WO1997027249A1 - Heteropolyfunctional reactive disaro dyes - Google Patents
Heteropolyfunctional reactive disaro dyes Download PDFInfo
- Publication number
- WO1997027249A1 WO1997027249A1 PCT/GB1996/003237 GB9603237W WO9727249A1 WO 1997027249 A1 WO1997027249 A1 WO 1997027249A1 GB 9603237 W GB9603237 W GB 9603237W WO 9727249 A1 WO9727249 A1 WO 9727249A1
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- Prior art keywords
- optionally substituted
- compound
- independently
- formula
- dyes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C09B62/4415—Disazo or polyazo dyes
Definitions
- This invention relates to organic chemicals suitable for use as reactive dyes, to intermediate compounds therefor and to processes for their manufacture and use.
- Reactive dyes have been known since the 1950's and are often applied to cellulosic substrates in a dyebath in conjunction with an alkali to assist covalent bond formation.
- the dyebath is not completely exhausted of dye leaving some dye in the dyebath.
- some dye only loosely adheres to the substrate and has to be washed at a later stage.
- Unused or hydrolysed dye in the dyebath or washings must be disposed of and this is a major burden on dyehouses. Therefore there is a need for dyes which are exhausted efficiently from dyebaths and fix well to substrates thereby reducing effluent.
- A is optionally substituted phenylene
- B and E are each independently optionally substituted phenylene or optionally substituted naphthylene; D is a coupling component; each R 1 independently is H or optionally substituted alkyl;
- X is a labile atom or group; and each Y independently is O or S.
- the total number of sulpho groups in the compound of Formula (1) is form 2 to 6.
- the optional substituents which may be present on A B, D, E and R 1 are preferably each independently selected from C ⁇ -alkyl, especially methyl; C M -alkoxy, especially methoxy; halo.especially Cl; nitro; amino; hydroxy; sulpho; cyano; carboxy; ureido; and C ⁇ -amido, especially acetamido.
- ⁇ B and E are preferably each independently optionally substituted 1,3- or 1,4- phenylene.
- D is preferably optionally substituted naphthylene, more preferably optionally substituted 2,6-, 2,7- or 2,8- naphthylene, especially optionally substituted naphthylene having a hydroxy group at the 1 -position of the naphthylene ring; optionally substituted phenylene, more preferably 1,3- or 1,4- phenylene; or an optionally substituted pyridonylene or pyrazolonylene group.
- Each R 1 independently is preferably H or C M -alkyl, especially H or methyl.
- Y is preferably O.
- X is preferably a pyridinium group, especially 3- or 4- carboxy pyridinium; more preferably a halo atom, especially F or Cl, more especially Cl.
- a preferred class of compounds according to the invention is of the Formula (2) or a salt thereof:
- R 2 and R 3 are each independently H, S0 3 H, C M -alkyl (preferably methyl),
- each R 4 independently is H, S0 3 H, C M -alkoxy, C ⁇ -alkyl or halo;
- R 5 is H or SO 3 H
- R ⁇ X and Y are as hereinbefore defined.
- R 5 is H.
- Compounds of the invention may be prepared by condensing compounds of Formula (3) and (4) wherein A, B, D, E, R 1 , X and Y are as hereinbefore defined:
- condensation of the compounds of Formula (3) and (4) is performed in an aqueous medium, especially water.
- the precise conditions will be chosen to prevent or limit side reactions such as hydrolysis of the dye.
- a temperature in the range 0°C to 50°C is used.
- Diazotisation conditions are well known in the art, for example treating an amine with NaN0 2 under acidic conditions at 0-5°C.
- the compounds of Formula (1) can be isolated from the medium in which they have been prepared by conventional methods used for isolation of water-soluble dyes, e.g. by salting out followed by filtration and drying by spray drying the reaction mixture. If desired, stabilisers such as alkali metal hydrogen phosphates, polyphosphates or diluents such as sodium chloride or urea can be added.
- the dyes may also be desalinated using techniques such as reverse osmosis and/or ultrafiltration to give formulations having high solubility in water.
- formulae includes salts of the compounds, and in particular the alkali metal salts such as the sodium, potassium, lithium or mixed sodium lithium salt.
