US 4,301,070 AGrant
Azo Dyes From a 5-Aminopyrazole Bearing 1 to 2 Sulfated Hydroxyalkoxycarbonyl or N-(Hydroxyalkyl) Carbamoyl Groups on Its Ring
Issue Date:1981-11-17
•4 Claims
Abstract
This invention relates to azo dyes in which the diazotized amino component bears 1 or 2 sulfated hydroxyalkoxycarbonyl or N-(hydroxyalkyl)carbamoyl groups on its ring. These dyes have excellent dyeing properties on polyamide fibers and also impart color to cellulose acetate fibers and wool. The dyes correspond to the formula: ##STR1## wherein when n is 1, R.sup.1 is selected from hydrogen, alkyl, aryl, alkylthio, carbamoyl, alkylcarbamoyl, acyl, cyanoalkyl, and halogen; R is selected from hydrogen, alkyl, aryl, acyl, alkylsulfonyl, arylsulfonyl alkylsulfamoyl, arylsulfamoyl, alkyl substituted with alkoxy, cyano, or halogen, and aryl substituted with alkoxy, halogen, or cyano; X' is O, NH, N(alkyl)--or N(aryl)--; Z is selected from straight- or branched-chain alkylene which may be substituted, for example, with phenyl, halogen, OSO.sub.3 M, alkoxy, aryloxy and the like; M is H, Na, K or NH.sub.4 ; n is 1 or 2; and the coupler C is selected from a variety of couplers including anilines, tetrahydroquinolines, phenols and the like.
Metadata
Assignee
- Eastman Kodak Company
Inventors
- Ralph R. Giles
- Max A. Weaver
Application Information
Application Number:US 1006266
Filing Date:1979-12-05
Priority Date:1979-12-05
Art Unit:117
Classifications
IPC:
C09B 29036C09B 2909C09B 2932C09B 2936
Field of Search:
260152;154;155;156;157;158;162;163;205;206;207;207.1;186;187
Patent Drawings
This patent does not have any drawings.
Description
This invention concerns novel dyes in which the diazo moieties contain sulfate groups. These dyes are substantially water soluble and are particularly useful for dyeing polyamide, wool and the like, and exhibit excellent properties including fastness to light and dyeability.
The dyes of this invention correspond to the general formula: ##STR2## wherein D is a pyrazol-5-yl radical which may be substituted further as defined below; C is the coupler portion of the molecule; X' is O, NH N(alkyl)--, or N(aryl)--; Z is selected from straight- or branched-chain alkylene, which may be substituted, for example, with phenyl, halogen, OSO.sub.3 M, alkoxy or aryloxy groups, --CH.sub.2 (CH.sub.2).sub.m V--CH.sub.2 (CH.sub.2).sub.p --, where m is 1, 2 or 3, p is , 1, 2 or 3, and V is O, S, SO.sub.2, --SO.sub.2 NH--, --SO.sub.2 N(alkyl)--, --SO.sub.2 N(aryl), --N(SO.sub.2 aryl)--, --NH, --NHCO--, --NHCONH, --N(SO.sub.2 alkyl), or --CON(alkyl); M is H, Na, K or NH.sub.4 ; and n is 1 or 2.
