GB1599550A

GB1599550A - Water-insoluble monoazo dyes

Info

Publication number: GB1599550A
Application number: GB2602678A
Authority: GB
Original assignee: Aziende Colori Nazionali Affini ACNA SpA; ACNA Chimica Organica SpA
Current assignee: Aziende Colori Nazionali Affini ACNA SpA; ACNA Chimica Organica SpA
Priority date: 1977-06-09
Filing date: 1978-05-31
Publication date: 1981-10-07
Also published as: DE2824710A1; FR2393833B1; FR2393833A1; JPS5416536A

Description

(54) WATER-INSOLUBLE MONOAZO DYES (71) We, AZIENDE COLORI NAZIONALI AFFINI ACNA S.p.A., of Largo Donegani 1/2, 20100 Milan, Italy, an Italian Company, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention consists in a group of a new monoazo dyes, insoluble in water and free from hydrosolubilizing groups, derived from 4-amino-thiazole, and conforming to the general formula::

wherein R and R', which may be the same or different, are cyano or alkoxycarbonyl (optionally substituted) having from 2 to 8 carbon atoms, and Y is the residue of a coupling component of the 1 - phenyl - 5 - amino - pyrazole, 1 phenyl - 5 - hydroxy - pyrazole, indole, N - mono - alkyl or N,N - dialkyl amino - benzene, N - mono - alkyl - amino - naphthalene or N,N - dialkyl amino - naphthalene, and 6 - hydroxy - 2 - pyridone series.

Suitable alkoxycarbonyl groups include COOCH3, COOC4Hg, COOCH2CH2OCH2CH2OCH3 and COOCH2CH2CI.

As examples of the coupling component (Y--H) may be mentioned: - - (p - tolyl) - 5 - amino - pyrazole - - (p - tolyl) - 3 - methyl - 5 - aminopyrazole I - phenyl - 3 - methyl - 5 - hydroxy - pyrazole 1 - (m - chlorophenyl) - 5 - hydroxy - pyrazole 1 - (m - chlorophenyl) - 3 - methyl - 5 - hydroxy - pyrazole I - phenyl - 3 - carbomethoxy - 5 - hydroxy - pyrazole I - methyl - 2 - phenyl - indole (3' - methoxy - 4' - hydroxy) - 2 - phenyl - indole I - (2' - cyanoethyl) - 2 - phenyl - indole I - (3' - hydroxypropyl)2 - phenyl - indole N - - acetoxyethyl - N - - cyanoethyl - amino - benzene N - ethyl - N - - cyanoethyl - amino - benzene N,N - diethyl - m - acetylamino - amino - benzene N,N - dimethyl - m(A - carbomethoxypropionyl)amino - benzene 1 - diethylamino - naphthalene 1 - phenylethyl - amino - naphthalene, and derivatives of 6 - hydroxy - 2 - pyridone of the general formula

wherein R1 is CN, COO-alkyl, CO-alkyl, CO-NH-alkyl, CO-N-(alkyl)2 or

X being -0- or -CH2-, n being 1 or 2; m being 1 or 2, and the sum of m and n being 3 or 4, the alkyl groups having from 1 to 8 carbon atoms, R2 is an alkyl group with from 1 to 8 carbon atoms, a heterocyclic group, or an aromatic group with from 6 to 10 carbon atoms, optionally substituted, and R3 is an alkyl or cycloalkyl group with from 5 to 8 carbon atoms, or an aryl group with from 6 to 10 carbon atoms, optionally substituted, or CH2)3-O-all:yl, CH2)3-O-(CH2)2-O- alkyl, -NH2, -NH-alkyl, -N-(alkyl)2, or

with for the last group the expressions X, n and m being as defined above and the alkyl groups having from 1--8 carbon atoms.

The dyes of the invention are particularly suitable, especially in a finely subdivided form, for dyeing textile materials, such as fibres, yarns, staple fibres, cloths and knitwear made of linear polyester, polyamides or secondary and tertiary cellulose acetate. The resulting dyeings are generally characterised by good stabilities, a high color intensity, and in most cases they are suitable for obtaining effects of white and coloured corrosion by the "alkaline resist" method.

The new dyes may be prepared by diazotizing the derivatives of 4aminothiazole of formula:

in which R and R' are as defined above, followed by coupling with coupling component Y-H, wherein Y is as defined above.

The derivatives of 4-aminothiazole (II) referred to herein and employed as diazotizing amines, were prepared as described by D. Wobig, in Lieb. Ann. Chem.

1972 764, 125-130 and by W. Walek et al, in Tetrahedron, 1976 32, 623-627, starting from carbon disulphide, KOH, cyanamide and chloroacetonitrile (or an alkyl chloroacetate), according to the scheme:

wherein R, R' are as already defined and Hal is chlorine, bromine or iodine.

