Thiophen-2-ylazopyrazole compounds as colorants for textile fibers

Abstract

Thiophen-2-ylazopyrazole dyes useful for dyeing polyesters, cellulose acetate esters, and polyamides in fast yellow shades have the general formula: ##STR1## wherein: X is alkyl, allyloxy, alkoxy, aryl, aryloxy, amino, alkylamino, arylamino, cyclohexyloxy,, thienyl, cycloalkylamino, N,N-dialkylamino, or N-alkyl-N-arylamino; Y is hydrogen, alkyl, or aryl; Z is alkyl, aryl, alkylsulfonyl, 2-benzothiazolyl, cyano or COX; R and R.sub.1 are alkyl or aryl; R.sub.2 is hydrogen, alkyl, aryl, acyl, benzothiazolyl, pyridyl, sulfolanyl, quinolyl, thiocarbamyl, carbamyl, alkoxycarbonyl, aroyl, aryl-carbamyl and alkanoyl; and wherein the hydrocarbon moieties of the above radicals may be substituted with up to three of --OH, alkoxy, hydroxyalkoxy, carbamyl, and similar groups conventionally used in the azo dye art.

Description

DESCRIPTION

This invention relates to thiophen-2-ylazopyrazole dyes useful for dyeing polyesters, cellulose acetate esters, and polyamides in fast yellow shades.

The present dyes have the general formula: ##STR2## wherein: X is alkyl, allyloxy, alkoxy, aryl, aryloxy, amino, alkylamino, arylamino, cyclohexyloxy, thienyl, cycloalkylamino, N,N-dialkylamino, or N-alkyl-N-arylamino; Y is hydrogen, alkyl, or aryl; Z is alkyl, aryl, alkylsulfonyl, 2-benzothiazolyl, cyano or COX; R and R.sub.1 are alkyl or aryl; R.sub.2 is hydrogen, alkyl, aryl, acyl, benzothiazolyl, pyridyl, sulfolanyl, quinolyl, thiocarbamyl, carbamyl, alkoxycarbonyl, aroyl, arylcarbamyl and alkanoyl; wherein the hydrocarbon moieties of the above radicals may be substituted with up to three of --OH, alkoxy, hydroxyalkoxy, carbamyl, alkylcarbamyl, alkylcarbamyloxy, dialkylcarbamyl, arylcarbamyl, arylcarbamyloxy, --NO.sub.2, alkanoylamino, alkanoyl, alkoxycarbonyl, alkanoyloxy, --CF.sub.3, aryloxy, halogen, alkoxyalkoxy, alkoxycarbonyloxy, aryl, --CN, alkenyl, succinimido, phthalimide, furyl, cyclohexyl, and cycloalkyl substituted with hydroxyalkyl; and wherein the alkyl groups or moieties within the above definitions of Y, Z, R, R.sub.1 and R.sub.2 contain from 1-8 carbons, of X contain from 1-10 carbons, and are straight or branched chain.

The dyes of this invention color polyester, cellulose acetate, and polyamides in clear yellow shades and have excellent lightfastness on all three substrates. This property is quite unusual in view of disperse dyes of similar type such as those of Br. Pat. No. 1,394,365. The present dyes, in general, also exhibit other improved properties such as fastnes to sublimation, chlorine, heat, ozone, oxides of nitrogen, gas, perspiration, crock, and wash, and exhibit good build, pH stability, bloom resistance, dye bath exhaustion, depth of shade, leveling, strike rate, migration, and the like.

The present dyes are prepared as shown by the reaction scheme below by diazotizing substituted 2-aminothiophenes II and coupling with 1,3-diketo couplers III to produce intermediate compounds IV, followed by reaction with hydrazine or substituted hydrazines to produce the dyes V. ##STR3##

Dyes V, when COX is an amide group, are best prepared by reacting the corresponding dye where X is OCH.sub.3 with ammonia or an aliphatic amine. Compounds II are prepared as disclosed in [Z. Chem., Volume 2, page 305, (1962)]; Chem. Ber., Volume 98, page 3571 (1965) and Volume 99, page 2712 (1966); Chem. Heterocyclic Compounds, Volume 2, page 285 (1966) and Volume 3, Page 178 (1967). Compounds III and the hydrazines are readily commercially available.

