GB2151651A - Acid dyes from 2-amino-5-heterocycle substituted thiophenes and anilines, tetrahydroquinoline or benzomorpholine couplers - Google Patents
Acid dyes from 2-amino-5-heterocycle substituted thiophenes and anilines, tetrahydroquinoline or benzomorpholine couplers Download PDFInfo
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- GB2151651A GB2151651A GB08333828A GB8333828A GB2151651A GB 2151651 A GB2151651 A GB 2151651A GB 08333828 A GB08333828 A GB 08333828A GB 8333828 A GB8333828 A GB 8333828A GB 2151651 A GB2151651 A GB 2151651A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3686—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing nitrogen and oxygen as heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0059—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only sulfur as heteroatom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
- C09B29/3643—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from quinolines or hydrogenated quinolines
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Abstract
New acid azo dyes of formula I give bright blue to reddish blue shades on polyamide fibers. <IMAGE> in which R is hydrogen, alkyl, -CN, -CO2 alkyl, -CO2H, -NO2, -CONH2, -CONHalkyl, or CON(alkyl)2, any alkyl group or moiety possibly being substituted, C<1> is an aniline, tetrahydroquinoline, or benzomorpholine type azo dye coupler which may be substituted, Het is a heterocyclic radical of thiazole, oxazole, imidazole, benzoxazole, benzothiazole, benzisothiazole, benzimidazole, benzoselenazole, pyrazine, pyrimidine, pyridine, or pyridazine, which may be optionally substituted, and wherein at least one water solubilizing group -SO3M or -SO4M is present in the dye molecule as a substituent on any or all of the various rings thereof, or as a substituent on any of the various substituents on the rings, M being a cation.
Description
SPECIFICATION
Acid dyes from 2 - amino - 5 - heterocycle substituted thiophenes and aniline,tetrahydroquinoline or benzomorpholine couplers
This invention relates to new acid azo dyes prepared from 2 - amino - 5 - heterocycle substituted thiophene compounds and aniline, tetrahydroquinoline and benzomorpholine couplers. These dyes give bright blue to reddish blue shades on synthetic fibers, particularly polyamide fibers, and exhibit improvements in one or more of such properties as bathochromic shift, fastness to light, sublimation, chlorine, heat, ozone, gas, perspiration, crock, and wash, build, pHstability, bloom resistance, depth of shade, leveling, strike rate, and migration.
The new azo compounds have the formula
wherein: R is selected from H, alkyl, -ON, -CO2alkyl, -CONHalkylene-OH, -CO2H, -NO2, -CON H2, -CONHalkyl and-CON(alkyl)2, any alkyl group or moiety possibly being substituted, C1 is an aniline, tetrahydroquinoline orheterocyclic radical which may be substituted. It is noted that at least one water solubilizing group-SO3M or-SO4M is present in the dye molecule benzomorpholine coupler which may be substituted; and "Het" is a heterocyclic radical as specified below, which may be substituted.At least one water solubilizing group -SO3M or-SO4M is present in the dye molecule and can be as a substituent on any or all of the various rings thereof, or as a substituent on any of the various substituents on the rings, and these solubilizing groups are hereby included in the definitions of all ofthe R through R15 groups or substituents defined in detail below.
Mis a cation preferably selected from H+, Na+, K+,
NH4+ and the colorless cations of salts of primary, secondary and tertiary aliphatic amines, such as triethylamine and trimethylamine.
The coupler C' is preferably selected from
wherein:
R1 and R2 are each selected independently from hydrogen,fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula -NH-X-R9 in which Xis -CO-, -COO-, or -SO2-and R9 is selected from alkyl and alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, and when Xis -CO- in the formula -NH-X-R9, R9 is furtherselected from hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, alkoxy substituted arylamino, aryl, a nd fu ryl; R3 and R4 are selected independently from hydrogen; cycloalkyl; cycloalkyl substituted with one or two of alkyl, hydroxy, alkoxy, halogen or hydroxy substituted alkyl; phenyl; phenyl substituted with one or two of alkyl, alkoxy, halogen, alkanoylamino, cyano oralkoxycarbonyl; alkenyl; alkyl; and alkyl substituted with 1-3 of the following independently selected substituents:
hydroxy; halogen; cyano; amino; alkoxy; succinimido (C4H402N-); glutarimido (C5H602N-); pheny
Icarbamoyloxy; phthalimido (C8H402N-); 2-pyrrolidono (C4H6ON-); cyclohexyl; phenoxy; phenyl; phenyl substituted with 1-3 of alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; o-benzoicsulfimido; alkylsulfonamido; benzothiazolylthio; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; aryloxycarbonyl; aroyloxy;alkenylcarbonylamino; arylcarbamoyloxy; groups of the formula
wherein Yis -NH-, -N-alkyl, -O-, -S-, or-CH2O-; -S-R10 wherein R10 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or
-OXR9; -NH-X-R9; -X-R9; -CONR"R11; -SO2NR"R"; wherein R9 and X are as defined above and each R11 is selected from H, alkyl, and alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, alkoxy, aryl, cyano, cycloalkyl, alkylsufonyl, alkylthio, alkanoyl, and alkanoyloxy; alkoxy substituted with 1-3 of hydroxy, cyano, alkanoyloxy, oralkoxy; phenoxy substituted with 1-3 of alkyl, alkoxy or halogen; and R3 and R4 combined to form pentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene which, with the nitrogen atom to which it is attached, forms a ring; and
R5, R6, B7 and R8 are each selected from hydrogen and alkyl. All ofthe above alkyl, alkylene, alkenyl, and alkoxy moieties or substituents within the definitions of Rthrough R11 contain upto six carbons and are straight or branched chain.