- a further feature of the present invention provides a process for the coloration of a substrate by applying thereto a compound of Formula (1)or (2).
- the compounds of Formula (1) can be applied to a wide variety of substrates, particularly those having -OH or -NH- groups, and are especially valuble as dyes for cellulosic materials such as cotton, jute, hemp and flax.
- the compound is applied in conjunction with an acid binding agent, e.g. an alkali metal carbonate or bicarbonate, at a temperature of 120°C to 180°C.
- an acid binding agent e.g. an alkali metal carbonate or bicarbonate
- the dyes are preferably applied using standard pad-dry-bake methods and are characterised by very high fixation and high wash-fastness with little colour loss during wash-off. Generally few wash-off steps are required and little effluent is generated.
- Stage b To a slurry of 4-amino-1,1 1 -azobenzene-3-sulphonic acid, 4 1 - sulphatoethylsulphonamide (44g, 0.02M) in ice water (300ml) was added concentrated hydrochloric acid (11 ml) followed by 2N NaN0 2 (11 ml). The mixture was stirred at 0- 5°C until diazotisation was complete and excess nitrous acid was destroyed by adding sulphamic acid. Sodium acetate was added to give a pH of 9.4 and the mixture was added to the product of stage a. NaHC0 3 was added to the mixture to pH6 and the mixture was stirred at pH6, 0-5°C for 2 hours. KCI (15% w/v) was added and the resultant precipitate filtered off, washed and dried.
- stage b The product from stage b (10.98g, 7.4 x 10 "3 moles) was dissolved in water (200ml). 3-( ⁇ -sulphatoethylsulphonamido)aniline (5.0g, 0.017 mole) was added and the mixture stirred at room temperature and pH6.3 for 1 day. The solution was salted to 10% w/v with KCI and the resultant precipitate filtered-off, washed and dried to give the title product (12.1g) having a ⁇ max at 528nm.
- the title product was applied to cotton by using the pad-dry-bake method and was found to have excellent fixation. After washing the wash liquors were essentially colourless.
- Example 1 The general method of Example 1 may be repeated except that the components used in stage a), b) and c) are as shown in Table 1 below wherein,
- Example 1 The method of Example 1 may be repeated except that in place of cyanuric chloride there is used cyanuric fluoride.
- the chlorine atom in product of Examples 1 to 8 may be replaced by a 3-carboxy pyridinium group by heating the dyes (1 part at 80°C) with 3-carboxy pyridine (1.2 parts) in water for approximately 1 hour.
- the resultant dye may be applied on cotton by the pad-dry-bake method.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
A compound of Formula (1) and salts thereof wherein: A is optionally substituted phenylene; B and E are each independently optionally substituted phenylene or optionally substituted naphthylene; D is a coupling component; each R1 independently is H or optionally substituted alkyl; X is a labile atom or group; and each Y independently is O or S. The compounds are useful for the coloration of a wide variety of substrates, particularly cellulosic substrates by the pad-dry-bake method.
Description
HETEROPOLYFUNCTIONAL REACTIVE DISARO DYES
This invention relates to organic chemicals suitable for use as reactive dyes, to intermediate compounds therefor and to processes for their manufacture and use.
Reactive dyes have been known since the 1950's and are often applied to cellulosic substrates in a dyebath in conjunction with an alkali to assist covalent bond formation. Usually the dyebath is not completely exhausted of dye leaving some dye in the dyebath. Furthermore some dye only loosely adheres to the substrate and has to be washed at a later stage. Unused or hydrolysed dye in the dyebath or washings must be disposed of and this is a major burden on dyehouses. Therefore there is a need for dyes which are exhausted efficiently from dyebaths and fix well to substrates thereby reducing effluent.
According to the present invention there is provided a compound of Formula (1) and salts thereof:
wherein:
A is optionally substituted phenylene;
B and E are each independently optionally substituted phenylene or optionally substituted naphthylene; D is a coupling component; each R1 independently is H or optionally substituted alkyl;
X is a labile atom or group; and each Y independently is O or S.
Preferably the total number of sulpho groups in the compound of Formula (1) is form 2 to 6.
The optional substituents which may be present on A B, D, E and R1 are preferably each independently selected from C^-alkyl, especially methyl; CM-alkoxy,
especially methoxy; halo.especially Cl; nitro; amino; hydroxy; sulpho; cyano; carboxy; ureido; and C^-amido, especially acetamido.
