5 as defined above.
Particularly preferred are compounds of formula I corresponding to formula la (with p and q = 0; m = 1 and n = 1 or 2); formula lb (with m, p and q = 0 and n = 1 or 2); formula Ic (with n and p = 0 and q = 1); and formula Id (with m and q = 0 and n and p = 1): -
Compounds of formula la,
Ba is mono- or dihydroxysubstituted C3_6alkylene or
R is Ra or
wherein R2, R3, R4 and Qb are as defined above, and R4 is more preferably a group as defined under (i) or (ii), provided that at least one of the two possible Q or Qb is a fibre-reactive group; and in which a) in the case where n is 1, F1-NH- has one of the following preferred significances: -
in which formula each of the -NH- groups is independently in the 4- or 5-position; in which compounds of formula la both groups may be the
same or different and in particular, only one of both groups Q is a fibre-reactive group.
Compounds of formula lb,
in which R is preferably Rb, and more preferably Rc, and in the case where n is 1, as well as in the case where n is 2, the same definitions apply to F1 as given for the compounds of formula la.
Compounds of formula Ic,
R2, R3, R4 and Qaare as defined above, and F1 and F2 have one of the following preferred significances: - a) F1-NH- is a group of the formula,
in which each t is independently 0 or 1 and each sulpho group is independently in the 3- or 4-position, each S1 is independently H, CH3, OCH3, NHCOCH3 or NHCONH2, and each S2 is independently H or OCH3.
Compounds of formula Id,
B1 is NH- or -CO(CH2)1_5 NH- , and R1 is
monohydroxysubstituted C2-4alkyl, dihydroxysubstituted C3-8alkyl, is
a group of the formula,
in which each t is independently 0 or 1 and the sulpho group is in the 3- or 4-position,
S3 is H or CH3 and S4 is -O-B1-R1 or
S3 is -NH-B1-R1 and S4 is H.
Preferably, in a compound of formulae la to Id, the fibre- reactive group is Q1.
When a compound of formula I containing sulpho and/or carboxy
groups is in the salt form, the cation of any sulpho and carboxy groups is not critical and may be any of those non-chromophoric cations conventional in the field of reactive dyestuffs provided that the corresponding salts as obtained are water-soluble. Examples of such cations are alkali metal cations and unsubstituted or substituted ammonium cations, e.g., lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, triethyl-ammonium, mono-, di- and tri-ethanolammonium.
The preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.
In a compound of formula I the cations of any sulpho and carboxy groups can be the same or different, i.e. they can also be a mixture of the above mentioned cations meaning that the compound of formula I can be in a mixed salt form.
The present invention further provides a process for the preparation of the compounds of formula I comprising reacting a compound of formula II,
Rx is hydrogen, alkyl or substituted alkyl, and each n' is independently 0 or 1 , with a compound of formula III,
Qa—Hal III in which
Qa is a cellulose fibre-reactive group, and
Hal is halogen,
using the corresponding amount of a compound of formula III necessary to "introduce 1 or 2 groups Qa per molecule of a compound of formula II,
This condensation may be effected in accordance with conventional methods.
The compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali metal salts, filtering and drying in vacuo.
Depending on the reaction and isolation conditions a compound of formula I containing sulpho and/or carboxy groups is obtained in free acid or preferably salt form or even mixed salt form containing, for example, one or more of the above-mentioned cations. It may be converted from free acid form to a salt form or mixtureof salt forms or vice versa or from one salt form to another by conventional means.
The starting compounds of formula II are known with regard to their chromophoric part. In order to introduce into the compounds of formula II those groups containing one or more of the groups (a) to (d) according to the invention, various ways of preparation may be used. All these methods concern processes known per se which therefore are analogous preparation processes.
For example, the following principles of synthesis are possible: -
(1) Preparation of compounds of formula II of type
(1a) reacting a compound F1-NHR with cyanuric chloride;
(1b) subsequently,reacting the resulting condensation product with a hydroxy group containing amino compound;
(1c) subsequently, reacting with a hydroxy group containing diamino compound.
Similarly, compounds of formula II corresponding to type
may be prepared using in step (1a), instead of cyanuric chloride, the condensation product consisting of two cyanuric chloride radicals linked together by a bridge; the process is otherwise effected in analogous manner.