Preferred within the above definitions: R3 and R4, are selected from H, and C-C4 alkyl which alkyl is optionally substituted with one to three of-CN, phenyl, succinimido, -OH, -Cl, -000-alkyl, -COOalkyi, -OCH2CH2O-alkyl, -SO3M or-SO4M; R2 is H, C1C4 alkyl orC,-C4alkoxyorthotothe -N: of couplers; R1 is H, C1-C4alkyl, C1-C4 alkoxy, or -NHCO-alkyl meta to the -N of coupler I; R5-R8
are each selected from H and methyl, and wherein
most preferably, at least one of R5-R7 is methyl.
The couplers are prepared by procedures well known in the art as shown in the patent literature, e.g.,
U.S. Patents 2,805,218; 2,827,450; and 2,839,523.
The heterocyclic radicals, "He', useful herein have the formulae
wherein the substituents R12-R15 are independently selected from H, -NO2, -CN, halogen, alkyl, alkoxy, -COOalkyl, -OOCalkyl, -CHO, and -COalkyl, and wherein the alkyl groups and alkyl segments or moieties, e.g., ofthe alkoxy groups, are straight or branched chain of 1-6 carbons and are unsubstituted or substituted with 1-3 of alkoxy, hydroxy, halogen, -CN, -SO2alkyl, -SO2Ph, -OOCalkyl, -COOalkyl, -CO NH2, -CON Halkyl, -OON(alkyl)2, -S-alkyl, -SO2NH2, -SO2NHalkyl, -SO2N(alkyl)2, -S-Ph, -O-Ph, and Ph.
Preferable substituents on these Het rings are H, halogen, alkyl, -OH and -SO3M.
The dyeing of a polyamidefibre with a dye of the
invention may be carried outforexample,from an
aqueous solution in the presence of a leveling agent
at 98"C. for 1 hour. The fibre is then scoured at 50 C.
with soap solution and sodium carbonate. In another
dyeing procedure, the dye compound, 16.7 mg., is dispersed in water or 5 cc. of2-methoxyethanol in a metal beaker. Approximately 1.0% ammonium sul fate owf and 1.5% lrgalev PBFowfis added with sufficient water to give a 30:1 dyebath, the pH adjusted to 6.0 with acetic acid and a 5 g. sample made of the nylon 6 fabric is placed in the dyebath.
The dyebath tem peratu re is brought up to the boil and maintained for one hour. The dyed sample is removed from the dyebath, rinsed in hot filtered water and then cold demineralized water, and then dried at 250 F. 'Irgalev PBF' is a trade mark.
The invention will be understood furtherfrom the following examples.
EXAMPLE I
2 - Amino - 3 - methoxycarbonyl - 5 - benzothiazolyl thiophene (2.9 g) was diazotised using 1:5 acid (1 part propionicto 5 parts acetic byvolume) in the normal fashion, then coupled to a solution of N - ethyl - 2, 2, 4, 7 -tetramethyltetrahydroquinoline in 1:5 acid at 000.
After 1 hour the reaction system was drowned into ice water, filtered and dried to yield 5.1 g of ester dye.
This dye was stirred with ethanolaminein N, N dimethylformamide and the mixture drowned into 10% aqueous sodium sulphate, filtered and dried to yield 4.9 g of amide dye. The amide dye was added slowly to concentrated sulphuric acid at 0-10 C. After stirring for 1 hourthe system was drowned into iced potassium chloride solution, neutralisedto pH 9 with potassium hydroxide solution, filtered, washed and dried to yield 4.8 g of acid dye. The acid dye was applied to the nylon fibre as described above and gave a blue dyeing of good fastness properties.
By application of the synthetic procedures outlined in example (1 ) or others, where appropriate, the following dyes were prepared.
