Azo dyes from 2-amino-5-cyanomethylthio-1,3,4-thiadiazole and aniline and tetrahydroquinoline couplers

Abstract

This invention relates to new azo dyes derived from 2-amino-5-cyanomethylthio-1,3,4-thiadiazole and aniline and tetrahydroquinoline couplers which may be extensively substituted. The dyes impart orange to violet shades on hydrophobic fibers, including polyesters, polyamides, and cellulose esters. They are of the particular interest for dyeing textured polyester fibers and have excellent properties such as fastness to light and sublimation.

Description

This invention relates to new azo dyes derived from 2-amino-5-cyanomethylthio-1,3,4-thiadiazole and aniline and tetrahydroquinoline couplers which may be extensively substituted. The dyes impart orange to violet shades on hydrophobic fibers, including polyesters, polyamides, and cellulose esters. They are of the particular interest for dyeing textured polyester fibers and have excellent properties such as fastness to light and sublimation.

The dyes of this invention have the formula: ##STR1## wherein C is the residue of an aniline or tetrahydroquinoline coupling component of the formulae ##STR2## wherein R.sup.1 and R.sup.2 are each selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R.sup.9 in which X is --CO--, --COO--, or --SO.sub.2 --, and R.sup.9 is selected from alkyl, aryl, cycloalkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R.sup.9 also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino or furyl; R.sup.3 and R.sup.4 are each selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two groups selected from alkyl, --OH, alkoxy, halogen and hydroxy substituted alkyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; straight or branched alkenyl of 2-6 carbons; and straight or branched alkyl; wherein the alkyl groups of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be substituted with 1-3 of the following: hydroxy; halogen; cyano; amino; alkoxy; alkoxyalkoxy, hydroxyalkoxy; succinimido; glutarimido; phenylcarbamoyloxy; phthalimido; phthalimidino; 2-pyrrolidono; cyclohexyl; phenoxy; phenyl or phenyl substituted with alkyl, alkoxy, alkoxycarbonyl, halogen, alkanoylamino or cyano; alkanoylamino; sulfamoyl; alkylsulfamoyl; acrylamido; benzoylsulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula ##STR3## wherein Y is --NH--, ##STR4## --O--, --S--, >CHOH, or --CH.sub.2 O--; --S--R.sup.10 wherein R.sup.10 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl or ##STR5## --SO.sub.2 R.sup.9 ; --COOR.sup.9 ; --OXR.sup.9 ; --NH--X--R.sup.9 ; --CONR.sup.11 R.sup.11 ; --SO.sub.2 NR.sup.11 R.sup.11 ; wherein R.sup.9 and X are as defined above and R.sup.11 is selected from H and R.sup.9 ; alkoxy substituted with hydroxy, cyano, alkanoyloxy or alkoxy substituted with hydroxy, cyano, alkanoyloxy or alkoxy; phenoxy; phenoxy substituted with 1-3 of alkyl, alkoxy or halogen; or R.sup.3 and R.sup.4 combined forms pentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene which, with the nitrogen atom to which it is attached, forms a ring; and R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each selected from hydrogen and alkyl; and wherein each of the above alkyl, alkylene, alkoxy, alkanoyl, and such hydrocarbon moieties contain 1-6 carbons.

A preferred group of compounds of this invention have the formula ##STR6## wherein R.sub.2 is H or alkyl; R.sub.3 and R.sub.4 are selected from hydrogen, alkyl, cycloalkyl and alkyl substituted with aryl, acyloxy, cyano, carbamoyl, sulfamoyl, alkylamino, phenylcarbamoyloxy, alkoxy, aryloxy, alkoxycarbonyl, succinimido or phthalimido; X is CO, COO or SO.sub.2 ; and R.sup.9 is as defined above.