(2) Preparation of compounds of formula II of type
F1— Y—B—NHR
in which Y is -O- or -NR-, B is hydroxysubstituted alkylene and R is hydrogen or substituted alkyl, comprising the following steps (2a) reaction of F1-NHR or F1-OH with a bifunctional chlorohydrin such as epichlorohydrin;
(2b) subsequent reaction with a hydroxy group containing amino compound.
(3) Preparation of compounds of formula II of tpye F1—Y—B—NHR in which Y is -NH- and B is -CO(CH2)—1-5 , comprising the steps
(3a) reaction of F1-NH2 with an α-chloro-acid chloride such as chloroacetic acid chloride; (3b) subsequent reaction with a hydroxy group containing amino compound.
(4) Preparation of compounds of formula II of tpye
in which Y is -O- or -NH-, B1 is hydroxysubstituted alkylene or -CO(CH2)—1-5 and R1 is hydroxysubstituted alkyl, comprising the steps
in which S is a protecting group, either with a bifunctional chlorohydrin such as epichloro
hydrin, or with an α-chloro-acid chloride such as chloroacetic acid chloride;
(4b) subsequent reaction with a hydroxy group containing amino compound; (4c) splitting off the protecting group.
The compounds of formula I and mixtures thereof are useful as fibre-reactive dyestuffs for dyeing or printing hydroxy group or nitrogen containing organic substrates. Preferred substrates are leather and fibre materials containing or consisting of natural or synthetic polyamides and, particularly, of natural or regenerated cellulose such as cotton, viscose and spun rayon. The most preferred substrate is textile material containing or consisting of cotton.
Dyeing or printing is effected in accordance with known methods conventional in the reactive dyestuff field. Especially preferred is the exhaust dyeing method. The most favourable and therefore preferred dyeing temperature is within the cold-dyeing range of from 30 to 60°C.
The compounds of this invention are well compatible with other reactive dyes; they may be applied per se or in combination with appropriate fibre-reactive dyestuffs of the same class having analogous dyeing properties, e.g., concerning common fastness properties, extent of ability to exhaust from the dyebath onto the fibre etc. The dyeings obtained with such combination mixtures have good fastness properties and are comparable to those obtained with a single dyestuff.
In view of their good build-up power the compounds of formula I give high exhaust and fixation yields. The dyeings and prints obtained show particularly good light fastness, but also good wet fastness properties such as fastness to washing, water, sea water and sweat. In particular, the present dyestuffs give dyeings and prints which show good resistance to any oxidative influences, e.g., chlorinated water, hypochlorite bleach and peroxide or perborate
containing wash liquors.
The following examples further serve to illustrate the invention. In the examples all parts and percentages are by weight or volume. The temperatures are in degrees Centigrade.
Example 1
18.5 Parts of cyanuric chloride are added to a mixture of 70 parts of water and 70 parts of ice. A solution of 57.2 parts of a compound of the formula
in the trisodium salt form (having a pH of approximately 7) is added to the suspension obtained. Stirring is effected at pH 5.5-6.5 until any free amino group is no longer detectable. Subsequently, 10.5 parts of diethylene glycole amine are added. The mixture is heated to 40°, and stirring is effected for one hour. During the reaction, the pH is kept at 7.0-7.5 by adding dilute sodium carbonate solution. To this reaction mixture 18 parts of 1,3-diaminopropanol-2 are then added. The mixture is stirred at 50° during four hours, whereby a pH in the range of 10.0-10.5 is kept by adding sodium hydroxide solution.
The dyestuff thus obtained is salted out using an appropriate amount of sodium chloride, and is filtered off. 13.5 Parts of 5-chloro-2,4,6-trifluoropyrimidine are added to the dye paste which is dissolved in 900 parts of water. Stirring is effected for two hours at 30-40°, and the pH is kept at 5-6 by adding dilute sodium carbonate solution. The obtained dyestuff is salted out with sodium chloride and isolated in conventional manner, it corresponds, in free acid form, to the formula
The dyestuff when dried is a dark-red powder which dissolves in water in a red colour. This dyestuff dyes cotton a red shade. The dyeings obtained show good light and wet fastness properties, especially they are stable to any oxidative influences.
