[1]3 , t 7 8 7 , 3 8 8 Umted States Patent Office atented Jan. 22, 1974 3,787,388 TEGAZOLYL-AZO-TETRAHYDROQUINOLM COMWOUNDS Max A. Weaver and David L Wallace, Kingsport,.Tenn., assignors to Eastman Kodak Company, Rochester. N.Y. 5 No Drawing. Continuation of abandoned appucation Ser. No. 590,188, Oct. 28, 1966. This appheation Apr. 19, IL972, Ser. No. 245,390 Int. Cl. C09b.29136 Claims 10 U.S. Cl. 260-155 8 ABSTRACT OF THE DISCLOSURE Thiazolyl-azo-tetrahydroquinoline compounds in which the nitrogen atom of the tetrahydroquinoline coupling 15 component is substituted with a group having the formula R3 \so2R2 20 ,wherein RI is alkylene and R2 and RI each is alkyl, cycloalkyl or aryl. The disclosed compounds are usdfijl for dyeing hy&ophobic textile materials such as polyest er fibers. 25 T'his application is a continuation of our application Ser. No. 590,188, filed Oct. 28, 1966, for "Azo Compounds for Hydrophobic Fibers," now abandoned This invention relates to certain novel azo col;@ounds and their use as dyes for hydrophobic textile fibers, yarns, 30 and f abries. T'he azo compounds of our invention have the general formula R7 R$ R-N=N R4 Rs 40 S02R2 wherein R represents a 2-thiazolyl gr(yup; 45 R' represents an alkylene group; R2 represents an alkyl group, a cycloalkyl group, or a monocyclic carbocyclic aromatic group of the benzene series; R3 represents an alkyl group or a cycloalkyl group; 50 R4, R5 and R6 are the same or different and elach represents hydrogen or lower alkyl;-and R7 and R8 are the same or different and each represents hydrogen, lower alkyl, lower alkoxy, halogen, or lower alkanoylamido. 55 The compounds of the invention are useful as dyes for hy&ophobic textile materials and, when applied thereto by conventional dyeing techniques, the azo compounds display excerent fastness properties, particularly light fastness. 60 Typical of the 2-thiazolyl groups represented by R are thiazol-2-YI, 5-nitrothia7ol-2-yl, 5-chlorothiazol-2-yl, 65 5-cyanothiazol-2-yl, 5-acetamidothiazol-2-yl, 4-methyl-5-nitrothiazol-2-yl, 4-methyl-5-cyanothiazol-2-yl, 4-methyl-5-methylsulfonylthiazol-2-yl, 70 4-ethoxycarbonylthiazol-2-yl, 5-chlorothiazol-2-YI, etc. Preferred groups represented by R can be characterized by the formula -N (X)-@ AS/ wherein X represents hydrogen, lower alkyl, e.g. methyl, ethyl, butyl; substituted lower alkyl such as haloalkyl, e.g. chloroniethyl, trifluoromethyl, cyanoalkyl, e.g. #cyanoethyl, nitroalkyl, e.g. 6- nitroethyl, hydroxyalkyl, e.g. 6-hydroxyethyl; p-cyanoethoxy, haloalkoxy, e.g. pbromoethoxy; alkoxyalkyl, e.g. p-methc>xyethyl; phenoxy@ alkyl, e.g. 6-phenoxyethyl; lower alkoxy, e.g. methoxy, ethoxy; substituted lower alkoxy such as cyanoalkoxy, e.g. phenylalkoxy, e.g. benzylqxy; lower alkanoylaniido, e.g. ac@ofamido; nitro; hal6gen, 6-g. chloro, bromo; cyano; lower alkylsulfonyl, e.g. methylsulfonyl; substituted lower alkyls,ulfonyl e.g. cyanoethylsulfonyl; carbamoyl; N-lower alkyl carbamo@l, e.g. N,N-dimethylcarbamoyll- hydioxyl; aryl; e.g. phenyl; lower alkanoyl, e.g. formyl; acetyl; benzamido; benzylamino; Nalkylarylamino, e.g. N-,methylphenylamino-I lower alkoxycarbonyl, e.g. ethoxycarbonyl, sulfamoyl; N@lower alkyl sulfamoyl, e.g. N-ethylsulfamoyl; lower alkylsulfonamido,. e.g.. methylsulfonamido; lower dicaib6xyli6acidimid6, e.g. succim'mido; thiocyanato; lower . alk@lthio, e.g. methylthio; combinations thereof; and m represents I or 2. As used in the above description and h6reinafter, the term lower is used in its conventional sense to mean an alkyl moiety having up to about 4 carbon atoms. The alkylene group represented by RI can be straight or branched chain, unsubstituted or substituted alkylene of up to about 8 carbon atoms. Preferably, RI represents a lower alkylene group having up to about 4 carbon atoms. Examples of the alkylene groups represented by RI are ethylene, prgpylene, iso-propylene, n-butylene, see-butyleii6, hexame.thylene, haloalkylene, e.g. 2-chloropropylene, 2-bromo ropylene, chloroethylone, hydroxyalkylene, e.g. p 2-hydr,6xy@iopylene, hydroxyethylene, lower alkanoylOXY41kylen6, eig. 2-acetoxypropylene, etc. The alkyl groups represented by R2 and R3 can contain up to about 8 carbon atoms and can be straight or branch chain, iinsubstituted or substitiit6d. Typical alkyl groups represented by R2 and R3 are methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyll hydroxyzilkyl, i--.g. hydroxyethyl,.polyhydroxyalkyl, e.g. 213-dihydroxypropyl, lower a,lkoiyalkyl, e.g. p-methoxyethyl, nitroalkyl, e.g. Pmtroeth@l, 'cyanoalkyl, e.g. 6-cyanoethyl, cyanoalkoxyalkyl, e.g. 6-cyanoethoxyethyl, lower alkanoyloxyalkyl, e.g. 6- acetoxyethy,l,. lower alkoxycarbonyl, e.g. p-ethoxycar,,, bonylethyl, ha,loalkyl, e.g. 6-chloroethyll gammachloropro@yt,- p-brombethyl, hydroxyhalogenoalkyl, e.g. gammachl6r6-'p-hydroxypropyl, lower alkanoylamidoalkyl, e.g. 6-deetamid6eh 1, carbamoylalkyl, e.g. p-carbomoylethyl, ty N-lower alkylcarbamoylalkyl, e.g. p-N-m ethylcarbamoylethyl, lower alkvlsulfonvlalkyl, e. p-mothylsulfonylethyl, g. lower di6@rl@oxylic acid imidoalkyl, e.g. succinimidgethyl; aryl,.e.g. beiftzyl; benzoyloxy, phenoxyalkyl, eg. ppheox eth lower alkylsulfonamidoalkyl, e.g. methylsuln y y fonamid6eth@l; N@-phenylcarbamoyloxy; etc. The alkyl group iopiese@ted by R2 and R3 are preferably lo@wer alkyl t6 e@@ou the alkyl e.g. tip t 4 carbon atoms. However, when group is gub tituied by a carbon containing substituent, e.g. alkoxy, the preferred substituted alkyl group can contain to. about 8 carbon atoms, e.g. delta-butoxybutyl. UP Es@ecially preferred compounds of the invention are those wherein R2 represents lower alkyl and R3 represents substituted lo@r@i alkyl. R2 and R3 can also represent cycloalkyll ha@i@'@ @@out 5 to 6 carbon atoms such as, for exam- cy6lohexyl. P,,, nie n@onocy,clic carbocyclic aromatic groups of the benzene seri@s r@presented by R2 include, for example, phenyl
[2]31787,388 3 and phenyl substituted with lower alkyl, lower alkoxy, nitro, halogen, etc. Illustrative of such groups are phenyl, p-tolyl, m-nitrophenyl, opdichlorophenyl, and p-anisyl. Typical of the lcywer alkyl groups represented by RI, Rr', R6, R7 and R$ are methyl, ethyl, propyl, isopropyl and butyl. Examples of lower alkoxy groups represented by R7 and R8 are methoxy, ethoxy, and butoxy. Chloro and bromo are typical halogen atoms represented by R7 and R8. Typical lower alkanoylamido groups repres@iited by R7 and R8 are acetamido, propionamido and butyramido. Generally, the groups X, R4, R5@ R6, R7 and R8 and the substituents on the groups represented by RI, R2 and R3 do not materially affect the usefuln6ss of the compounds of the invention as dyes for hydrophobic textile fibers. These groups