GB2074565A - 3-Amino-6-methyl-7- cyanoisothiazolo(4,3-c) Pyridine - Google Patents
3-Amino-6-methyl-7- cyanoisothiazolo(4,3-c) Pyridine Download PDFInfo
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- GB2074565A GB2074565A GB8109921A GB8109921A GB2074565A GB 2074565 A GB2074565 A GB 2074565A GB 8109921 A GB8109921 A GB 8109921A GB 8109921 A GB8109921 A GB 8109921A GB 2074565 A GB2074565 A GB 2074565A
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- amino
- monoazo dye
- pyridine
- methyl
- represents hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0096—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds from other diazotized amino heterocyclic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
The novel compound 3-amino-6- methyl-7-cyanoisothiazolo [4,3-c] pyridine is useful as a diazo component in the preparation of azo dyes, especially disperse dyes having fast blue and turquoise shades.
Description
SPECIFICATION
Heterocyclic Compounds
This invention relates to heterocyclic compounds and more particularly to 3-amino-6-methyl-7cyano isothiazolo [4,3-c] pyridine and azo dyes derived therefrom.
3-Amino-6-methyl-7-cyanoisothiazolo [4,3-c] pyridine is a novel chemical compound which may be prepared by the hydrogen peroxide oxidation of 3-thiocarbamoyl-4-amino-5-cyano-6methylpyridine which itself may be prepared by the selective thiohydration of 4-amino-3,5-dicyano-6methylpyridine. The latter compound is obtained by reacting diacetonitrile with malononitrile and triethyl orthoformate.
The 3-amino-6-methyl-7-cyanoisothiazolo [4,3-c] pyridine may be diazotised and coupled with a coupling component to give azo dyes having the general formula:
wherein E represents the residue of a coupling component.
The residue of the coupling component represented by E may be the residue of any of the known series of coupling components (that is to say compounds which react with a diazonium compound forming an azo dye). Thus, E may be the residue of a coupling component of the acylacetarylamide, pyrazolone, aminopyrazole, phenol, naphthol, 2,6-dihydroxy-pyridine, 2,6-diaminopyridine, indole or arylamine series and may contain any of the substituents appropriate to such residues.
Of particular interest are the disperse monoazo dyes in which E is the residue of a coupling component containing no sulphonic acid or other water-solubilising groups.
A preferred class of disperse dyes has the formula:
wherein R1 represents hydrogen or an optionally substituted alkyl, alkenyl, aralkyl, cycloalkyl or aryl radical, R2 represents hydrogen or an optionally substituted alkyl, alkenyl or aralkyl radical, R3 represents hydrogen, chlorine, bromine or an alkyl, alkoxy or acylamino radical and R4 represents hydrogen or an alkyl or alkoxy radical.
The alkyl radicals which may be represented by Rt, R2, R3 and R4 are preferably lower alkyl radicals and the alkoxy radicals which may be represented by R3 and R4 are preferably lower alkoxy radicals. The alkenyl radicals which may be represented by R3 and R4 preferably contain from two to four carbon atoms. Substituents which may be present on the optionally substituted alkyl radicals represented by R' and R2 include hydroxy, alkoxy, cyano, carboxy, alkoxycarbonyl, hydroxyalkoxy, alkoxyalkoxy, alkoxyalkoxycarbonyl, acyloxy, chloro, alkoxycarbonyloxy and acylamino.
Acylamino groups which may be represented by R3 include groups of the formulae -NHCOT1 and -NHSO2T2 wherein T1 represents hydrogen, alkyl, alkoxy, aryl, amino or alkylamino and T2 represents C,, alkyl or aryi.
Aryl groups which may be present in the dyes include phenyl and tolyl, aralkyl groups include benzyl and cycloalkyl groups include cyclohexyl and methylcyclohexyl.
Examples of coupling components which may be used in making the disperse dyes include N,Ndiethyl-m-amino acetanilide, 2,5-dimethoxyaniline, N,N-diethylaniline, N,N-di(p-hydroxyethyl)-m- toluidine, N,N-di(,B-cyanoethyl)-anil ine, N-ethyl-N-(p-ethoxyethyl)ani line, N,N-di(p-carbomethoxyethyl)- m-tolu id ine, N-[p '-methoxyethoxy-carbonyl)ethyl]-m-toluidine, 2-methoxy-5-acetylamino-N-[p ss'- methoxyethoxycarbonyl)ethyl]a ni line, N,N-di(p-acetoxyethyl)-m-toluidine, N-ethyl-N-(P- cya noethyl)an line, N-ethyl-N-(6-acetoxybutyl)an iline and N-ethyl-N-benzyl-m-toluidine.