The present dyes exhibit improvements in one or more properties such as fastness to light, sublimation, chlorine, heat, ozone, gas, perspiration, crock, and wash, build, pH stability, bloom resistance, depth of shade, leveling, strike rate, energy of dyeing, migration, and the like, over such dyes as disclosed in U.S. Pat. Nos. 3,639,384; 3,639,385; 3,738,802; 3,762,861; 3,453,556; 3,657,215; and 3,657,215.

The invention can be better appreciated by reference to the following examples:

EXAMPLE 1

Preparation of 2-amino-5-cyanomethyl-1,3,4-thiadiazole

A mixture of 2-amino-5-mercapto-1,3,4-thiadiazole (66.5 g, 0.50 mol.), and ethanol (500 ml) is heated to reflux and chloroacetonitrile (41.1 g, 0.55 mol.) is added dropwise at reflux. Heating is continued for four hours and then about 400 ml of distillate is removed using a Dean-Stark trap. The clear solution is cooled to about 75.degree. C. and water (150 ml) is added, allowing the temperature to drop to about 50.degree. C. After adjusting the pH to about seven by adding slowly a solution of Na.sub.2 CO.sub.3, the mixture is cooled to room temperature and the gray product is collected by filtration and washed with water. The moist filter cake is recrystallized from 300 ml of ethanol to yield the desired product which melts at 163.degree.-164.degree. C.

EXAMPLES 2-11

Diazotization and Coupling

To sulfuric acid (25 ml) is added sodium nitrite (3.6 g) portionwise with stirring, allowing the temperature to rise. The pale yellow solution is cooled and 100 ml of 1:5 acid (1 part propionic:5 parts acetic acid) are added below 15.degree. C. To the chilled mixture is added portionwise 2-amino-5-cyanomethylthio-1,3,4-thiadiazole (8.6 g, 0.05 mol.) at 0.degree.-5.degree. C. After being stirred for 1.5 hours at 0.degree.-5.degree. C., the diazotization reaction mixture (0.005 mol. aliquot) is added to a chilled solution of each of the following couplers, prepared by dissolving 0.005 mol. of the coupler in 20 ml of 1:5 acid.

Example 2--3-Acetamido-N,N-diethylaniline Example 3--3-Acetamido-N,N-di-n-propylaniline Example 4--3-Acetamido-N-benzyl-N-ethylaniline Example 5--3-Benzamido-N,N-di-n-propylaniline Example 6--5-Acetamido-N-ethyl-2-methylaniline Example 7--5-Acetamido-N-cyclohexyl-2-methylaniline Example 8--3-Acetamido-N,N-dibenzylaniline Example 9--50/50 Mixture of couplers of Examples 2 and 3 Example 10--7-Acetamido-N-ethyl-1,2,3,4-tetrahydro-2,2,4-trimethylquinoline Example 11--N,N-Diethyl-3-methanesulfonamidoaniline

Ammonium acetate is added to the cold coupling mixtures until the mineral acid is neutralized (Congo Red test paper). After allowing to stand one hour, water is added to the coupling mixtures to precipitate the dyes, which are collected by filtration, washed with water, and dried in air. Any dyes which are not filterable solids are washed by decantation and dried in air. All of the dyes are crystallized from hot methanol for purification. The dyes color textured polyester bright red shades. For example, the dye of Example 1 has a visible absorption maximum (.lambda.max) at 525 nm.

The following tables give additional exemplary dyes of the present invention.