Het R C Shade
I II .- / 2 4 4 i//\ii/\ 1/ 3 2 1 3 9-- CONHC2H SO K 33 Blue 2Hg 2H5 3 H3 3 /COUCH3 CH Reddish Blue \\ /\ \ 3 2H4SCOH43K - C2H5 4 a 8 .- CONHCH3 . \ - Reddish Blue H C2H4SO4K 7/ /SOCH3 5 l - /CONHCH3 -HHC2H5 Reddish Blue CH,o/ 6 nl l /CONHCZH40H I I G Reddish Blue ci( " / 2 4 3 2H45033K 7/ \./ \ 7 1 ,COHHC2H4SO4K CH3 < X \t XCH3 Blue H3 8 / \ XCONH2 33 Reddish Blue 8 \ /\ I 1/ 2H4504K 9 Co CH 3 \ = / NXC H SO K Bluish Red / 2 3 .=. \CZHqS03K Cm 10 C))\/ ,COHHC2 I i Reddish Blue \ 7/\ \ CH3 2H4503K i Reddish Blue 11 tNv \ SCONHCH3 I ii Reddish Blue CR,,3 \\/\ \ CH3 2H4504K 12 . rl \. .# \. / Reddish Blue ONHC2H40H CR,,1 U 3 \\ 7 24 4 13:. rC02CH Bluish Red 13 .) \ \ XC02CH3 Red c2ii S K \ cR,,3 4 'T C2H5 14/cm X s5 / v < NzC2H5 Bluish Red -. N(C2Hs 15 1 < il ,C02CH3 \ - / CZH4SOJK Bluish Red The following tables show additional exemplary dyes of the present invention, wherein the R12-R15 substituents given apply to all of the heterocyclic radicals and represent examples of specific dyes, with the qualification that only the R12-R15 substituents which are possible on the ring apply, as for example, an R14 substituent would not apply to Rings
A, B and J, but the R12 and R13 substituents in that row would, while the R14 substituent in that row would apply to all ofthe other rings.
Table I
R12 R13 R14 R15 R R1 R2 R3 R4 H H H H H H H -CH2CH2SO4K -CH2CH2OOCCH3 2 2 4 2 2 3
NO2 CH2SO4K CN H H F H -CH2CH2Cl -CH2CH2NHCOCH3 CH2SO3Na Cl Cl H CN H Cl -CH2CH2OOCCH3 -CH2CH2COCH3
CH2SO4K CH3 H H CO2CH3 OCH3 OEt -CH2CH2CN -CH2CH2-(NO2C5H6)
OC2H5 H OCH2OCH3 H CO2H C6H11 H -CH2CH2SO4K -CH2CH2COOCH3 H CH2CH2SO4K Br Br 2 NHSO2CH3 OCH3 H H
H H CH2SO3Na OCH3 COHH2 SCH3 H -CH2CH3 -CH2CH2OH 2 3 2 2
COOCH3 H CH2SO3Na H CONHCH3 NHCOCH3 OPh -CH2CH2Br -CH2CH2-(NO2C4H4) OOCC2H5 H CH2SO3Na H CON(C2H5)2 NHCOOCH3 SPh -CH2CH2C6H11 -CH2CH2COOC6H5 CHO H CH2SO3Na H C4H9-n CH3 H -CH2CH2NH2 -CH2CH2-OOCNHPh
COCH3 H COCH3 H C3H7-i NHSO2CH3 OCH3 -CH2CH2OC2H4SO4K -CH2C6H4-p-SO4K
H CH2OCH3 H H H NHCOCH2Cl H -C6H10-4-CH3 -CH2CHCH2-SO3-N+ H(CH3)3
OH
CH2-SO4-N+H(CH3) CH3 CH3 OCH2Cl CO2CH3 NHCOC2H4OH H -C6H9-2,4-di-OH -CH2CH2OH COOCH2CN CH2CH2-SO4-N+(CH3)3 CH3 H CN NHCOCH2OPh H -C6H10-4-OCH3 ., -CH2CH2-NO2C8H4
COCH2SO2CH3 CH2-SO4-N+H(CH3)3 H H CO2CH3 NHCOCH2Ph H -C6H10-4-Cl -CH2CH2-NOC4H6
CH2SO2Ph CH2-SO4-N+H(CH3)3 H H CO2C2H5 NHCOCH2CN H -C6H10-4-CH2OH -CH2CH2COOCH3
CH2CH2-SO4K CH2OCH2OOCCH3 H H CO2C2H5 -CH3 H -Ph -CH2CH2Ph
CH2CH2-SO4K H H CH2COOCH3 CONHC2H4SO4K -CH3 H -CH2CH2OH -CH2CH2C6H11
CH2CH2-SO4K CH2CONH2 H H CO2H -CH3 H -CH2CH2COOCH3 -CH2CH2OOCCH3 CH2CONHCH2-SO3K H H H CN -CH3 H -Ph-p-CH3 -CH2CHCH2SO4K
OH
CH2CH2-SO4K CH2CH2SCH3 Cl H NO2 -CH3 H -Ph-p-OCH3 -CH2CH2CN CH2CH2-SO4K CH2SO2NH2 H CH3 H -NHCONH2 H -Ph-p-Br -CH2CH2Cl