The coupling components Y-H may be prepared in a known manner; for example, N - methyl - 3 - cyano - 4 - methyl - 6 - hydroxy - 2 - pyridone (formula III R1=CN, R2 and R3=CH3) can be prepared by heating ethyl-acetate, ethyl-cyanoacetate and methylamine as described by Guareschi in Zentralblatt 1907, I 875).

Several important classes of dyes in accordance with the present invention specific members of which are described hereinafter, are set out in the appended Claims 2 to 8.

The following examples illustrate how the invention may be carried into effect.

Unless otherwise specified, the parts are by weight; the rationship of parts by weight and volume herein is that of grams to cubic centimeters.

EXAMPLE 1 3.93 parts of the compound of formula II in which R=R'=COOCH3 were added whilst stirring at 0--50C in the course of about 30 minutes to a mixture of 30 parts by volume of acetic acid, 15 parts by volume of propionic acid and 7.5 parts by volume of 2 N solution of NOHSO4 in concentrated H2SO Stirring was continued at 0--5"C for 1 hour. The resulting diazonium salt solution was treated with sulphamic acid for elimination of the existing NOHSO4 and was then added at e5"C to a solution of 2.8 parts of 1 - (p - tolyl) - 3 methyl - 5 - amino - pyrazole dissolved in 100 parts by volume of acetic acid, buffered at pH=65 with sodium acetate crystals.

After stirring at --50C for a further 30 minutes, the whole was poured into water, and the resulting precipitate was filtered and washed until the washings were neutral. The washed precipitate was dried in an oven under vacuum at 600 C, yielding 5.6 parts of a dye having the following formula:

The I.R. spectrum exhibited two bands of the COOCH3 group at 1700 and 1738 cm-'.

The dye was microfined to a fluid suspension with about 1.5 parts by volume of ethylene glycol and about the same weight of Saltetra SS (condensate of formaldehyde, m- and p-cresol and Schaffer acid) and 87 parts of water. 100 parts of the liquid microfined dye were then mixed with 150 parts of Lamitex L10 (a thickening agent based on sodium alginate), ("Lamitex" is a Registered Trade Mark), 2 parts of sodium chlorate, 3 parts of citric acid and 745 parts of water. The liquid so obtained was utilized to pad a polyester cloth.

After drying at 8O900C the cloth was printed with a paste for white corrosion containing 90 parts of sodium bicarbonate, 66 parts of polyethylene glycol, 33 parts of glycerine, 400 parts of Lamitex L10 (R.T.M.), 210 parts of water and 200 parts of an emulsion containing 80% of white spirit, 6% of emulsifier Diphasol FY (based on a long-chain condensate of ethylene oxide with a branched alcohol C16-C18) ("Diphasol" is a Registered Trade Mark) and 14% of water. It was then steamed at 1700C for 8-10 minutes. After washing and bleach-cleaning with NaOH (4 g/l) and hydrdsulphite (2 g/l) at 70--800C a bright yellow dyeing was obtained having an intensity of about 1/3 E.C.E. and being perfectly white in the zones subjected to "corrosion".

The same observation on the corrodibility could be made using 400 parts of the liquid microfined dye. In this case the dyeing had an intensity of about 1/1 E.C.E.

The dyeings exhibited good stability to sublimation and to laundering, as well as excellent fastness to sunlight.

The aminothiazole derivative employed for the synthesis of the dye of Example 1 was prepared as follows: 76 parts of CS2 and 42 parts of cyanamide dissolved in 75 parts by volume of methanol were introduced into a reactor equipped with a stirrer, a cooler and a thermometer.

113 parts of KOH dissolved in 350 parts by volume of methanol were then added, making sure that the temperature did not exceed 25"C after a further 30 minute stirring 200 parts of methyl chloroacetate were added, whereupon the reaction mixture was heaped under reflux for 1 hour. It was cooled to 50"C, 21 parts by volume of triethylamme were added and refluxing was resumed for 15 minutes.

At the end of this period, 160 parts by volume of methanol were distilled, the residue was cooled to 5-100C and the resulting solid precipitate was filtered. The precipitate was dispersed in 3000 parts of water and stirred for an hour at room temperature, filtered again and dried in oven under vacuum at 600 C.

There were obtained 127 parts of a product having a melting point of 98 100"C, which exhibited, on I.R. examination, two bands of the COOCH3 group respectively at 1668 and 1735 cm-', the primary NH2 at 3290 and 3460 cm-' and the thiazole ring at 1300, 1380 and 1520 cm-'.