and substituents function primarily as auxochrome groups to control the shade of the compouiads, the basic color of which is attributable to the thiazol ylazotetrahydroquinoline nucleus as is well known in the art. However, when R3 is substituted alkyl, the compounds of the invention display unexpectedly good fastness to light and sublimation. The azo compo-unds of the invention are prepared by cgupling diazonium salts of 2- aminothiazoles having the formula (11) RNH, with a tetrahydroquinoline coupling components having the formula R7 RC a RI Rs RI S02R2 wherein R, RI, R2, R3, R4, R5, R6, R7 and RB are defined above. PREPARAT'ION OF THE COUPLERS The coupling components having the Formula M are prepared according to methods well known in the art. The following example illustrates one method of preparing the couplers. Example A 3.5 g. (0.025 mol) of 1-(2-chloroethyl)-1,2,3,4-tetrahydro - 2,2,4,7- tetramethylquinoline, 3.5 g. (0.025 mol) N-2-hydrox yethylmethanesulfonamide, 3.5 g. (0.025 mol) potassium carbonate, and 50 cc. of dimethyl formamide are reffuxed together for 2 hours. The reaction mixture is drowned into water, and the product extracted with chloroform. 'ne chloroform is separated and evaporated to give 7.5 g. of thep roduct having the formula cm CH3 OH. 8H@CH2 S02CHS By substituting equimolar quantities of other tetra hydroquinolines and sulfonamides, the couplers conforming to Formula III can be prepared employed the procedure described above. PREPARATION OF THE DYES Example I (a) Diazotization.-2.9 g. of 2-a-mino-5-nitrothiazole are stirred in 60 cc. of water and 32 cc. of @oncentrated sulfuric acid. The resulting solution is cooled to -lo,- C. and a solution of 1.4 g. of NaNO2 in 10 cc. of water 4 is added at -10' C. to-5' C. Stirring at -5' C. is continued for 10 minutes. (b) Coupling.-7.1 g. of the coupler prepared in Example A is dissolved in 100 cc. of 15% aqueous sulfuric acid. The coupling solution is cooled i-n an ice bath and the diazonium solution from Example I (a) is added. After an hour, the mixture is drowned in water, futered, washed with water, and air dried. The product dyes cellulose acetate and polyester fibers a brilhant blue shade 10 having excellent fastness properties. It has the structure: -N CH3 02N@l S@N=N CIL 15 C ClI2cH20H CH2 02CH3 20 Example 2 2.9 g. of 2-amino-5-nitrothiazole are diazotized and coupled with 6.5 g. of the coupler 1-(N-methyl-N-methylsulfonylamino ethyl)-1,2,3,4-tetrahydro - 2,2,4,7 - tetra25 methylquinoline according to the procedure of Example 1 to yield a product which imparts a blue shade to cellulose acetate and polyester fibers. It has the formula 30 -N CHS 02N@l N=N CH3 CII3 35 C 8 02CM Example 3 40 2.9 g. of 2-amino-5-nitrothiazole are diazotized and coupled with 5.94 g. of the coupler 1-(N-methyl -Nm ethylsulfonylaminoethyl) - 1,2,3,4 - tetrahydro-2,7-dimethylquinoline according to the procedure employed in Example 1. The product dyes cellulose acetate and poly45 ester fibers a brilliant blue shade of excellent fastness properties. The dye has the formula -N 50 0,N N CH3 55 CH2CH2N S 02CHS Example 4 2.9 g. of 2-amino-5-nitrothiazole are diazotized and 60 coupled with 6.54 g. of the coupler 1-(N-2-hydroxyethylNmethylsulfonylaminoethyl) - 1,2,3,4 - tetrahydro - 2,7dimethylquinoline according to to the procedure of Example 1. The product obtained gives brilliant blue dyeings on cellulose acetate and polyester fibers having ex65 cellent fastness properties. It has the formula -N ON@s I 70 )-N@N CH@ CH2011. @H2cm 75 S 02CHS