CH2SPh-p-SO3Na CH3 H CH3 CONH2 -CH3 H -CH2CH2SO2CH2CH2
CH2Ph-p-SO4K CH3 H H CONH2 -NHCOCH2C6H11 H -Ph-p-NHOCCH3 -CH2CH2OPh
CH2OPh-p-SO4K H Br Br CONHCH2CH2OH -NHCOCH2SO2CH3 H -Ph-p-CN -CH2CH2CN
CH2CH2-SO3K CH2CH2Cl H H CONHC2H5 -NHCOCH2SCH3 H -CH2CH2OOCCH3 -CH2CH2OOCCH3
CH2CH2-SO3K CH3 CH2OC2H5 H CON(C3H7-n)2 -NHCOCH2OOCCH3 -CH3 -Ph-o-COOCH3 -CH2CH2NHCOCH3
CII2So2MHCH3 CH3 H H COM(C3II7-n)2 -NHCOCH20CH3 -CH3 CH2CH-CH2 -CHtCH3)CH2CH2-504K H H H H CM H -OCH3 H -C6H10-4-So3K 2 H CII H H -CII3 H -CH2CH20CH2CH20H -CH2CH2So2CH2-504M+II(CH3)3 H Cl Cl H H -hHCOH H H -CHsPh-p-504K CH3 CH3 H H CM -MHCOHH2 H CH2CHg504K -CH2CH20CH3 OC2H5 H H CO CII -hHCOCHCH2 H CII2CH2-So4K -CHCH tH,Ca,CH,CH, H H Br Br COCH -HHCOhHCH3 H CII2CH2-So4K - -C,H-CHfCH(CH3)2 H H H OCH3 No2 -hHCOh(C2H5)2 H CH2CHpSOP -CH2SHH(CH2)H20W COOCH3 H H H CONH2 -MHCOMHPh H CH2CII2-So4K -CH(CHdtHH3 OOCC H H Br H COMHCH3 -ligCOPh CH3 CH2CH2-So4K -C6H11 CHO H Br H CCM(C2II5)2 -hHCOfuryl H CH2CH2-So4K -CH2CH2s-1UH COCH3 H COCH3 H C4Hg-n H H -CHfS 4h HtCH3)3 -CH2So2NHC II 33 H COCH1 H 25,, II CHCHJ 3 H H C3II7-l H H -CH2-504H H(CH3)3 -CH2CH2S0211H2 33 CH3 CH3 CH3 OCH2Cl H H H -CH2CII2-504K -CH2CsHS COOCII2CM H CH3 H COUCH3 H H -CH2CH2-504K -Ph COCII2So2CH3 H H H CM H H -CH2CH2-So4K -EH2CH2SCH3 CH2S02Ph H H II EQCH3 H H H -CH2CII2-504K -CH2CH2COOCH3 H CH20CH2WCCH3 H H CO2C2H5 H H -tH2CH2-SD41( -CH2CH(OH)CH20H CH3 H H eH2EMH3 CO2C2II5 H II 5H2EH2S0 -CH2CH2-(C4H402H) CH3 CH2COIIH2 H H CCMH2 H H C 2C -CH2CH2-So4K -CH2CH20Ph-p-Cl CH2COnHCH3 H H H CO2II H H -CH2CH2-So4K -CH2CH20502CH3 2 3 CH3 CH2CH2SCH3 Cl H CII H H -CH2CHfS04K -CH2CH2OOCCH3 CH3 CH2502NH2 H CH3 No2 H H -CII2CII2 -SO K -W2CEWCsH5H 3 4 65 tH2SPh CH3 H CH3 H H H -CH2CHfSO4K -CH2CH2SO2CH3 CBPh CH3 H H COMH2 H H -CH2CH2OOCCII3 -CH2CH200CCH2-503H CBOPh-p-SOqK H er Br COSH2 H . H -CH2CH2502CH2CH2 CH2-So4K CH2CH2CI H H CCMHC2H5 Cl C1 H -CH2CH20CH2CH2Ch CH -SO K CH3 CH20C2H5 H COIIHC2H5 CH3 H -CH2CH3 -CHCII(OOCCH)CHOOCCII 2 4 3 2 25 25 3 2 3 2323 CII2So2MHCH2So4K CH3 H H COM(C3H7-n)2 CH3 H -CH2CH3 -C2cH3 H H H H COM(C3II7-n)2 CH3 H -CH2CH2-So4K -CH2CH20Ph Mo2 H CM H CM CH3 H .CH2CH2-So4K -CH2CH2So2MH2 H Cl C1 H H CH3 H -CH2CHS504K -CH2CH21tH2 22 222 CH3 CH3 H H H CH3 H -CH2CH2-504K -CH2CH2hH2 OC2H5 H H H CM hHCOCH3 H -CH2CH2-504K C 2 3 H H Br Br CO2CH3 MHCOCII H -CH2CH2-504K -CH2CH2WCCH3 3 22 22 H H H OCH3 W2H HHCOCH3 H -CII2CII2-So4K -(CH2CH20)2CH2CH3 COOCH3 H H H NO2 hHCOC6H5 H -CH2CH2-504K -CII2CII2CCMH2 oOCC2H5 H Br H CCMH2 WHCOCsH5 CH3 CH2CII2-So4K -CH2CH2tlH502CH3 CMo H Br H CONCH3 hHCOCH3 OCH3 -CH2CII2-So4K -CH2EH2llmOPh COCH3 H COCH3 H COh(C2H5)2 hHCOCH3 OCH3 -CH2CHiSOE -CII2CH2COOCH3 II CH2CCII3 II H H c4H9-n NHCOCH3 ECHO -CII CII 2 f 4 -CH2CH(oH)CH3 3 2 2 4 2 3 CH3 CH3 CH3 W2C1 C3H7-4 hHCOCH3 OCH3 -CH2CH20H -CH2CH20H COOCH2CN H CH3 H H MeCOCH3 OCH3 -CH2CH20COCH3 -CII2CH2CCOCH2-So4K COCH2502CH3 H H 2 H CO2CII3 MeCOCH3 OCH3 -CH2CH3 C6H10-4-So4K tH2S02Ph H H H CM hHCOCH3 H -CH2CH3 -CH2CH200CI(HPh-p-SOql( H CH2CCII2OCCCH3 H H 2 3 MOOCH3 H -CH2CII2-So4K - ihrI ./ CH2CII2S\/ Table 11