Examples 2 to 134
By analogy with the method described in Example 1 further compounds of formula I may be prepared which are listed in the following Tables 1 to 5. Concerning the preparation processes with respectto the used starting materials, intermediate compounds prior to introducing the fibre-reactive group, reference is made to the corresponding passages in the description.
Examples 2 to 64
The compounds are listed in Table 1; they correspond to formula IV,
The compounds are listed in Table 2; they correspond to formula V,
The compounds are listed in Table 3; they correspond to formula VI,
The compounds are listed in Table 4; they correspond to formula VII,
The compounds are listed in Table 5; they correspond to formula VIII,
in which the symbols are as defined in Table 5. Cellulose fibres may be dyed with the dyestuffs listed in the tables, in particular using the conventional exhaust dyeing method. In column I of each of the Tables 1 to 4 the shade of the dyeing on cotton is given, whereby a is greenish-yellow h is bluish-red b is yellow i is ruby c is golden-yellow j is violet d is orange k is blue
e is red-orange l is greenish-blue f is scarlet m is turquoise g is red n is navy.
The cotton dyeings obtained with the compounds of Table 5 are all reddish-yellow.
Generally, the resultant cotton dyeings have good light and wet fastness properties, they are especially resistant to any oxidative influences.
Further compounds of formula I which may be prepared by analogous method as described in Example 1 are given by the following examples :-
Examples 135 and 136
The compounds correspond to the formula
i
n which for Example 135, X is -NHCH2CH2OH; for Example 136, X is
each of them dyes cotton a navy shade.
Example 137
The compound corresponds to the formula
In the following list maximum absorption wavelengths (αmax. in nm) as available for the exemplified dyestuffs are given. The values
were determined using an aqueous solution of the dyestuffs.
Ex.No. αmax.(nm) Ex.No. αmax.(nm) αmax.(nm)
1 540 33 503 75 505
2 542 34 506 76 496
3 545 35 485 78 541
4 545 36 482 80 606
5 542 37 515 81 605
6 515 38 496 82 606
7 512 39 498 83 514
8 512 40 600 84 515
9 515 41 384 85 485
10 402 42 386 86 487
11 404 43 492 87 485
12 405 44 493 88 485
13 402 47 555 119 384
14 418 50 540 120 384
15 416 53 596 121 382
16 416 54 606 122 382
17 400 55 606 123 381
18 402 56 604 124 382
19 401 57 606 125 384
20 401 58 607 126 383
21 424 59 606 127 384
22 426 60 604 128 383
23 426 65 541 129 382
24 424 66 516 130 382
25 418 67 515 131 381
26 410 68 402 132 382
27 496 69 401 133 384
28 495 70 400 134 384
29 496 71 424 135 605
30 497 72 496 136 606
31 505 73 497 137 512
32 503 74 506
In accordance with the method as described the dyestuffs of Examples 1 to 137 are obtained in the sodium salt form. They may, depending on the reaction/isolation conditions or by reacting the sodium salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms containing one or more cations indicated in the description above.
In the following examples the application of the compounds of this invention is illustrated.
Application Example A (exhaust dyeing)
0.3 Parts of the dyestuff of Example 1 or 135 are dissolved in 300 parts of demineralised water and 15 parts of Glauber's salt (calcined) are added. The dyebath is heated to 40°, then 10 parts of cotton fabric (bleached) are added. After 30 minutes at 40°, 6 parts of sodium carbonate (calcined) are added to the bath portionwise every 10 minutes applying quantities of 0.2, 0.6, 1.2 and finally 4.0 parts thereof. During the addition of sodium carbonate the temperature is kept at 40°. Subsequently, dyeing is effected for a further one hour at 40°. The dyed fabric is then rinsed with running cold water for 3 minutes and afterwards with running hot water for a further 3 minutes. The dyeing is soaped at the boil for 15 minutes in 500 parts of demineralised water and 0.25 parts of sodium lauryl sulphonate. After rinsing with running hot water (for 3 minutes) and centrifuging, the dyeing is dried in a cabinet dryer at ca. 70°. A red (navy) cotton dyeing is obtained which shows good light fastness and wet fastness properties and which is resistant to any oxidative influences.