[3]82787,388 5 Example 5 2.9 g. of 2-amino-5-nitrothiazole are diazotized and coupled with 7.94 g. of the coupler 1-(N-2-acetoxyethylN-methylsulfonylaminoethyl) - 1,2,3,4 - tetrahydro-2,2, 4,7- tetra,methylquinoline as described in Example I to 5 yield a product which imparts blue shades to cellulose acetate and polyester fibers of excellent fastness properties. This dye has the formula -N CH3 10 02N@l S@N=N CH3 CI_L CH3cH20OCCHO 15 02CM The compounds set forth in following examples are similarly prepared according to the procedure employed in Example 1. Equimolar quantities (0.02 mol) of the 20 appropriate 2-aminothiazole of Formula II and the appropriate coupling component having Formula III are reacted to yield azo compounds having the formula -N R7 Ra (X) 25 -ts@ N=NRs R8 3o RI S02R, T'he color given for each compound refers to dyeings on polyester fibers. 6 for dyeing such hydrophobic materials, they should be free of water-solubilizing groups such as sulfo and carboxyl. In general, the compounds of the invention have excellent fastness, for example, to light, washing, gas (atmospheric fumes) and sublimation. The compounds display exceptionally good sublimation and light-fastness when used as dyes on polyesters. As described above, the present compounds have the characteristic structure of Formula I. This distinctive structure imparts unexpected properties to the compounds, including the above-described light fastness and sublimation resistance. Thus, we have found the compounds of the invention to possess properties superior to similar but distinct and different compounds when used as dyes and tested by methods such as described in the A.A.T.C. Technical Manual, 1965 edition. The compounds of the invention can be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, acrylic, polyamide, etc., fibers in the manner described in U.S. Pat. 2,880,050, 2,782,187, 2,757,064 and 3,043,827. ' The following example illustrates a method by which the compounds of the invention @an be used to dye poly@ ester textile materials. Example 21 0. 1. 9. of the dye is dissolved in the dye pot by warming in 5 cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium lignin sulfonate aqueous solution is added, with stirring, until a fine emulsion is obtained. Water is then slowly added to a total volume of 200 cc. Then, 3 cc. of "Dacronyx" (a chlorinated benzene emulsion) are added and 10 grams of a textile fabric made of poly(ethylene terephthalate) polyester fibers are entered. The fabric is worked 10 minEx. No. x R7-R8 R4-RsRe Ri R2 R3 Color 6 -------------- 5-NO2 None None - 01120HZ- -0113 -C2HS Blne. 7 -------------- 5-NO2 None None - (CH2)3- -C2]15 -C2H5 Do. 7-OCH3 'H2)3 8 -------------- 5-NO2 2-CH: -((@ - -C2H5 -c2H401 Do. 9 -------------- 5-NO2 7-Cl 2- CH (OH2)3-- -CH2CH20CHs -C2HiO CHs Do. 10 ------------- 5-NO2 5.CHS 2-CEECIE[3 H a -CH2CH201 0 Do. @HB - CH2bn -C2H406cirs 11 ---------- @-- 5-NO2 8-CH3 same as above---- saine as above---- 0 0 Do. -CH2CH206CHS -C2H40 101 COH3 12 ---- - ------- 5-NO2 7-NHCOCHS 2-CIls - CH2C]12- -COH5 -C4Hg Do. 13 ------ ; ------- 5-NO2 7-CHs 2-CH3 - CH2CH2- -C:>-CHS -C4Hg Do. --- z-- -4-OFS 7-CH3 2-CH3 -OH2CH2- -CH3 -C2H40N Violet; 15 ------------- 4-CO2C2H5 7-CH3 2-CHa - CH2CH2- -CH$ 0 Do. -C2II4@, N]12 16 ------------- 4-N]EICOC]13 7-CHs 2-C]E[3 - CH2CE[2- -C]E[3 Oll Do. -C]E[2@HClf2CI 17 ----- ------ 4-Cas 7-Clta 2- CH3 ci -CH3 0 Do. - CE2@ll-CH2- -C2II408NHCXs 15 ------------- 5-01 7-C]13 2-CHs Same as above- -CH3 -C2H4002C2Hs Do. 19 ------------- 4-CHS, 5-COCHs 7-CE[3 2-CH3 - CH2CH2- -OH3 0 Do. I -02114NH6cH3 20 ------------- 5-SO2C4119 7-OH3 2-CH3 - CH2cHT- -CH$ -C2H40N Blue. 21 ------------- 5-CN 7-CH3 2-CH3 - CH2cHr- -CHs -C2H4SO2SHS Do. 22 ------------- 5-SO2CHS 7-CH3 2-CH3 - 0112CH2- -CE3 -C2]E[dSO20HS Do. 23 ------------- B-NO2 7-CH3 2-CHa - CH2CH2- -CHo Do. T'he thiazolylazo compounds of the invention can -be used for dyeing textfle materials, including protein and 70 synthetic polymer fibers, yarn and fabrics, giving a variety of fast brilliant pink to violet shades when applied thereto by conventional dye methods. The compounds have high affinity for cellulose ester, polyester and nylon fibers. When the thiazolylazo compounds are used 75 utes without heat and -then for 10 minutes at 80' C. The dye bath is then brotight to the boil and held at the boil for one hour. Following this, the fabric is rinsed in warm water, then scoured in aqueous 0.2% soap, 0.2% soda ash solution. After scourin,-, the fabric is rinsed with water and dried. When the compounds are used to dye polyamide textile materials, the above described proce-
[4]32787)388 7 dure can be employed except the "Dacronxy" dyeing assistant need not be used. Accordingly, since the thiazolylazo compounds of the invention are water-insoluble, they can be applied from aqueous dispersions in the manner of the so-called "dispersed dyes." However, coloration can also be effected, for example, by incorporatin.- the compounds into the spinning dope and spinning the fiber as usual. The compounds of the invention are not necessarily equivalents when used as dyes. The degree of dye affinity varies, for example, de_pending upon the material being dyed and the formula of the thiazolylazo compound. Thus, for example, all the dyes wiff not have the same degree of affinity for the same material. Polymeric linear poiyester materials of the terephthalate type are illustrative of the linear aromatic polyester textile materials than can be dyed with the new compounds of our invention. Examples of such linear polyester materials are those prepared from ethylene glycol and dimethylterephthalate and those prepared from 1,4- cyclohexanedimethanol and dimethylterephthalate. Polyester textile materials prepared from 1,4-cyclohexanedimethanol and dimethylterephthalate are more particularly described in U.S. Pat. 2,901,446. Poly-(ethylene terephthalate) fibers are described, for example, in U.S. Pat. 2,465,319. The polymeric linear polyester materials disclosed in U.S. Pats. 2,945,010, 2,957,745 and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 2001 C. Examples of the polyamide fibers that can be dyed with the compounds of the invention are those consisting of nylon 66, made by the polymerization of adipic acid and hexamethylenediamine, nylon 6, prepared from epsilonaminocaproic acid lactam, and nylon 8. The invention has been described in considerable 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 as described above and as defined in the appended claims. We