R12 R13 R14 R15 R R1,R2,R5,R6,R7,R8 R3
tH2CH2SOE H H H H 2,7-dt-CII3 -C2II4OH Mo II CM II H H 2,5-dl-CHf8-OCH3 -CHsH(OH)CH2-503H 2 3 3 2 2 3 CH2-So4K Cl Cl H CM 2.2.4,7-tetra-CII3 -C2Hqtam2 CHfSO4K K CH3 H H CO2CH3 2,2,4-tri-CH -C2H4NHCOCHfSO4K 4 3 24 2 4 OE2H4SOP H H H H CO2II 2-CH3-?-M4COCH3 -C2II4CM 0C2II4-So K H Br Br Mo2 Z2s4-tr1-CHf7-NHCOCH3 -C 2II4C1 OC2HPOE H H OCH3 CONH2 2-CII(CH3)2-7-MCoCH3 -C2II4COOCII3 COCCII2-So H H H II COMaCH3 7-CH3 -C II CC II 4 24 25 EOCC2II4So4K H H H H COM(C2H5)2 3.7-dt-CII3 -C2H4COtlHC2H5 CHO H H H C4II9-n 7-CH3 -C2H4COHHC2H4-504H H( 3)3 CCCH2-SC4K H CINCH II C3II7-i 7-CH3 -C 2II4COaMHCII C II -p-So4K H CHZOCH3 H H H H 7-CH3 -C2H400COC2H4-504K CII2-So3K CH3 CH3 UH2C1 CO2CH3 2,2,4-d-CHfS,8-d1-OCH3 -rH41*TOQCH2 COOCH2C'4 H CH3 OCH2C1 CM 2,2,4-tr-CHfB-OCH3 -CII C H -p-SoM+H(CII ) 264 4 3B CCCII2So2CII2-So H II H II C02CH3 2-CH3-7-MHCOCH3 -C2II4COlCII OH CH2502Ph H H H 2H5 7-CH3 -CII -CoHIIC2H4-So4k H CH20CH200CH3 H II CO2C2H5 2,7-d-CH3 -C2H4050 3 CII2-So3Ma H CH3 CH2COOCH3 COMIIC2H4So 4K 2,5-di-CH3-OCII3 -C2H4502'4H2 CII2-So3Ma CH2COIIH2 H H Co2II 2,2.4.7-tetra-CH3 -C So2C II 25 CH2COIIHCH3 H H H CM 2,2,4-tr-CH3 -C2H45CHfS04K 2CH2-So3Ma CII2CH2SCH3 Cl II Mo2 2-HJ7-mOCH3H,CH,S-4 CH CH -SO So tH2S021HZ H II CH3 H 2,2,4-trt-CII3-7-MCOCH3 CII2SPh-p-So4K CH3 H CH3 COSH2 2,2,4-trl-CHf7-NHCOC2H5 -C2II5 CII2Ph-p-So4K CH3 H H COSH2 2-CH(CHI2-7-IMMKH1 -EH2tHZICIJUL CM2oPh-p-So4K H Br Br CBMHH2CII2OH 7-CH3 -C284 * CO-'4-CH ' CH2 4Ma CII2CII2Cl H H CO-C2H5 7-CII3 C2H4iH2 3 CH2-So4Ma CH3 CH20C2H5 H CO!4(C3Hfn) 7-CH3 -CH2,CHCH20H M"CC.t C25 211CH2-5 4K CH3 H H COM(C3H7-n)2 7-CH -C2H4-1 < | CH2-So4K H H H CM 7-CH3 MO CII -So K CII H H 2s2.4-trl-CHf5aB-dl-OCH3 -C H2 2 CH2-SO 24 3 3 2.2.-trisHJs,sdiOCHJ 2422 H Cl Cl H H 2.2,4-trl-CII3-B-OCII3 -C2II4-6H3p-So4K ,CO- H CH2-So3Ma CH3 H H CM 2-CH3-7-NHCoCH3 -C2H4-1( H2 OC2-$" II H II CC2CII3 7-CII3 JOCH2 "'CCCII"
SO K H H Br Br CC2H 2,7-dl-CH3 -C2H4-X504K CH2-504K H H OCH3 h 2 25-dl-CH3-B-UH3 I(co;;t COOCH-50311a H H H CONY2 2,2,4,7-tetr-CH3 -C2HiS?CktHL OOCC H4-503ha H Br H COIIHCH3 2,2.4-tri-CII3 -t2HI- 'EH2 CHO H H H COIItC H ) 2~CHf7-11HCOCH3 -C2H4Hcy Ai-504K COCHZ-S05 K COCH -504ha H COCH3 H C4Hg-n 2g2b4-trl-CHf7-NHCOCH3 -C2H4hllC 4 CH2-S04K CH20CH3 H H C3II7-i 2-eH(CH3)2-7.IHCOCH3 -CHZCHZ-S-IH CH3 CH3 CH3 OCHIEI H 7-CH3 -CH2CHfl( ç 4 COOCII2CM K CII3 II CO2CII3 7-CH3 -C2H40H COCII2So2CII2-So H H H II CM 7-CH3 -CII2CH2 CII2SC2Ph-p-So4K H H H C02CH3 2,2,4,7-tetra-CH3 -CH2CH2ss011Ho ~.