EXAMPLE 2 Operating as indicated in Example 1 with the same 4-aminothiazole (II) in an amount of 5.24 parts and with 10 parts by volume of a 2 N solution of NOHSO4 in concentrated H2SO4, a solution of the diazonium salt of the abovesaid thiazole was obtained. The solution was then added, whilst stirring at 0--50C, to a solution previously cooled to 0--50C, of 4.14 parts of 2 - phenyl - 1 - methyl - indole dissolved (at an elevated temperature) in 100 parts by volume of acetic acid. During the addition, the pH was kept at 4--5 by adding sodium acetate. After stirring for 30 minutes at 0--5"C the reaction mass was poured into water, filtered, and the resulting precipitate washed until the washings were neutral.The precipitate was then dried in an oven under vacuum at 600 C. 8.6 parts of a dye having following formula:

and exhibiting two bands of the COOCH3 group at 1710 and 1739 cm-', were obtained.

Identical effects of white corrosion were obtained by carrying out the alkaline corrosion process as set out in Example 1 with a likewise microfined liquid. The dyeings exhibited a bright gold-yellow shade and were endowed with good stabilities to sunlight, sublimation and laundering.

By using the 4-aminothiazoles and the coupling components indicated in the following table instead of those specified in the foregoing examples, dyes having similar behaviour were obtained.

4-amino thiazole Coupling Shade on Ex. No. (II) Component polyester

C X H3 3 R=COOCH3 N R'=COOCH3 H yellow HO N 4-amino thiazole Coupling Shade on Ex. No. (11) Component polyester

--C 13 R'=COOCH3 H H3 yellow 1 5R=COOCH, {R'=COOCH3 1 NZC2H4C N orange N 6 R=COOCH3 N(C2H5) R'=COOCH3 )4 ::OCH3 n-CH3 rR=CN H N/ \N/ tR'=CN H2 NNCH3 yellow '-Hg R'=CN orange { R=CN tN(CH3)2 violet HCO(CH2)2COOCH3 10 (R=CN tN(C2Hs)2 violet R'=CN Il R'=CN g N H(C H2)2 violet EXAMPLE 12 3.93 parts of 4-aminothiazole II as used in Examples 1 and 2 were suspended, by stirring, in a mixture of 20 parts by volume of acetic acid and 10 parts by volume of propionic acid. After cooling to 0--5"C, 3.75 parts by volume of 4 N nitrosylsulphuric acid in concentrated H2SO4 were introduced, whilst stirring, in the course of 30 minutes.

The diazonium salt solution so prepared was added at 5--10"C and at a pH value=4--5, (established by addition of hydrated sodium acetate) to a suspension of the coupling component of formula III, in which Rl=CN= and R2=R3=CH3 prepared by dissolving 2.62 parts of the coupling agent in 127 parts of 6.3 11 NaOH and precipitating with 25 parts of acetic acid.

After filtering and washing, 6 parts of a yellow dye of the formula:

were obtained. The I.R. spectrum exhibited two bands of the COOCH3 group at 1690 and 1730 cm1 and a band of the C=O group at 1650 cm-'.

2 parts of the dye so obtained were microfined with 64.7 parts of a solution containing 3.9% of Chemitrol 1 (sodium lignin sulphonate), ("Chemitrol" is a Registered Trade Mark), 10.3% of ethylene glycol and 85.8% of water. 200 parts of the microfined liquid were mixed with 100 parts of Lamitex L10 (RTM) (a thickening agent based on sodium alginate), 2 parts of sodium chlorate, 3 parts of citric acid and 695 parts of water. The resulting liquid was utilized to pad a polyester fabric. After drying at 8--900C the fabric was printed with a white corrosion paste containing 90 parts of sodium bicarbonate, 66 parts of polyethylene glycol, 33 parts of glycerin, 400 parts of Lamitex L10 (RTM), 210 parts of water and 200 parts of an emulsion containing 80% of white spirit, 6% of emulsifier Diphasol EV (RTM) and 14% of water.

The fabric was then steamed at 1700C for 8-10 minutes. After washing and bleach-cleaning with 4 g of NaOH/liter and 2 g of hydro-sulphite/liter at 70--SOOC, a bright yellow dyeing was obtained, that exhibited an intensity of about 1/1 E.C.E., being thoroughly white in the areas subjected to corrosion. The same observation on the corrodibility could be made by using 400 parts of the microfined liquid. The dyeings exhibited good stability to sublimation, laundering and sunlight.

EXAMPLE 13 By operating as in Example 12 and with the same 4-aminothiazole (II) but with the pyridone of formula III, where R1=CN, R2=CH3 and R3=C2Hs, 6.2 g of a yellow dye of formula:

were obtained.

The I.R. spectrum exhibited two bands of the -COOCH3 group at 1690 and 1740 cm-' and a band of the C=O group at 1645 cm-'. Identical white corrosion effects were obtained by carrying out the alkaline corrosion process indicated in Example 12 with a similarly microfined liquid dye, operating either with 100 g/l. or with 200 g/l or with 400 g/l printing paste. The dyeings exhibited a bright yellow shade and good stability to sunlight, sublimation and laundering.