Application Example B (printing)
A printing paste consisting of
40 parts of the dyestuff of Example 6 or 38
100 parts of urea 340 parts of water
500 parts of a 4% sodium alginate thickener and
20 parts of sodium carbonate
1000 parts
is applied to cotton fabric in accordance with a conventional printing method.
The printed fabric is dried and fixed in steam at 105° for one minute. It is then rinsed in hot water, soaped at the boil (according to the method described in Application Example A) and dried. A red (red-orange) print is obtained which has good general fastness properties and is stable to any oxidative influences.
Similarly, the dyestuffs of the other examples or mixtures of the dyestuffs of Examples 1 to 137 may be employed to dye or print cotton in accordance with the method given for Application Examples A and B.
Claims
1. A compound which corresponds to formula I,
and salts thereof, in which each of F1 and F2 is independently a water-soluble organic dyestuff radical, each Y is independently -O- or , each B is independently a divalent bridge member, m is independently 0 or 1, each R is independently hydrogen, alkyl or substituted alkyl, n is 0, 1 or 2, each Q is independently hydrogen, alkyl, substituted alkyl or a cellulose fibre-reactive group, provided that at least one of the two possible groups Q is a cellulose fibre- reactive group;
B is a divalent bridge member,
R1 is alkyl or substituted alkyl, p is 0 or 1,
B2 is a tri- or tetravalent bridge member, Qa is a cellulose fibre-reactive group, r is 1 or 2, q is 0 or 1, whereby n + q is at least 1, and q is 0 if n is 1 or 2, provided that a compound of formula I contains at least one of the groups listed below, —
(a) hydroxy groups
(b) ether groupings
(c) carbonyl groups
2. A compound according to Claim 1, in which each of F1 and F2 is independently a water-soluble dyestuff radical of the metalfree or metallised mono-, dis- or polyazo, anthraquinone, phthalocyanine, oxazine, dioxazine, nitro or formazan series.
3. A compound according to Claim 1 or 2, in which Q or Qa is one of the following groups Q1 to Q5: -
in which X1 is alkyl or halogen substituted alkyl;
in which X2 is NH2 or any amine group;
4. A compound according to any one of Claims 1 to 3, in which m is 1 and n is 1 or 2, Y is -NR- and -B-NR-Q is a group of the formula,
Qb is hydrogen, alkyl, substituted alkyl or is one of the groups Q1 to Q5 as defined in Claim 3, provided that at least one of the two possible Qb is a fibre-reactive group,
R3 is independently hydrogen, alkyl or substituted alkyl,
5. A compound according to any one of Claims 1 to 3, in which m is 1, n is 1 or 2 and p is 0, B is mono- or dihydroxy substituted C3-6alkylene or -CO(CH2)1-3-,
Y is -O- or - NH-,
7. A compound according to any one of Claims 1 to 3, in which m and q are 0, p is 1 and n is 1 or 2, R is hydrogen,
Y is -O- or -NH-,
8. A compound according to any one of Claims 1 to 3, in which p and n are 0, q and r are 1,
Y is -NH-,
R is hydrogen and -B2-NH-Qa is a group (a),
in which R2 is chlorine, or -OR5, R3 is independently hydrogen, alkyl or substituted alkyl, R5 is monohydroxy substituted C2-6alkyl, di- or polyhydroxy substituted C3-8alkyl, or ( CH2)1-5-COOH, and
R4 is (i) monohydroxy substituted C2-6alkylene or di- or polyhydroxy substituted C3-8alkylene, (ii) C2-6alkylene, or
(iii) together with the groups -NR3- to which R4 is attached and in which R3 is hydrogen, forms a piperazine ring, provided that in case of (ii) and (iii), R2 is defined as and
Qc is one of the groups Q1 to Q5 as defined in Claim 3.
9. A process for the preparation of a compound of formula I, defined in Claim 1, comprising reacting a compound of formula II,
Rx is hydrogen, alkyl or substituted alkyl, and each n' is independently 0 or 1, with a compound of formula III,
Qa-Hal III in which
Qa is a cellulose fibre-reactive group, and
Hal is halogen, using the corresponding amount of a compound of formula III necessary to introduce 1 or 2 groups Qa per molecule of a compound of formula II.