94 CH20tHZWCCH3 II II C02C2II5 2 2 5 2,2,4,7-tetra-CH3 < Table III
R12 R13 R14 R15 R R1,R2,R5 R3
H H H H H 3,6-di-CH3 -C2H4SO3K
NO2 CH2CH2-SO4-N+H(CH3)3 CN H H 3-CH3 -CH2CH(OH)CH2OH
CH2-SO4K Cl Cl H CN 3-CH3-6-NHCOCH3 -C2H4CONH2
CH2-SO4K CH3 H H CO2CH3 6-NHCOCH3 -C2H4NHCOCH3
OC2H4-SO3Na H H H CO2H 3,6-di-CH3 -C2H4CN
OC2H4-SO3Na H Br Br NO2 3-CH3 -C2H4Cl
OC2H4-SO3Na H H OCH3 CONH2 3-CH3-6-NHCOCH3 -C2H4OOCC2H6
COOCH2-SO4K H H H CONHCH3 6-NHCOCH3 -C2H4OC2H5
OOCC2H5 H H H CON(C2H5)2 3,6-di-CH3 -C2H4CONHC2H4-SO4K
CHO H Br H C4H9-n 3-CH3 -C2H4CONHC2H4-SO4K
COCH3 H COCH3 H C3H7-i 3-CH3-6-NHCOCH3 -C2H4CONHCH2C6H4-p-SO4K
II CHtOCHJ H H H H 6-HOCOCH3 -C2H4CCCC2II4 -So4K CH2-503Ra CH3 CH3 OCBCI C02CH3 3,6-di-CH3 -C2II4MHCCCIICH2 COOCH2C H CH3 H CM 3-CH3 -CII2C6H4p-So3Ma COCH2502CH2-504K H H H CC2CII3 3-CH3-6-NHCOCH3 -C2H4CollHCH20H CH250 Ph-p-SO Ha H H H C02C2H5 6-HaCOCH3 -C3H6hHCOHHC2H5 CII2CII2-So4K CH20m,OOCCH, 2 2 3 H HH II tOZt2Hg 3,6-di-CH3 -C2H5 CII2CII2 4 H H CII2COCCII3 CCMHC2H4So4K 3-CH3 -C2II4So2MH2 CH2CII2-So4K CH2COhH2 H H CC2H 3-CH3-6-NHCUH3 -C2H4SO2MHC2II5 CH2CEMaCII2-So4C H H H CM 6-hHCOCH3 -C2HSCII3 ""'\ / CHfS0311a CH2CH25CH3 CI H Mo2 3,6-di-CH3 2 2 tS CH2-SO1Wa CH2S02WH2 H CH3 H 3-CH3 -CH2CH2-5-H CII SPh-p-SO K CH3 H CH3 CCMH 3 -6-MaCOCH 3 2 2 CII 2 4 3 3 2 3 3 2 2 \Ca2 CH2Ph-p-504K CH3 H H CONY2 6-hHCOCH3 C2II4C\ 2 CO~lt-CH2-SO4Ks CH20Ph H Br Br CONHCH2CH20H 3,6-di-CH3 2 CO-M-CH2-So4K' CH2-So K CII2CII Cl H H UmHC2H5 3-CH3 ~ -CH2cHCH20H 4 2 5 2bII 2 CII2-So4K CH3 CH20C2H5 H CWI(C3H7-n) 3-CH3-BMCOCH3 < OO-N2 CH2So2MHCII2 3Ha 3 H H CMI(C3H7.n)Z 6-lHCOCH3 -t24-./tO-FHZ CCCII CH250211HCH2-503Na H H H CII 3,6-di-CH3 (COC > 2 2 H CM H H 3-CH3 -C2II4-6II3-p-So3Ma - C1 C1 H a-cq-cmrom, -c,l CC-NH CH2-So4C CI Cl II 3-CII3-6MCBCII3 C2II4.0[ CCCII CII SO K CH3 H H 6-llHCOCH3 -CZH TOCH2 OC2H5 H H II 3 3,6-di-CH3 -C2H4-X~504 5C,,'\,/i CH2-So4K H Br Br CC2II 3-CII3 CH2-So4K H H OCH3 MO2 3-CH3-6-MHCCCH3 -C2H4-S!C COCCII2-So3Ma H H H COIIH2 6-NeCOCH3 2 t(COjH2 OOCC H -So Ma H H H CCMHCII 3,6-di-CH3 -C2H41lHC\ 24 3 3 3 2 4 \ CMo H II II COM(C2H5)2 3-CII3 5)2 3 C 3 -CCII2-So4K CCCII -SO K H COCH3 H C4Hg-n 3-CH3-6-hHCOCH3 -CH2CH2~5-5pH 2 4 3 4s 3 3 2 2
/Ccx CH20tH3 3 H H C3II7-i 6-hHCOCH3 -CH2CH CH2-So4K CH3 CH3 CCH2CI II 3.6-dl-CH3 -C2H40H Ma COOCH2CH H CII3 H CC2CII3 3-CH3 -CH2CH2- 2 I 3 ft/ CUH2502CH3 H H H CII 3,6-di-CH3 -CH2CH28CNH > . -504K I.
-CII CII .\-SO K CH2S02Ph H II H C02C 3 3,6-d1-CH3 -CH2CH/1 H I 4
Claims (19)
1. A compound having the formula