Λ B and E are preferably each independently optionally substituted 1,3- or 1,4- phenylene.
D is preferably optionally substituted naphthylene, more preferably optionally substituted 2,6-, 2,7- or 2,8- naphthylene, especially optionally substituted naphthylene having a hydroxy group at the 1 -position of the naphthylene ring; optionally substituted phenylene, more preferably 1,3- or 1,4- phenylene; or an optionally substituted pyridonylene or pyrazolonylene group.
Each R1 independently is preferably H or CM-alkyl, especially H or methyl.
Y is preferably O.
X is preferably a pyridinium group, especially 3- or 4- carboxy pyridinium; more preferably a halo atom, especially F or Cl, more especially Cl.
Thus a preferred class of compounds according to the invention is of the Formula (2) or a salt thereof:
wherein:
R2 and R3 are each independently H, S03H, CM-alkyl (preferably methyl),
C -alkoxy (preferably methoxy) or halo (especially chloro); each R4 independently is H, S03H, CM-alkoxy, C^-alkyl or halo;
R5 is H or SO3H; and
R\ X and Y are as hereinbefore defined.
In compounds of Formula (2) it is preferred that when the -NR1- group is at the 6- position shown on the naphthalene ring then R5 is H.
Compounds of the invention may be prepared by condensing compounds of Formula (3) and (4) wherein A, B, D, E, R1, X and Y are as hereinbefore defined:
2NH-CH2CH2-Y-SO3H
(3)
Preferably condensation of the compounds of Formula (3) and (4) is performed in an aqueous medium, especially water. The precise conditions will be chosen to prevent or limit side reactions such as hydrolysis of the dye. Generally a temperature in the range 0°C to 50°C is used. A pH of 5 to 7, preferably 6 to 6.5, is convenient for the condensation.
Compounds of Formula (4) are known in the literature.
Compounds of Formula (3) can be prepared by diazotising and coupling r-^N-B- N=N-A-S02NH-CH2CH2-Y-S03H onto H-D-NR1-s-triazine(-X)2 wherein B,
Y, R1, D and X are as hereinbefore defined. Preparation of the necessary intermediates is illustrated in the EΞxamples and analogous compounds can be prepared by experienced dyestuff chemists without difficulty.
Diazotisation conditions are well known in the art, for example treating an amine with NaN02 under acidic conditions at 0-5°C.
The compounds of Formula (1) can be isolated from the medium in which they have been prepared by conventional methods used for isolation of water-soluble dyes, e.g. by salting out followed by filtration and drying by spray drying the reaction mixture. If desired, stabilisers such as alkali metal hydrogen phosphates, polyphosphates or diluents such as sodium chloride or urea can be added. The dyes may also be desalinated using techniques such as reverse osmosis and/or ultrafiltration to give formulations having high solubility in water.
Although compounds of Formula (1) have been shown in their free-acid form in this specification, it is intended that the formulae includes salts of the compounds, and in
particular the alkali metal salts such as the sodium, potassium, lithium or mixed sodium lithium salt.
A further feature of the present invention provides a process for the coloration of a substrate by applying thereto a compound of Formula (1)or (2).
The compounds of Formula (1) can be applied to a wide variety of substrates, particularly those having -OH or -NH- groups, and are especially valuble as dyes for cellulosic materials such as cotton, jute, hemp and flax. Typically the compound is applied in conjunction with an acid binding agent, e.g. an alkali metal carbonate or bicarbonate, at a temperature of 120°C to 180°C. The dyes are preferably applied using standard pad-dry-bake methods and are characterised by very high fixation and high wash-fastness with little colour loss during wash-off. Generally few wash-off steps are required and little effluent is generated.
The invention is further illustrated but not limited by the following [Examples in which all parts and percentages are by weight unless otherwise indicated.
Example 1
Preparation of the compound of Formula
Stage a
A solution of 1-hydroxy-3-sulpho-6-amino naphthalene (5.04g, 0.02M) in water (60ml) at pH 6.5 was added dropwise to a suspension prepared by dropwise addition of cyanuric chloride (4.06g, 0.22M) in acetone (50ml) to ice/water (50g). After addition the mixture was stirred at 0-5°C for a further 2 hours.