TABLE I__________________________________________________________________________ ##STR7##Ex.No. R.sub.1, R.sub.2 R.sub.3 R.sub.4__________________________________________________________________________12 H C.sub.2 H.sub.5 C.sub.2 H.sub.513 3-CH.sub.3 " "14 3-Cl " "15 2-OCH.sub.35-Cl H "16 2-OCH.sub.35-CH.sub.3 " "17 2,5-di-OCH.sub.3 " "18 2,5-di-CH.sub.3 " "19 2,5-di-Cl " "20 2-SCH.sub.3 " "21 3-OC.sub.6 H.sub.5 C.sub.2 H.sub.5 "22 3-SC.sub.6 H.sub.5 " "23 3-Br " "24 3,5-di-NHCOCH.sub.3 " "25 3,5-di-CH.sub.3 " "26 3-NHCOCH.sub.3 C.sub.2 H.sub.4 OC.sub.2 H.sub.5 C.sub.2 H.sub.4 OC.sub.2 H.sub.527 3-NHCOCH(CH.sub.3).sub.2 C.sub.2 H.sub.5 C.sub.3 H.sub.7n28 3-NHCOC.sub.4 H.sub.9n CH.sub.3 CH.sub.329 3-NHCOCH.sub.2 Cl " "30 3-NHCOCH.sub.2 OCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 C.sub.2 H.sub.531 3-NHCOCH.sub.2 OC.sub.6 H.sub.5 CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.332 3-NHCOCH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CN C.sub.2 H.sub.533 3-NHCONHC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CONH.sub.2 "34 3-NHCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 C.sub.6 H.sub.535 3-NHCOC.sub.6 H.sub.11 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.336 3-NHCOC.sub.6 H.sub.4p-OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.537 3-NHCOCH.sub.2 CN " "38 3-NHCOCH.sub.2 CH.sub.2 OCOCH.sub.3 " "39 3-NHCOCH.sub.2 SCH.sub.3 " "40 3-NHCHO " "41 3-NHSO.sub.2 C.sub.6 H.sub.5 " "42 2-CH.sub.35-NHSO.sub.2 CH.sub.3 C.sub.6 H.sub.11 H43 2-CH.sub.35-NHCOCH.sub.3 CH(CH.sub.3)C.sub.2 H.sub.5 " 44 ##STR8## C.sub.2 H.sub.5 C.sub.2 H.sub.5 45 3-NHCONH.sub.2 " "46 3-CH.sub.3 CH.sub.2 CH.sub.2 CN "47 " CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5 "48 " CH.sub.2 CH.sub.2 OCONHC.sub.2 H.sub.5 "49 " CH.sub.2 CH.sub.2 OCONHC.sub.6 H.sub.5 "50 " CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.4p-CH.sub.3 "51 " CH.sub.2 CH.sub.2 OH CH.sub.2 C.sub.6 H.sub.552 " CH.sub.2 CH(CH.sub.3)OH C.sub.6 H.sub.1153 " CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 C.sub.2 H.sub.554 " CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 " 55 " ##STR9## " 56 " CH.sub.2 CH(OH)CH.sub.2 Cl "57 " CH.sub.2 CH.sub.2 NHCOCH.sub.3 " 58 " ##STR10## " 59 " ##STR11## " 60 " ##STR12## " 61 " ##STR13## " 62 " ##STR14## " 63 3-NHCOCH.sub.3 ##STR15## " 64 " ##STR16## " 65 " CH.sub.2 CH.sub.2 NHCOC.sub.6 H.sub.5 " 66 " ##STR17## " 67 " ##STR18## " 68 " CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2 "69 " CH.sub.2 CH.sub.2 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 "70 " CH.sub.2 CH.sub.2 SO.sub.2 NHC.sub.2 H.sub.4 OH "71 " CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3 "72 " CH.sub.2 CH.sub.2 SCH.sub.3 "73 " CH.sub.2 CH.sub.2 SC.sub.6 H.sub.5 "74 " CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5 " 75 " ##STR19## " 76 " ##STR20## " 77 " CH.sub.2 CH.sub.2 CON(C.sub.2 H.sub.5).sub.2 "78 " CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 "79 " CH(CH.sub.3)CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 "80 " CH.sub.2 CH.sub.2 NHCOCHCH.sub.2 "81 " CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.282 3-CH.sub.3 CH.sub.2 CH.sub.2 CN CH.sub.2 CH.sub.2 OCOCH.sub.383 " " CH.sub.2 CH.sub.2 OC.sub.2 H.sub.584 " CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.285 " CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.286 " CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.387 3-Cl " "88 H " "89 3-NHCOCH.sub.3 CH.sub.2 C.sub.6 H.sub.11 C.sub.2 H.sub.590 " CH.sub.2 CH.sub.2 NHCO.sub.2 C.sub.2 H.sub.5 "91 " CH.sub.2 CH.sub.2 NHCOCH.sub.2 OH "92 " CH.sub.2 CH.sub.2 CN "93 2-CH.sub.35-NHCOCH.sub.3 CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 "94 " CH.sub.2 CH.sub.2 CONH.sub.2 " 95 3-CH.sub.3 ##STR21## " 96 " ##STR22## " 97 " ##STR23## " 98 " C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCOCH.sub.399 " C.sub.6 H.sub.11 CH.sub.2 CH.sub.2 CN100 " CH.sub.2 C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 CN101 " " CH.sub.2 CH.sub.2 OCOCH.sub.3102 " C.sub.6 H.sub.11 CH.sub.2 CH.sub.2 OCOCH.sub.3103 " CH.sub.2 CH.sub.2 CN CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5104 " " CH.sub.2 CH.sub.2 CN105 3-NHCOCH.sub.3 CH(CH.sub.3)C.sub.2 H.sub.5 H106 " CH.sub.2 CH.sub.2 OCOCH.sub.3 C.sub.2 H.sub.5107 3-CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 "__________________________________________________________________________ TABLE 2______________________________________ ##STR24##Ex.No. R.sub.1, R.sub.2, R.sub.5, R.sub.6, R.sub.7 R.sub.3______________________________________108 H C.sub.2 H.sub.5109 " CH.sub.2 C.sub.6 H.sub.5110 7-CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3111 2-CH.sub.3 CH.sub.2 C.sub.6 H.sub.4p-COOCH.sub.3112 2-CH.sub.37-Cl C.sub.2 H.sub.5113 5-CH.sub.38-OCH.sub.3 "114 7-NHCOCH.sub.3 "115 2-CH.sub. 37-NHCOCH.sub.3 "116 2-CH.sub.37-OC.sub.2 H.sub.5 "117 2-CH.sub.37-NHCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOCH.sub.3118 2-CH.sub.37-NHCOCH(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 CN119 2,2,4-tri-CH .sub.37-NHCOCH.sub.2 CH.sub.3 "120 " C.sub.2 H.sub.5121 " CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5122 2,7-di-CH.sub.3 CH.sub.2 C.sub.6 H.sub.5123 " CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5124 " CH.sub.2 CH.sub.2 OCONHC.sub.6 H.sub.5125 " CH.sub.2 CH.sub.2 OCONHC.sub.2 H.sub.5126 " CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5127 " CH.sub.2 CH.sub.2 CH.sub.2 NHCOCH.sub.3128 " CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3129 " CH.sub.2 CH.sub.2 NHCOC.sub.6 H.sub.5130 " CH.sub.2 CH.sub.2 CH.sub.2 NHCOOC.sub.2 H.sub.5131 " CH.sub.2 CH.sub.2 NHCOC.sub.6 H.sub.11132 " CH.sub.2 CH.sub.2 CONH.sub.2133 " CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5134 " CH.sub.2 CH.sub.2 SCH.sub.3 135 " ##STR25## 136 " ##STR26## 137 " ##STR27## 138 " ##STR28## 139 " ##STR29## 140 " ##STR30## 141 2,2,4-tri-CH.sub.3 CH.sub.2 CH.sub.3142 " CH.sub.2 C.sub.6 H.sub.5143 2,2,4,7-tetra-CH.sub.3 CH.sub.2 CH.sub.3144 " CH.sub.2 CH.sub.2 OCOCH.sub.3145 " CH.sub.2 CH.sub.2 OCONHC.sub.6 H.sub.5146 " CH.sub.2 CH.sub.2 OCOCH.sub.2 OCH.sub.3147 " CH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5148 " CH.sub.2 C.sub.6 H.sub.4p-COOCH.sub.3149 " CH.sub.2 C.sub.6 H.sub.11150 2,7-di-CH.sub.3 CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2151 " CH.sub.2 CH.sub.2 SO.sub.2 NHC.sub.2 H.sub.4 OH152 " CH.sub.2 CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3153 2,2,4-tri-CH.sub.37-NHSO.sub.2 CH.sub.3 CH.sub.2 CH.sub.3154 2,2,4-tri-CH.sub.37-NHCHO "155 2,2,4-tri-CH .sub.27-NHCONHC.sub.2 H.sub.5 "156 2,2,4-tri-CH.sub.37-NHCOC.sub.6 H.sub.5 "157 2,2,4-tri-CH.sub.37-NHCOC.sub.6 H.sub.11 "158 2,2,4-tri-CH .sub.37-NHCOCH.sub.2 CN "______________________________________