WHAT WE CLAIM IS: 1. Monoazo dyes of the general formula (I) hereinbefore defined.

2. Monoazo dyes according to Claim 1 of the formula:

wherein a and b are each -H or -CH3, and R and R' are each CN, or COO-alkyl wherein the alkyl group has 2-8 carbon atoms.

3. Monoazo dyes according to Claim 1 of the formula:

wherein c is Cl or Br, when n is 1 or 2; c is H when n is 0, d is CH3-COO-alkyl or CONH2-CH2COO-alkyl (the alkyl groups having 1--4 carbon atoms) or CH2CONHC6H5, and R1 and R2 are CN-COO-alkyl the alkyl group having 2-8 carbon atoms.

4. Monoazo dyes according to Claim 1, of the formula:

wherein e is phenyl, optionally substituted by OH and/or C1-C4 alkoxy, f is H, C1-C4 alkyl optionally substituted by OH or CN, or is COO-alkyl wherein the alkyl group has 1-5 carbon atoms, and R and R' are CN or COO-alkyl wherein the alkyl group has 2-8 carbon atoms.

5. Monoazo dyes according to Claim 1, of the formula:

wherein R1 is alkyl, (optionally substituted by OH; O-alkyl, O-CO-alkyl; CO-O- alkyl; Cl: Br: CN), benzyl, phenyl, or (CH2)2OCONHC2H5 (and wherein any alkyl groups have 14 carbon atoms); R2 is H, alkyl (optionally substituted by OH; Oalkyl, O-CO-alkyl; CO-O-alkyl; OCOOCH3: Cl; Br; CN) or (CH2)2OCONHC2Hs (and wherein any of the designated alkyl groups has 1-4 carbon atoms), g is alkyl, O-alkyl, Cl, Br, OCH2CN. OCH2CONH2* OCH2COOCH3.

NH(CH2)2CN. NHCO-alkyl, NHCOC6Hs, NHCOCH2CH2COO-alkyl, NHCONHalkyl, NHCONHC6Hs. or NHSO2CH3 (and wherein any of the designated alkyl

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. with 200 g/l or with 400 g/l printing paste. The dyeings exhibited a bright yellow shade and good stability to sunlight, sublimation and laundering. WHAT WE CLAIM IS:

1. Monoazo dyes of the general formula (I) hereinbefore defined.

2. Monoazo dyes according to Claim 1 of the formula:

3. Monoazo dyes according to Claim 1 of the formula:

4. Monoazo dyes according to Claim 1, of the formula:

5. Monoazo dyes according to Claim 1, of the formula:

groups has 1-4 carbon atoms): h is H, CH3, or O-alkyl the alkyl group having 1--4 carbon atoms: and R and R' are CN or COO-alkyl the alkyl groups having 2-8 carbon atoms.

6. Monoazo dyes according to Claim 1 of the formula:

wherein R3 is methyl or ethyl optionally substituted by phenyl, R4 is H, C1-C4 alkyl or phenyl, and R and R' are CN or COO-alkyl wherein the alkyl groups have 2-8 carbon atoms.

7. Monoazo dyes according to Claim 1 of the general formula:

wherein R and R', which may be the same or different, are cyano or carbalkoxy having 2 to 8 carbon atoms; R1 is CN, COO-alkyl, CO-alkyl, CONH-alkyl, or CONdialkyl optionally forming with the N atom a heterocyclic ring having 5 or 6 members; R2 is an alkyl or a heterocyclic ring or an aryl, optionally substituted; R3 is an alkyl, a cycloalkyl or an aryl, optionally substituted, or is (CH2)3O-alkyl, (CH2)3O(CH2)2O-alkyl or an amino, monoalkylamino or dialkylamino group optionally forming with the N atom a heterocyclic ring having 5 or 6 atoms; and R1, R2 and R3 having from 1 to 8 carbon atoms when they are alkyl, from 5 to 8 when cycloalkyl and from 6 to 10 when aryl.

8. Monoazo dyes according to Claim 7, having the formula:

wherein R and R' are CN or COO-alkyl the alkyl group having 1--8 carbon atoms, R2 is CH3 and R3 is an alkyl group of 1--8 carbon atoms.

9. A dye according to Claim 8, having the formula:

10. A dye according to Claim 8, having the formula:

11. A process for preparing monoazo dyes according to Claim 1, in which the diazo component of an amine having the general formula (II) hereinbefore defined is coupled in an acid medium, with a coupling component H-Y wherein Y is as hereinbefore defined.

12. Processes according to Claim 11, substantially as hereinbefore exemplified.

13. Monoazo dyes when made by a process according to Claim 11 or 12.

14. Textile materials comprising polyester fibres, polyamides, or secondary or tertiary cellulose acetate, dyed with a dye according to any of Claims 1--10 or 13.