10. A process for dyeing or printing hydroxy group or nitrogen containing organic substrates comprising applying to the substrate a compound of formula I, according to any one of Claims 1 to 8, or a mixture thereof as dyeing or printing agent.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3447891 | 1984-12-31 | ||
DEP3447891.4 | 1984-12-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1986004080A1 true WO1986004080A1 (en) | 1986-07-17 |
Family
ID=6254168
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1985/000745 WO1986004080A1 (en) | 1984-12-31 | 1985-12-23 | Improvements in or relating to organic compounds |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0205607A1 (en) |
JP (2) | JPS62501371A (en) |
WO (1) | WO1986004080A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2169306B (en) * | 1984-12-31 | 1989-05-04 | Sandoz Ltd | Azo dyes containing a trihalopyrimidinyl reactive group |
US5227476A (en) * | 1987-01-14 | 1993-07-13 | Sandoz Ltd. | 2-(3,6,8-trisulfonaphth-2-ylazo)-5-[2-chloro-4-[2-(5-chloro-2,4-difluoropyrimid-6-ylamino)-2-methyl-ethyl]amino-1,3,5-triazin-6-ylamino]phenyl urea salts thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB952620A (en) * | 1959-08-24 | 1964-03-18 | Ici Ltd | New pyrimidine azo dyestuffs |
GB995793A (en) * | 1961-02-07 | 1965-06-23 | Farbenfabriken Bayer Aktiengesellschaft | |
DE1950311A1 (en) * | 1968-10-01 | 1970-06-04 | Interquim S A | New fiber-reactive dyes and dyeing processes using these dyes |
US3822263A (en) * | 1967-09-01 | 1974-07-02 | Bayer Ag | Reactive anthraquinone dyestuffs containing a fluoropyrimidinyl group |
US4007164A (en) * | 1968-03-19 | 1977-02-08 | Bayer Aktiengesellschaft | Azo dyestuffs containing 6-fluoro-pyrimidinyl 4-reactive group |
EP0069703A2 (en) * | 1981-07-07 | 1983-01-12 | Ciba-Geigy Ag | Reactive dyestuffs, their preparation and their use |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS596149B2 (en) * | 1976-05-31 | 1984-02-09 | 三菱電機株式会社 | Commutation capacitor voltage detection circuit for current source inverter |
-
1985
- 1985-12-23 JP JP50068786A patent/JPS62501371A/en active Pending
- 1985-12-23 EP EP19860900670 patent/EP0205607A1/en not_active Withdrawn
- 1985-12-23 WO PCT/EP1985/000745 patent/WO1986004080A1/en not_active Application Discontinuation
- 1985-12-27 JP JP29333685A patent/JPS61162556A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB952620A (en) * | 1959-08-24 | 1964-03-18 | Ici Ltd | New pyrimidine azo dyestuffs |
GB995793A (en) * | 1961-02-07 | 1965-06-23 | Farbenfabriken Bayer Aktiengesellschaft | |
US3822263A (en) * | 1967-09-01 | 1974-07-02 | Bayer Ag | Reactive anthraquinone dyestuffs containing a fluoropyrimidinyl group |
US4007164A (en) * | 1968-03-19 | 1977-02-08 | Bayer Aktiengesellschaft | Azo dyestuffs containing 6-fluoro-pyrimidinyl 4-reactive group |
DE1950311A1 (en) * | 1968-10-01 | 1970-06-04 | Interquim S A | New fiber-reactive dyes and dyeing processes using these dyes |
EP0069703A2 (en) * | 1981-07-07 | 1983-01-12 | Ciba-Geigy Ag | Reactive dyestuffs, their preparation and their use |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2169306B (en) * | 1984-12-31 | 1989-05-04 | Sandoz Ltd | Azo dyes containing a trihalopyrimidinyl reactive group |
US5227476A (en) * | 1987-01-14 | 1993-07-13 | Sandoz Ltd. | 2-(3,6,8-trisulfonaphth-2-ylazo)-5-[2-chloro-4-[2-(5-chloro-2,4-difluoropyrimid-6-ylamino)-2-methyl-ethyl]amino-1,3,5-triazin-6-ylamino]phenyl urea salts thereof |
Also Published As
Publication number | Publication date |
---|---|
JPS62501371A (en) | 1987-06-04 |
JPS61162556A (en) | 1986-07-23 |
EP0205607A1 (en) | 1986-12-30 |
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