Typical useful hydrazines include the following: ##STR4##

The preferred dyes are those where: X is alkoxy or alkylamine; Y is H or alkyl; Z is carbalkoxy, acyl, CONHaryl, cyano, or aryl; R and R.sub.1 are alkyl or aryl; and R.sub.2 is H, aryl, or alkyl, and sulfolanyl. The most preferred dyes are those of Examples 2, 3, 4, 26, 90, 92, and 93 herein.

The following examples will further illustrate the invention.

EXAMPLE 1

Diazotization and Coupling

Sodium nitrite (3.6 g.) was added portionwise to 25 ml of concentrated H.sub.2 SO.sub.4, allowing the temperature to rise. The solution was cooled and 50 ml of 2:5 acid (2 parts propionic acid:5 parts acetic acid--by volume) was added at <20.degree. C. After further cooling, 2-amino-3,5-dicarbethoxy-4-methylthiophene (12.9 g., 0.05 m) was added at 0.degree.-5.degree. C. and then another 50 ml of 2:5 acid was added at <5.degree. C. Stirring was continued at 0.degree.-5.degree. C. for 1.5 hr.

For the coupling, 2,4-pentanedione (5 g., 0.05 m) was dissolved in about 200 ml of water containing 75 g. of sodium acetate. Crushed ice was added for cooling and the above diazo solution added. Additional water/ice mixture was added as needed as thickening occurred. The reaction mixture was stirred for 15 min. at about 10.degree.-15.degree. C., heated to about 70.degree. C. and filtered hot. The intermediate dye was collected by filtration, washed with water, and dried in air, and has the following structure: ##STR5##

EXAMPLE 2

Reaction With Hydrazine

The dye from Example 1 (1.84 g., 0.005 m) was added to a solution of 64% hydrazine hydrate (0.5 g.) in methanol (10 ml) and heated to reflux. As the reaction mixture approached reflux temperature the yellow product crystallized. After 5 min. at reflux, the reaction mixture was cooled and the dye (1.5 g) was collected by filtration, washed with methanol and dried in air. The dye has the structure ##STR6## and produces bright yellow shades on cellulose acetate, polyamide, and polyester fibers.

EXAMPLE 3

Reaction With 2-Hydroxyethylhydrazine

The dye derived from diazotizing 2-amino-3,5-dicarbomethoxy-4-methylthiophene and 2,4-pentanedione as illustrated in Example 1 (3.0 g), N,N-dimethylformamide (10 ml), and 2-hydroxyethylhydrazine--90% (1.0 g) were mixed and heated at 65.degree. C. for 5 min. After cooling, methanol (40 ml) was added to precipitate the yellow dye (2.0 g) which was collected by filtration, washed with methanol and dried in air. The dye has the structure ##STR7## and produces bright yellow shades on cellulose acetate, polyamide, and polyester fibers. This dye can be reacted further on the hydroxyethyl group to give additional functional derivatives.

EXAMPLE 4

Reaction With 2-Hydrazinobenzothiazole

A mixture of the 1,3-diketo dye from Example 1 (0.5 g), 2-hydrazinobenzothiazole (0.3 g.) and N,N-dimethylformamide (10 ml) was heated at 95.degree.-100.degree. C. for 1 hr. During the last portion of the heating period the dye crystallized. Ethanol (10 ml) was added to further precipitate the dye and the mixture cooled. The dye was collected by filtration, washed with ethanol, and dried in air. It has the structure ##STR8## and produced bright lightfast shades on polyester and has excellent pH stability and fastness to sublimation.

EXAMPLE 5

Reaction With Propionic Anhydride

The dye of Example 1 (0.5 g), propionic anhydride (20 ml), and a trace of concentrated H.sub.2 SO.sub.4 were heated at reflux for 6 hrs. Upon cooling the yellow dye crystallized and was filtered, washed with methanol and dried in air. The acylation product has the structure ##STR9##

The following table gives additional specific dyes of the present invention.