in which R is selected from hydrogen, -ON, -002- alkyl, -CO2H, -NO2, -CONH2, -CONHalkyl, and
CON(alkyl)2 any alkyl group or moiety possibly being substituted, Cl is an aniline, tetrahydroquinoline, or benzomorpholinetype azo dyecouplerwhich may be substituted, Het is a heterocyclic radical ofthiazole, oxazole, imidazole, benzoxazole, benzothiazole, benzisothiazole, benzimidazole, benzoselenazole, pyrazine, pyrimidine, pyridine, or pyridazine, which may be optionally substituted, and wherein at least one water solubilizing group-SO3M or-SO4M is present in the dye molecule as a substituenton any or all of the various rings thereof, or as a substituent on any of the various substituents on the rings, M being a cation.
2. A compound of Claim 1 wherein the coupler hastheformula
wherein:
R' and R2 are each selected from hydrogen, fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula -NH-X-R9 in which Xis -CO-, -COO-, or-SO2and R9 is selected from alkyl and alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, or alkoxy, and when Xis -CO- in the formula -NH-X-R9, R9 also can be hydrogen, amino, alkenyl, alkylamino, dialkylamino, arylamino, alkoxy substituted arylamino, aryl, orfuryl;; R3 and R4 are selected from hydrogen; cycloalkyl; cycloalkyl substituted with one ortwo groups selected from alkyl,-OH, alkoxy, halogen and hyd roxy substituted alkyl; phenyl or phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; straight or branched alkenyl; straight or branched alkyl and such alkyl substituted with 1-3ofthefollowing: hydroxy; halogen; cyano; amino; alkoxy; hydroxyalkoxy; succinimido; glutarimido; phenylcarbamoyloxy; phthalimido; phthalimidino; 2-pyrrolidono; cyclohexyl; phenoxy; phenyl orphenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; o-benzoicsulfimido; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; ary loxycarbonyl; aroyloxy; alkenylcarbonylamino; arylcarbamoyloxy; groups of the formula
wherein Y is -NH-, -N-alkyl, -O-, -S-, or-OH2O-; -S-B10 wherein R10 is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, akanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or
-OXR9; -NH-X-R9; -X-R9; -CONB11 B11; -SO2NR11R11; wherein R9 and X are as defined above and each B11 is selected from H, alkyl, and alkyl substituted with 1-3 of halogen, hydroxy, phenoxy, alkoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyl, and alkanoyloxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy substituted with one or more of alkyl, alkoxy or halogen; or R3 and R4 combined form pentamethylene, ethyleneoxyethylene or ethylenesulfonylethylene which, with the nitrogen atom to which it is attached, forms a ring; and
R5, R6,R7and B0 are each selected from hydrogen and alkyl.