Stage b
To a slurry of 4-amino-1,11-azobenzene-3-sulphonic acid, 41- sulphatoethylsulphonamide (44g, 0.02M) in ice water (300ml) was added concentrated hydrochloric acid (11 ml) followed by 2N NaN02 (11 ml). The mixture was stirred at 0- 5°C until diazotisation was complete and excess nitrous acid was destroyed by adding sulphamic acid. Sodium acetate was added to give a pH of 9.4 and the mixture was added to the product of stage a. NaHC03 was added to the mixture to pH6 and the mixture was stirred at pH6, 0-5°C for 2 hours. KCI (15% w/v) was added and the resultant precipitate filtered off, washed and dried.
Staαe c
The product from stage b (10.98g, 7.4 x 10"3 moles) was dissolved in water (200ml). 3-(β-sulphatoethylsulphonamido)aniline (5.0g, 0.017 mole) was added and the mixture stirred at room temperature and pH6.3 for 1 day. The solution was salted to 10% w/v with KCI and the resultant precipitate filtered-off, washed and dried to give the title product (12.1g) having a λmax at 528nm.
Stage d
The title product was applied to cotton by using the pad-dry-bake method and was found to have excellent fixation. After washing the wash liquors were essentially colourless.
-Examples 2 to 7
The general method of Example 1 may be repeated except that the components used in stage a), b) and c) are as shown in Table 1 below wherein,
Column II - the listed naphthalene compound is used in place of 1-hydroxy-3-sulpho-6- amino naphthalene.
Column III - the listed azo compound is used in place of 4-amino-1 ,11-azobenzene-3- sulphonic acid, 41-sulphatoethyl sulphonamide ("AASAS" for short). Column IV - the listed aniline compound is used in place of 3-(β-sulphatoethyl sulphonamido) aniline ("Beta" for short).
TABLE 1
Example Column II Column III Column IV
No. naphthalene compound azo compound aniline compound
2 1 -hydroxy-3,6-disulpho-8- AASAS BETA amino naphthalene
3 1 -hydroxy-3-sulpho-6- AASAS BETA amino naphthalene
4 1 -hydroxy-3-sulpho-6- AASAS 4-(β-sulphatoethyl amino naphthalene sulphonamido) aniline
5 1 -hydroxy-3, 5-disulpho-6- AASAS BETA amino naphthalene
6 1 -hydroxy-3, 5-disulpho-6- 2-sulpho-4- BETA amino naphthalene (azophenyl-41- [sulphatoethyl sulphonamide])-5- acetamido aniline.
7 1 -hydroxy-3, 5-disulpho-6- 4-amino-1,11- BETA amino naphthalene azobenzene-41- sulphatoethyl sulphonamide
Example 8
The method of Example 1 may be repeated except that in place of cyanuric chloride there is used cyanuric fluoride.
.Example 9
The chlorine atom in product of Examples 1 to 8 may be replaced by a 3-carboxy pyridinium group by heating the dyes (1 part at 80°C) with 3-carboxy pyridine (1.2 parts)
in water for approximately 1 hour. The resultant dye may be applied on cotton by the pad-dry-bake method.
Claims
1. A compound of Formula (1) and salts thereof:
wherein:
A is optionally substituted phenylene;
B and E are each independently optionally substituted phenylene or optionally substituted naphthylene;
D is a coupling component; each R1 independently is H or optionally substituted alkyl;
X is a labile atom or group; and each Y independently is O or S.
2. A compound according to claim 1 wherein A, B and E are optionally substituted phenylene.
3. A compound according to any one of the preceding claims wherein D is optionally substituted naphthylene.
4. A compound according to any one of the preceding claims wherein each R1 independently is H or CM-alkyl.
5. A compound according to any one of the preceding claims wherein Y is O.
6. A compound according to any one of the preceding claims wherein X is a halo atom or a pyridinium group.
7. A compound of the Formula (2) or a salt thereof:
wherein: R2 and R3 are each independently H, S03H, C^-alkyl
CM-alkoxy or halo; each R4 independently is H, S03H, C^-alkoxy, C^-alkyl or halo; R5 is H or S03H, and X, each Y and each R independently are as defined in claim 1.