More particularly, the dyes correspond to the formula above wherein D represents the radical ##STR3## wherein the pyrazol-5-yl ring, in addition to the ##STR4## group where n is 1, may have a substituent R.sup.1 selected from hydrogen, alkyl, aryl, alkylthio, carbamoyl, alkylcarbamoyl, acyl, cyanoalkyl, and halogen; R is selected from hydrogen, alkyl, aryl, acyl, alkylsulfonyl, arylsulfonyl, alkylsulfamoyl, arylsulfamoyl, alkyl substituted with alkoxy, cyano, or halogen, and aryl substituted with alkoxy, halogen, or cyano; and the coupler C is selected from ##STR5## wherein R.sup.2 and R.sup.14 each represents up to three groups selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R.sup.3 in which X is --CO--, --COO--, or --SO.sub.2 -- and R.sup.3 is selected from alkyl and alkyl substituted with halogen hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R.sup.3 also is selected from hydrogen, amino, alkylamino, alkylcarbamoyl, dialkylamino, arylamino, aryl, and furyl;
R.sup.4 and R.sup.5 are each selected from hydrogen, alkyl, aryl, cycloalkyl, and R.sup.4 and R.sup.5 together represent a single, combined group --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 --, and --CH.sub.2 CH.sub.2 --SO.sub.2 --CH.sub.2 CH.sub.2 --;
R.sup.8 is one or two groups each selected from hydrogen, alkyl and alkyl substituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, cyclohexoxy, --OH, --Cl and Br;
R.sup.9, R.sup.10 and R.sup.11 are each selected from hydrogen, alkyl, phenyl, or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkylthio, benzylthio, cyclohexylthio, phenylthio and substituted phenylthio;
Q and Q' are each selected from --CO--, --SO.sub.2 --, or --CN; R.sup.12 and R.sup.13 are each selected from hydrogen, alkyl, hydroxyalkyl, alkoxy, alkoxycarbonylamino, trifluoromethyl, phenyl or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkoxycarbonylalkyl, cyanoalkyl, amino, haloalkyl, alkylamino, alkylthio, benzylthio, cyclohexylthio, phenylthio and substituted phenylthio; R.sup.12 and R.sup.13 may combine to form an alkylene bridge of 2 or 3 carbons, or to form an arylene or cycloalkylene radical of 5-6 carbons connecting Q and Q'; R.sup.16 and R.sup.17 are selected from hydrogen, cycloalkyl, aryl, alkyl, and alkyl substituted with alkoxy, hydroxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, sulfamoyl, acylamido or alkenylsulfonyl, and aryl substituted with hydroxyalkyl; e is 1 or 2; and t and t' are each 1 or zero. It is noted that when t or t' is zero, the corresponding Q or Q' group is --CN;
Each of the aliphatic portions of the above alkyl, cycloaliphatic, alkoxy, alkanoyl and the like groups, as well as the aryl and aryloxy groups, may be substituted further with up to three of the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; ##STR6## wherein Y is --NH--, --NH-alkyl--, --O--, --S--, or --CH.sub.2 O--; --S--R.sup.6 wherein R.sup.6 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, triazolyl, or ##STR7## --SO.sub.2 R.sup.3 ; --COOR.sup.3 ; --OXR.sup.3 ; --NH--X--R.sup.3 ; --X--R.sup.3 ; --OCO--R.sup.3 ; --CONR.sup.7 R.sup.7 ; --SO.sub.2 NR.sup.7 R.sup.7 ; wherein R.sup.3 and X are as defined above and each R.sup.7 is selected from H and R.sup.3 ; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy or phenoxy substituted with one or more of alkyl, alkoxy or halogen. All of the aliphatic portions of the various groups herein contain from 1-6 carbons, and are straight or branched chain.
The dyes of this invention impart red to blue shades on fibers, particularly polyamides, and are especially useful for dyeing polyamide (nylon) carpets, giving good fastness to light ozone, oxides of nitrogen, washing, sublimation, crocking and the like, and having good leveling, transfer, exhaustion, and build properties.