3. A compound of Claim 1 wherein the coupler has one of the formulas
wherein R1 is alkyl, alkoxy, alkanoylamino, or alkoxycar- bonylamino;
R2 is hydrogen, alkyl, or alkoxy; R3 and R4 are the same or different and selected from hydrogen, alkyl and alkyl substituted with hydroxy, alkoxy, alkoxyalkoxy, hydroxyalkoxy, carbamoyl, alkylcarbamoyl, alkanoylamino, phenyl, cyclohexyl, 2-pyrrolidono, phthalimidino, succinimido, cyano, phenoxy, alkylsulfonyl, phthalimido, o-benzoicsulfimido, triazolylthio, alkylsulfonamido, -SO2NHR11, phenylsulfonamido, alkoxycarbonylamino, alkylcarbamoyloxy, alkoxycarbonyl, alkoxycar- bonyloxy,
R5 and R7 are each hydrogen oralkyl.
4. A compound according to any of Claims 1,2 or 3 wherein the heterocyclic radical has the formula
wherein the substituents R'2-Rr5 are independently selected from H,-NO2,-CN,halogen,alkyl,alkoxy, -COOalkyl, -OOCalkyl, -CHO, and -COalkyl, and wherein the alkyl groups and alkyl segments or
moieties, e.g., of the alkoxy groups, are unsubstituted
or substituted with 1-3 of alkoxy, halogen, -CN, -SO2alkyI, -SO2Ph, -OOCalkyl, -COOalkyl, -CONH2, -CONHalkyl, -CON(alkyl)2, -S-alkyl, -SO2NH2,
-SO2NHalkyl, -SO2N(alkyl)2, -S-Ph, -O-Ph, and Ph.
5. A compound according to any of Claims 1,2,3 or4wherein R'2-R15 are independently selected from -H, -Cl, -NO2, and -CO2CH3, and R is H, -CN, -CO2CH3, -NO2, -CONH2, or-CONHCH3.
6. The compound according to Claim 1 having the formula
7. The compound according to Claim 1 having the formula
8. A compound according to Claim 1 having the formula
9. A compound according to Claim 1 having the formula
10. A compound according to Claim 1 having the formula
11. The compound according to Claim 1 having the formula
12. Thecompound according to Claim 1 having the formula
13. The compound according to Claim 1 having the formula
14. The compound according to Claim 1 having the formula
15. The compound according to Claim 1@ 1 having the formula
16. A compound according to Claim 1 having the formula
17. The compound according to Claim 1 having the formula
18. Thecompound accordingto Claim 1 having the formula
19. Acompound according to Claim 1 havingthe formula
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08333828A GB2151651B (en) | 1983-12-20 | 1983-12-20 | Acid dyes from 2-amino-5-heterocycle substituted thiophenes and aniline, tetrahydroquinoline or benzomorpholine couplers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08333828A GB2151651B (en) | 1983-12-20 | 1983-12-20 | Acid dyes from 2-amino-5-heterocycle substituted thiophenes and aniline, tetrahydroquinoline or benzomorpholine couplers |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8333828D0 GB8333828D0 (en) | 1984-02-01 |
| GB2151651A true GB2151651A (en) | 1985-07-24 |
| GB2151651B GB2151651B (en) | 1987-08-26 |
Family
ID=10553530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08333828A Expired GB2151651B (en) | 1983-12-20 | 1983-12-20 | Acid dyes from 2-amino-5-heterocycle substituted thiophenes and aniline, tetrahydroquinoline or benzomorpholine couplers |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2151651B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0335234A2 (en) * | 1988-03-29 | 1989-10-04 | BASF Aktiengesellschaft | Azo isoathiazole dyes |
| US5071968A (en) * | 1989-03-06 | 1991-12-10 | Ciba-Geigy Corporation | Azo dyes containing a 7-sulfoalkanoylamino-1,2,3,4-tetrahydroquinoline coupling component |
-
1983
- 1983-12-20 GB GB08333828A patent/GB2151651B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0335234A2 (en) * | 1988-03-29 | 1989-10-04 | BASF Aktiengesellschaft | Azo isoathiazole dyes |
| EP0335234A3 (en) * | 1988-03-29 | 1990-01-17 | Basf Aktiengesellschaft | Azo isoathiazole dyes |
| US4960873A (en) * | 1988-03-29 | 1990-10-02 | Basf Aktiengesellschaft | 3-pyridylisothiazoleazo compounds useful as disperse dyes |
| US5071968A (en) * | 1989-03-06 | 1991-12-10 | Ciba-Geigy Corporation | Azo dyes containing a 7-sulfoalkanoylamino-1,2,3,4-tetrahydroquinoline coupling component |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8333828D0 (en) | 1984-02-01 |
| GB2151651B (en) | 1987-08-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19921220 |