8. A process for the preparation of a compound of Formula (1) and salts thereof, as defined in claim 1 , comprising condensing a compound of Formula (3) and a compound of Formula (4):
-SO2NH-CH2CH2Ύ-SO3H
(4)
(3)
wherein A, B, D, E, R\ X and Y are as defined in claim 1.
9. A process for the coloration of a substrate comprising applying thereto a compound of Formula (1), as defined in claim (1), or a compound of Formula (2), as defined in claim 7.
10. A process according to claim 9 wherein the substrate is a cellulosic material.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9811592A GB2323369B (en) | 1996-01-27 | 1996-12-24 | Heteropolyfunctional reactive disaro dyes |
| AU12042/97A AU1204297A (en) | 1996-01-27 | 1996-12-24 | Heteropolyfunctional reactive disaro dyes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9601696.9A GB9601696D0 (en) | 1996-01-27 | 1996-01-27 | Organic chemicals |
| GB9601696.9 | 1996-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997027249A1 true WO1997027249A1 (en) | 1997-07-31 |
Family
ID=10787700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1996/003237 Ceased WO1997027249A1 (en) | 1996-01-27 | 1996-12-24 | Heteropolyfunctional reactive disaro dyes |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU1204297A (en) |
| GB (1) | GB9601696D0 (en) |
| WO (1) | WO1997027249A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1041122A1 (en) * | 1999-03-30 | 2000-10-04 | Ciba SC Holding AG | Reactive dyes, process for their preparation and their use |
| US6451072B1 (en) | 1999-03-30 | 2002-09-17 | Ciba Specialty Chemicals Corporation | Reactive dyes, process for their preparation and their use |
| CN102433028A (en) * | 2011-09-29 | 2012-05-02 | 天津德凯化工股份有限公司 | Azo red reactive dye and intermediate thereof |
| 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 |
| WO2013189813A1 (en) | 2012-06-18 | 2013-12-27 | Dystar Colours Distribution Gmbh | Reactive dyes, process for the production thereof and their use |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1228601A (en) * | 1958-06-10 | 1960-08-31 | Basf Ag | Process for the production of azo dyes |
| FR1256161A (en) * | 1960-03-04 | 1961-03-17 | Ici Ltd | Reactive azo dyes for natural and artificial textile materials |
| GB1118785A (en) * | 1964-11-13 | 1968-07-03 | Ici Ltd | Water-soluble phthalocyanine reactive dyestuffs |
| FR1546109A (en) * | 1966-11-29 | 1968-11-15 | Ici Ltd | New reactive water soluble anthraquinone dyes |
-
1996
- 1996-01-27 GB GBGB9601696.9A patent/GB9601696D0/en active Pending
- 1996-12-24 AU AU12042/97A patent/AU1204297A/en not_active Abandoned
- 1996-12-24 WO PCT/GB1996/003237 patent/WO1997027249A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1228601A (en) * | 1958-06-10 | 1960-08-31 | Basf Ag | Process for the production of azo dyes |
| FR1256161A (en) * | 1960-03-04 | 1961-03-17 | Ici Ltd | Reactive azo dyes for natural and artificial textile materials |
| GB1118785A (en) * | 1964-11-13 | 1968-07-03 | Ici Ltd | Water-soluble phthalocyanine reactive dyestuffs |
| FR1546109A (en) * | 1966-11-29 | 1968-11-15 | Ici Ltd | New reactive water soluble anthraquinone dyes |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1041122A1 (en) * | 1999-03-30 | 2000-10-04 | Ciba SC Holding AG | Reactive dyes, process for their preparation and their use |
| US6451072B1 (en) | 1999-03-30 | 2002-09-17 | Ciba Specialty Chemicals Corporation | Reactive dyes, process for their preparation and their use |
| CN102433028A (en) * | 2011-09-29 | 2012-05-02 | 天津德凯化工股份有限公司 | Azo red reactive dye and intermediate thereof |
| WO2013189813A1 (en) | 2012-06-18 | 2013-12-27 | Dystar Colours Distribution Gmbh | Reactive dyes, process for the production thereof and their use |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9601696D0 (en) | 1996-03-27 |
| AU1204297A (en) | 1997-08-20 |
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