The couplers used in this invention are prepared according to known procedures. The dyes may be prepared by reacting the coupler with a diazonium salt which contains one or two carbalkoxy groups. The product is reacted first with an aminoalcohol H--X'--Z--OH (X' is NH, Z is alkylene) to convert to a N-(hydroxyalkyl)carbamyl group, or with an alkanediol H--X'--Z--OH (X' is O, Z is alkylene) to convert to a hydroxyalkoxycarbonyl group. Subsequently, the material is reacted with concentrated sulfuric acid to form the sulfate ester: ##STR8## Alternatively, a diazotizable amine containing a hydroxyalkoxycarbonyl group or a N-(hydroxyalkyl)carbamyl group may be sulfated before diazotization and coupling:
This invention will be further illustrated by the following examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention. The compounds listed in the tables below can be prepared by procedures well known in the art. In these tables, the "Position" column refers to the position of the ##STR10## group or groups on the pyrazol-5-yl ring.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims
We claim:
1. A dye of the formula: ##STR30## wherein R.sup.1 is selected from hydrogen, alkyl, aryl, alkylthio, carbamoyl, alkylcarbamoyl, alkanoyl, cyanoalkyl, and halogen; R is selected from hydrogen, alkyl, aryl, alkanoyl, alkylsulfonyl, arylsulfonyl, alkyl sulfamoyl, arylsulfamoyl, alkyl substituted with alkoxy, cyano, or halogen, and aryl substituted with alkoxy, halogen or cyano; and C is selected from ##STR31## wherein R.sup.2 and R.sup.14 each represents up to three groups selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R.sup.3 in which X is --CO--, --COO--, or --SO.sub.2 -- and R.sup.3 is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R.sup.3 also is selected from hydrogen, amino, alkylamino, dialkylamino, arylamino, aryl, and furyl; R.sup.4 and R.sup.5 are each selected from hydrogen, alkyl, aryl, cycloalkyl, and alkyl substituted with halogen, CN, OH, alkoxy, aryloxy, alkoxyalkoxy, alkanoyl, alkanolyloxy, carbamoyl, alkylcarbamoyl, sulfamoyl, alkylsulfamoyl, alkoxyalkanoyloxy, and cycloalkyl, and R.sup.4 and R.sup.5 together represent a single, combined group --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 --, or --CH.sub.2 CH.sub.2 --SO.sub.2 --CH.sub.2 CH.sub.2 --; R.sup.8 represents one or two groups each selected from hydrogen, alkyl and alkyl substituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, phenyl, cyclohexoxy, --OH, --Cl and Br; R.sup.9, R.sup.10 and R.sup.11 are each selected from hydrogen, alkyl, phenyl, or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkylthio, benzylthio, cyclohexylthio and phenylthio; Q and Q' are each selected from --CO--, --SO.sub.2 --, or --CN; R.sup.12 and R.sup.13 are each selected from alkyl, hydroxyalkyl, alkoxy, alkoxycarbonylamino, trifluoromethyl, phenyl or phenyl substituted with 1-3 groups selected from Cl, Br, alkyl or alkoxy, alkoxycarbonylalkyl, cyanoalkyl, amino, haloalkyl, alkylamino, alkylthio, benzylthio, cyclohexylthio and phenylthio; and R.sup.12 and R.sup.13 together comprise --CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2 --, or 1,2-C.sub.6 H.sub.4 -- connecting Q and Q'; R.sup.16 and R.sup.17 are selected from hydrogen, cycloalkyl, aryl, alkyl, and alkyl substituted with alkoxy, hydroxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, sulfamoyl, alkanoylamino, or alkenylsulfonyl, and aryl substituted with hydroxyalkyl; e is 1 or 2; t and t' are each 1 or zero; X' is O, NH, N(alkyl)--, or N(aryl)--; Z is selected from straight- or branched-chain alkylene, and such alkylene substituted with phenyl, halogen, OSO.sub.3 M, alkoxy or aryloxy groups, --CH.sub.2 (CH.sub.2).sub.m V--CH.sub.2 (CH.sub.2).sub.p --, where m is 1, 2 or 3, p is 0, 1, 2 or 3, and V is O, S, SO.sub.2, --SO.sub.2 NH--, --SO.sub.2 N(alkyl)--, --SO.sub.2 N(aryl), --N(SO.sub.2 aryl)--, --NH, --NHCO--, --NHCONH, --N(SO.sub.2 alkyl), or --CON(alkyl); M is H, Na, K or NH.sub.4 ; n is 1 or 2; and wherein each of the above alkyl and alkoxy groups contain from 0 to three of the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkyl-sulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxybonyloxy; ##STR32## wherein Y is --NH--, --NH-alkyl--, --O--, --S--, or --CH.sub.2 O--; --S--R.sup.6, wherein R.sup.6 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or ##STR33## --SO.sub.2 R.sup.3 ; --COOR.sup.3 ; --OXR.sup.3 ; --NH--X--R.sup.3 ; --X--R.sup.3 ; --SO.sub.2 NR.sup.7 R.sup.7 ; wherein R.sup.3 and X are as defined above and each R.sup.7 is selected from H and R.sup.3 ; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; or phenoxy substituted with one or more of alkyl, alkoxy or halogen.
2. The dye according to claim 1 of the formula ##STR34##
3. The dye according to claim 1 of the formula ##STR35##
4. The dye according to claim 1 of the formula ##STR36##