TABLE I__________________________________________________________________________ ##STR10##Ex. X Y Z R R.sub.1 R.sub.2__________________________________________________________________________ 6 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 C.sub.6 H.sub.5 H 7 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 C.sub.6 H.sub.5 C.sub.6 H.sub.5 H 8 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 C.sub.6 H.sub.5 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OH 9 CH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 310 OC.sub.2 H.sub.5 H C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 C.sub.2 H.sub.4 Cl11 OC.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CN12 OCH.sub.2CHCH.sub.2 CH.sub.3 Ph CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CONH.sub. 213 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OCONHC.su b.6 H.sub.514 OCH.sub.2 CH.sub.2 CN CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OCONHC.su b.2 H.sub.515 OCH.sub.3 Ph CO.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.516 OCH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.517 OCH.sub.2 CH.sub.2 CON(C.sub.2 H.sub.5).sub.2 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CONH.sub.218 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.519 Php-CF.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CO.sub.2 C.sub.6 H.sub.520 OCH.sub.3 CH.sub.3 CN CH.sub.3 CH.sub.3 CH.sub.321 OCH.sub.2 CH.sub.2 CN CH.sub.3 CO.sub.2 C.sub.4 H.sub.9n CH.sub.3 CH.sub.3 ##STR11##22 Ph CH.sub.3 CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 ##STR12##23 OCH.sub.2 Ph CH.sub.3 CO.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9n CH.sub.3 CH.sub.3 C.sub.6 H.sub.524 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 C.sub.6 H.sub.4p-OCH.sub.325 OCH.sub.3 CH.sub.3 CH.sub.3 C.sub.4 H.sub.9n C.sub.4 H.sub.9n C.sub.6 H.sub.4p-NO.sub.226 OC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 ##STR13##27 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 ##STR14##28 OCH.sub.3 CH.sub.3 CO.sub.2 Ph CH.sub.3 CH.sub.3 ##STR15##29 NH.sub.2 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 ##STR16##30 OCH.sub.3 CH.sub.3 COPh CH.sub.3 CH.sub.3 ##STR17##31 NHC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 ##STR18##32 Php-NO.sub.2 CH.sub.3 CONH.sub.2 CH.sub.3 CH.sub.3 ##STR19##33 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 ##STR20##34 NHPh H COCH.sub.3 C.sub.3 H.sub.7n C.sub.3 H.sub.7n H35 OCH.sub.3 H OPh CH.sub.3 CH.sub.3 H36 OC.sub.6 H.sub.11 H COCH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CON(C.sub .2 H.sub.5).sub.237 OCH.sub.3 H ##STR21## CH.sub.3 CH.sub.3 C.sub.6 H.sub.538 OCH.sub.3 H CN CH.sub.3 CH.sub.3 H39 NHC.sub.6 H.sub.11 H CN C.sub.6 H.sub.5 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 NHCOCH.su b.340 OCH.sub.3 H SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 ##STR22##41 OCH.sub. 2 CH.sub.2 NHCOCH.sub.3 H Ph CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH42 N(C.sub.2 H.sub.5).sub.2 H C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H43 OCH.sub.3 CH.sub.3 CONHPh CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CF.sub.344 OC.sub.4 H.sub.9n CH.sub.3 CO.sub.2 C.sub.4 H.sub.9n CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH45 OCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OPh46 OC.sub.10 H.sub.21n CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.547 OC.sub.8 H.sub.17n CH.sub.3 CO.sub.2 CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 n CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH48 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.104- OH49 NCH.sub.3 (Ph) CH.sub.3 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub. 4 OC.