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 compound of the formula ##STR31## wherein C is a coupling component selected from ##STR32## wherein R.sup.1 and R.sup.2 are each selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R.sup.9 in which X is --CO-- or --COO--, and R.sup.9 is selected from alkyl, aryl, cycloalkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--, R.sup.9 is further selected from hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino and furyl;

R.sup.3 and R.sup.4 are each selected from hydrogen; cycloalkyl; cycloalkyl substituted with one or two groups selected from alkyl, --OH, alkoxy, halogen and hydroxy substituted alkyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; straight or branched alkenyl of 2-6 carbons; and straight or branched alkyl; or R.sup.3 and R.sup.4 combined forms pentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene which, with the nitrogen atom to which it is attached, forms a ring;

wherein the alkyl groups of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are unsubstituted or substituted with 1-3 of the following: hydroxy; halogen; cyano; amino; alkoxy; alkoxyalkoxy; hydroxyalkoxy; succinimido; glutarimido; phenylcarbamoyloxy; phthalimidino; 2-pyrrolidono; cyclohexyl; phenoxy; phenyl or phenyl substituted with alkyl, alkoxy, alkoxycarbonyl, halogen, alkanoylamino or cyano; alkanoylamino; sulfamoyl; alkylsulfamoyl; acrylamido; phthalimido; benzoylsulfonicimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; alkenylcarbonylamino; groups of the formula ##STR33## wherein Y is --NH--, ##STR34## --O--, --S--, >CHOH, or --CH.sub.2 O--; --S--R.sup.10 wherein R.sup.10 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or a radical of the formula ##STR35## --SO.sub.2 R.sup.9 ; --COOR.sup.9 ; --OXR.sup.9 ; --NH--X--R.sup.9 ; --CONR.sup.11 R.sup.11 ; --SO.sub.2 NR.sup.11 R.sup.11 ; wherein R.sup.9 and X are as defined above and R.sup.11 is selected from H and R.sup.9 ; alkoxy substituted with hydroxy, cyano, alkanoyloxy or alkoxy; phenoxy; phenoxy substituted with 1-3 of alkyl, alkoxy or halogen; and

R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each selected from hydrogen and alkyl.

2. A compound according to claim 1 wherein C is ##STR36## and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined therein.

3. A compound according to claim 1 wherein C is ##STR37## and R.sup.1, R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are as defined therein.

4. A compound according to claim 1 having the formula ##STR38## wherein R.sub.2 is H or alkyl; R.sub.3 and R.sub.4 are selected from hydrogen, alkyl, cycloalkyl and alkyl substituted with aryl, --OXR.sup.9, cyano, carbamoyl, sulfamoyl, alkylamino, phenylcarbamoyloxy, alkoxy, aryloxy, alkoxycarbonyl, succinimido or phthalimido; X is --CO-- or --COO--; and R.sup.9 is as defined in claim 1.

5. The compound of claim 1 having the formula ##STR39##

6. The compound of claim 1 having the formula ##STR40##

7. The compound of claim 1 having the formula ##STR41##

8. The compound of claim 1 having the formula ##STR42##

9. The compound of claim 1 having the formula ##STR43##

10. The compound of claim 1 having the formula ##STR44##