The reactions leading to the formation of the dyes of the invention may be performed using conditions that have been fully described in the prior art for such reactions. Similarly the dyes may be isolated by known methods.
The dyes of the invention are valuable for colouring synthetic textile materials, in particular secondary cellulose acetate and cellulose triacetate textile materials, polyamide textile materials such as nylon 6 and nylon 66 textile materials and, above all, aromatic polyester textile materials such as polyethylene terephthalate textile materials. Such materials can be in the form of filaments, fibres or woven or knitted materials. The dyes may be applied to the synthetic textile materials by any of the methods conventionally employed for the application of disperse dyes to such materials.
When applied to synthetic textile materials, the dyes of the invention give blue to turquoise shades having excellent fastness to light and to wet and dry treatments. The dyes also have excellent dyeing properties, particularly on aromatic polyester textile materials. The dyes can also be used for the mass coloration of synthetic polymers which are subsequently to be converted into fibres or filaments or they can be applied to synthetic textile materials by the process of transfer colour printing optionally at reduced air pressures or under wet or humid conditions.
The invention is illustrated but not limited by the following Examples in which all parts are by weight unless otherwise stated.
Example 1 (A) Preparation of 4-amino-3,5-dicyano-6-methylpyridine
Diacetonitrile (492 parts) is added to ethanol (1 500 parts) and dissolved by warming to 300C.
After cooling to 200C, a solution of malononitrile (396 parts) in triethyl orthoformate (888 parts) is added with stirring. After stirring overnight, the suspended solid is filtered off, washed with ethanol and dried.
(B) Preparation of 4amino-5-cyano-6-methyl-3-thiocarbamoylpyridine
A solution of 4-amino-3,5-dicyano-6-methylpyridine (35 parts) in pyridine (400 parts) and triethylamine (28 parts) is prepared at room temperature. To this solution is added 16% ammonium sulphide aqueous liquor (110 parts) and the whole is maintained at 450C for 10 hours.The solution is then drowned into ice/water (2000 parts) and the precipitate is filtered off, washed with water and dried to give 22.6 parts of product which is characterised as follows:- Mass spectrum molecular ion M+ 1 92 I.R. 3370, 3300, 3200, 2850 (free+bonded CSNH2 and aromatic NH2), 2215 (CN), 1630 (C=N) cm-' N.M.R. (proton) a 2.31 (s.3, CH3),6.52 (s.2, CSNH2), 8.19 (s.1, aromatic H), 9.63 (s.2, NH2).
(C) Preparation of 3-a mino-6-methyl -7-cyanoisothiazolo[4,3-c] pyridine
To a solution of 4-amino-5-cyano-6-methyl-3-thiocarbamoylpyridine (20 parts) in methanol (1000 parts) at 35 OC is added 30% hydrogen peroxide (20 parts). A precipitate slowly forms and is filtered off after 10 minutes boiling to 13.3 parts of product.
(D) Preparation of dye
To a solution of 98% sulphuric acid (167 parts) and water (1 5 parts), cooled below 70C, is added 3-amino-6-methyl-7-cyanoisothiazolo [4,3-c] pyridine (15.2 parts). When solution is complete, it is cooled to 2oC and 40% nitrosyl sulphuric acid (28 parts) is added and the solution is stirred at --5 to OOC for 80 minutes.
The diazo solution so prepared is added to a coupling solution prepared from N,N-diethyl-m
aminoacetanilide (37.6 parts), ice-water (400 parts), sulphamic acid (4 parts) and concentrated sulphuric acid (6.4 parts). During coupling, acidity (Congo Red indicator) is periodically removed by the addition of solid sodium acetate. The solution is then stirred for a further 30 minutes at O5 C OC and the precipitate is filtered off, washed with warm water and dried giving 9.6 parts of the dye:
When applied to polyester textile fibre by a conventional dyeing method, a turquoise shade of excellent fastness is obtained.