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H50 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.2 Ph CH.sub.3 CH.sub.3 H51 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.2 OPh CH.sub.3 CH.sub.3 H52 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.2 Cl CH.sub.3 CH.sub.3 H53 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.4 CN CH.sub.3 CH.sub.3 H54 OCH.sub.3 CH.sub.3 CO.sub.2 Ph CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.1155 OCH.sub.3 CH.sub.3 ##STR23## CH.sub.3 CH.sub.3 H56 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.4 NHCOCH.sub.3 CH.sub.3 CH.sub.3 H57 NH.sub.2 CH.sub.3 COCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH58 NH.sub.2 CH.sub.3 COC.sub.2 H.sub.5 CH.sub.3 CH.sub.3 C.sub.6 H.sub.559 NHC.sub.2 H.sub.4 OH H (CH.sub.3).sub.2 CHCO CH.sub.3 CH.sub.3 H60 NHC.sub.2 H.sub.4 OH Ph COPh CH.sub.3 CH.sub.3 H61 NHC.sub.2 H.sub.4 OH Ph CN CH.sub.3 CH.sub.3 H62 NHC.sub.2 H.sub.4 OH H CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H63 NHC.sub.2 H.sub.4 OH H CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 H64 NHC.sub.2 H.sub.4 OH H Ph CH.sub.3 CH.sub.3 H65 NHC.sub.2 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H66 NHCH.sub.2 CH.sub.2 C.sub.2 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H67 NHC.sub.4 H.sub.9 n CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H68 NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H69 ##STR24## CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 COC.sub.2 H.sub.570 N(C.sub.2 H.sub.5).sub.2 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 ##STR25##71 N(CH.sub.3)Ph CH.sub.3 COCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH72 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 ##STR26##73 OCH.sub.3 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 ##STR27##74 OCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9n CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OH75 Ph CH.sub.3 CO.sub.2 Ph CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OH76 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.6 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OH77 OCH.sub.3 CH.sub.3 CO.sub.2 C.sub.6 H.sub.11 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OH78 OCH.sub.3 CH.sub.3 CONH.sub.2 CH.sub.3 CH.sub.3 ##STR28##79 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9n CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 COCH(CH.sub.3).sub.280 NHC.sub.2 H.sub.4 OH CH.sub.3 NHC.sub.2 H.sub.4 OH CH.sub.3 CH.sub.3 H81 ##STR29## CH.sub.3 ##STR30## CH.sub.3 CH.sub.3 H82 NHC.sub.8 H.sub.17n CH.sub.3 CO.sub.2 CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 H83 OCH.sub.3 CH.sub.3 ##STR31## CH.sub.3 CH.sub.3 H84 OCH.sub.3 H COCH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 ##STR32##85 OCH.sub.3 Ph COCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH86 Ph H COCH.sub.3 CH.sub.3 CH.sub.3 H87 ##STR33## CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H88 ##STR34## CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H89 OCH.sub.2 C.sub.6 H.sub.5 CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H90 OCH.sub.3 CH.sub.3 ##STR35## CH.sub.3 CH.sub.3 H91 OCH.sub.3 CH.sub.3 ##STR36## CH.sub.3 CH.sub.3 ##STR37##92 OCH.sub.3 H COCH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 H93 OCH.sub.3 H COCH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH94 OCH.sub.3 CH.sub.3 ##STR38## CH.sub.3 CH.sub.3 H95 OCH.sub.3 H ##STR39## CH.sub.3 CH.sub.3 H96 OC.sub.2 H.sub.5 H ##STR40## CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OH__________________________________________________________________________

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. A dye of the formula: ##STR41## wherein: X is alkyl; Y is hydrogen or alkyl; Z is COQ where Q is alkoxy, alkylamino, arylamino, or 2-thienyl; R and R.sub.1 are each alkyl; R.sub.2 is hydrogen, alkyl, benzothiazolyl, or sulfolanyl; and wherein the hydrocarbon moieties of the above are unsubstituted or substituted with hydroxy or alkoxy.

2. The dye according to claim 1 having the formula ##STR42##

3. The dye according to claim 1 having the formula ##STR43##

4. The dye according to claim 1 having the formula ##STR44##

5. The dye according to claim 1 having the formula ##STR45##

6. The dye according to claim 1 having the formula ##STR46##

7. The dye according to claim 1 having the formula ##STR47##

8. The dye according to claim 1 having the formula ##STR48##