The following Table gives further Examples of dyes which are prepared from 3-amino-6-methyl7-cyanoisothiazolo [4,3-c] pyridine by the method described in Example 1. In these Examples, the N,Ndiethyl-m-aminoacetanilide used in Example 1 is replaced by an equivalent amount of the coupling components identified in the Table.
Example Coupling Component Amax (nm) 2 N,N-diethyl-m-toluidine 619
3 N-benzyl-N-ethyl-m-toluidine 602
4 N-p-acetoxyethyl-N-ethyl-m-toluidine 598
5 N,N-bis-ss-acetoxyethyl-m-toludine 580
6 N,N-diallyl-m-aminoacetanilide 61 3 7 N,N-bis-ss-acetoxyethyl-m-aminoacetanilide 605
Claims (13)
1. 3-Amino-6-methyl-7-cyanoisothiazolo [4,3-c] pyridine.
2. A method for the preparation of 3-amino-6- methyl-7cyanoisothiazolo [4,3-c] pyridine which comprises oxidising 3-thiacarba moyl4amino-5-cyano6methylpyridine.
3. A method according to claim 2 conducted substantially as hereinbefore described with reference to Example 1.
4. A monoazo dye of the formula
wherein E represents the residue of a coupling component.
5. A disperse monoazo dye of the formula given in claim 4 wherein E is the residue of a coupling component containing no sulphonic acid or other water-soiubilising groups.
6. A disperse monoazo dye according to claim 5 having the formula:
wherein R1 represents hydrogen or an optionally substituted alkyl, alkenyl, aralkyl, cycloalkyl or aryl radical, R2 represents hydrogen or an optionally substituted alkyl, alkenyl or aralkyl radical, R3 represents hydrogen, chlorine, bromine or an alkyl, alkoxy or acylamino radical and R4 represents hydrogen or an alkyl or alkoxy radical.
7. A disperse monoazo dye according to claim 6 and specifically identified herein.
8. A method for the preparation of a monoazo dye as defined in claim 4 which comprises diazotising 3-amino-6-methyl-7-cyanoisothiazolo [4,3-c] pyridine and coupling the resulting diazo compound with a coupling component.
9. A method according to claim 8 conducted substantially as hereinbefore described with reference to any one of the foregoing Examples.
10. A monoazo dye whenever prepared by a method claimed in claim 8 or claim 9.
11. A process for the colouration of synthetic textile materials which comprises applying thereto a monoazo dye as claimed in any one of claims 4 to 7 and 10.
12. A process according to claim 11 wherein the synthetic textile material is an aromatic polyester textile material.
13. Synthetic textile materials whenever coloured by the process claimed in claim 11 or claim 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8109921A GB2074565A (en) | 1980-04-11 | 1981-03-30 | 3-Amino-6-methyl-7- cyanoisothiazolo(4,3-c) Pyridine |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8012098 | 1980-04-11 | ||
| GB8109921A GB2074565A (en) | 1980-04-11 | 1981-03-30 | 3-Amino-6-methyl-7- cyanoisothiazolo(4,3-c) Pyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2074565A true GB2074565A (en) | 1981-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8109921A Withdrawn GB2074565A (en) | 1980-04-11 | 1981-03-30 | 3-Amino-6-methyl-7- cyanoisothiazolo(4,3-c) Pyridine |
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| Country | Link |
|---|---|
| GB (1) | GB2074565A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380846A (en) * | 2020-10-21 | 2022-04-22 | 杭州布朗生物医药科技有限公司 | Preparation method of 3-amino-6-methyl-7-cyanoisothiazolo [4, 3-c ] pyridine |
-
1981
- 1981-03-30 GB GB8109921A patent/GB2074565A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380846A (en) * | 2020-10-21 | 2022-04-22 | 杭州布朗生物医药科技有限公司 | Preparation method of 3-amino-6-methyl-7-cyanoisothiazolo [4, 3-c ] pyridine |
| CN114380846B (en) * | 2020-10-21 | 2023-08-15 | 杭州布朗生物医药科技有限公司 | Preparation method of 3-amino-6-methyl-7-cyano isothiazolo [4,3-c ] pyridine |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |