US2136135A - Pseudo-azimido-benzene-amino-acyloacetic acid esters - Google Patents
Pseudo-azimido-benzene-amino-acyloacetic acid esters Download PDFInfo
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- US2136135A US2136135A US153279A US15327937A US2136135A US 2136135 A US2136135 A US 2136135A US 153279 A US153279 A US 153279A US 15327937 A US15327937 A US 15327937A US 2136135 A US2136135 A US 2136135A
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- amino
- pseudo
- phenyl
- azimidobenzene
- benzene
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- 150000002148 esters Chemical class 0.000 title description 4
- 239000002253 acid Substances 0.000 title description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000000835 fiber Substances 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 9
- 239000003518 caustics Substances 0.000 description 8
- 150000008049 diazo compounds Chemical class 0.000 description 8
- -1 phenyl pseudo-azimidobenzene Chemical compound 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 235000013311 vegetables Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000007859 condensation product Substances 0.000 description 6
- 229940093858 ethyl acetoacetate Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000002790 naphthalenes Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YKYIFUROKBDHCY-ONEGZZNKSA-N (e)-4-ethoxy-1,1,1-trifluorobut-3-en-2-one Chemical group CCO\C=C\C(=O)C(F)(F)F YKYIFUROKBDHCY-ONEGZZNKSA-N 0.000 description 2
- PFRYFZZSECNQOL-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)diazenyl]aniline Chemical compound C1=C(N)C(C)=CC(N=NC=2C(=CC=CC=2)C)=C1 PFRYFZZSECNQOL-UHFFFAOYSA-N 0.000 description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CXNVOWPRHWWCQR-UHFFFAOYSA-N p-chloro-o-methylaniline Natural products CC1=CC(Cl)=CC=C1N CXNVOWPRHWWCQR-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- BQDAFHDHPLPCLC-UHFFFAOYSA-N 2-methoxy-4-phenyldiazenylaniline Chemical compound C1=C(N)C(OC)=CC(N=NC=2C=CC=CC=2)=C1 BQDAFHDHPLPCLC-UHFFFAOYSA-N 0.000 description 1
- DLURHXYXQYMPLT-UHFFFAOYSA-N 2-nitro-p-toluidine Chemical compound CC1=CC=C(N)C([N+]([O-])=O)=C1 DLURHXYXQYMPLT-UHFFFAOYSA-N 0.000 description 1
- PKUPAJQAJXVUEK-UHFFFAOYSA-N 2-phenoxyacetyl chloride Chemical compound ClC(=O)COC1=CC=CC=C1 PKUPAJQAJXVUEK-UHFFFAOYSA-N 0.000 description 1
- PBGKNXWGYQPUJK-UHFFFAOYSA-N 4-chloro-2-nitroaniline Chemical compound NC1=CC=C(Cl)C=C1[N+]([O-])=O PBGKNXWGYQPUJK-UHFFFAOYSA-N 0.000 description 1
- WRZOMWDJOLIVQP-UHFFFAOYSA-N 5-Chloro-ortho-toluidine Chemical compound CC1=CC=C(Cl)C=C1N WRZOMWDJOLIVQP-UHFFFAOYSA-N 0.000 description 1
- WOBMMZXAGSQVCE-UHFFFAOYSA-N 6-methyl-1-nitrocyclohexa-2,4-dien-1-amine Chemical compound CC1C=CC=CC1(N)[N+]([O-])=O WOBMMZXAGSQVCE-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- ICHNIWWYEHETFJ-UHFFFAOYSA-N bis(4-methoxyphenyl)diazene Chemical compound C1=CC(OC)=CC=C1N=NC1=CC=C(OC)C=C1 ICHNIWWYEHETFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- SHLTXWFNRJQZTQ-UHFFFAOYSA-N n-chloro-2-methylaniline Chemical class CC1=CC=CC=C1NCl SHLTXWFNRJQZTQ-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
Definitions
- the present invention relates to new arylides of Ji-ketone-carboxylic acids which are valuable intermediate products for the manufacture of dyestuffs. It comprises the new arylides, the
- R. stands for an aryl radical of the benzene or naphthalene series such as the 5-amino- 2-phenyl-pseudo-azimidobenzene, the 5 -'ain'ino 6-methyl-2-phenyl-pseudo azimidobenzene, the 5-amino-2-(4'-methoxy) -phenyl-p'seudo azimidobenzene, the 5-amino-2(4- ethoxy) phenylpseudo-azimidobenzene, the 5-ami'no-6-methy1- 2- (4'-methoxy) -phenyl-pseudo azimidobenzene, the 5-amino-6-methyl 2 -"(4'- ethoxy) -p-henylp
- arylides thus correspond to the general formula in which R stands for a member of the group consisting of aryl nuclei of the benzene and naphthalene series, R1 stands for a member of the group consisting of methyl and phenyl, and y stands for a member of the group consisting of H, CH3 and O-alkyl.
- R stands for a member of the group consisting of aryl nuclei of the benzene and naphthalene series
- R1 stands for a member of the group consisting of methyl and phenyl
- y stands for a member of the group consisting of H, CH3 and O-alkyl.
- R stands for a member of the group consisting of aryl nuclei of the benzene and naphthalene series
- R1 stands for a member of the group consisting of methyl and phenyl
- y stands for a member of the group consisting of H, CH3 and O-alkyl
- the new arylides which represent valuable intermediate products for the manufacture of dyestuffs, dissolve in aqueous caustic alkalies owing to the presence of the -COCH2CO- group.
- the alkali salts of the new arylides possess a marked affinity for the Vegetable fiber, which is entirely surprising, since the similar arylides from the isomeric amino-azimides do not possess such an afiinity for the vegetable fiber.
- azo-dyestuffs Since they combine with diazo compounds to azo-dyestuffs they are inter alia very suitable for the production of azo-dyestuffs on the vegetable fiber (cotton, ram-ie, flax, jute and the like) as well as on regenerated cellulose (viscose or cuprammonium silk), and also on animal fibers such as wool, natural silk or loaded silk, according to the methods usual in dyeing with ice colours.
- Such methods are, for example, padding the fiber in an alkaline solution of the new arylide and developing with a diazo compound, preferably one containing no hydroxy-, carb'oxyor sulfo-groups.
- Such diazo-compounds are, for instance, those derived from aniline, ethers or esters of amino-phenols, for example orthoor para-anisidine, 4-chloroZ-amino-diphenylether, 4:4'-dichloro-2-aminodiphenylether; those derived from monoacylated products from 2:5-diaminohydro-quinone-diethylor -dimethy1ether and benzoylchloride or phenoxy-acetic-acidchloride; aminoazo dyestuffs, for instance, 4- amino-5-methoxyazobenzene, l-amin'o 2:5 dimethoxyazobenzene, ortho-amino-azo toluene; further those derived from chlorotoluidines, for instance l-chloro-2-methyl-l-aminobenzene, 4- chloro-1-methyl-2-aminobenzene; those from ni-' tranalines such as ortho
- preparations or printing colors containing them may also be prepared which contain an alkali salt of the new derivatives and a stabilized diam-compound in the form of a nitrosamine or of a diazoamino-compound.
- These preparations may be printed on the fiber and then developed to dyestuifs by suitable treatment, for example by passage through an acid. It is also possible to print mixtures of the free diazotizing components or the corresponding Nnitramines and alkali salts of the new coupling components on the fiber and to convert such mixture into dyestufis by development with nitrous acid, and, if desired, subsequent treatment in alkali.
- dyestuffs which are derived from ortho-hydroxylated or ortho-carboxylated diazoare added gradually 15 parts of ethylacetoacetate. Condensation is continued for 2 hours, during which time the alcohol formed and some chlorobenzene are distilled. When condensation is complete, the mass is cooled, the chlorobenzene is distilled in steam and the condensation prodnot left behind is filtered; it is dissolved in dilute caustic alkali lye and, after filtration from some impurities, the solution is treated with dilute hydrochloric acid to reprecipitate the condensation product.
- dobenzene +5-amino-6-ch1oro-2-phenyl-psoudo-azimidobenzene Alcohol 185 0. Do +5-am1n0-6-met y1- )mapllthyl-pseudo-azimidobenzene Ohlorobenzene 209 C. Benzoyl acetic ester. +5-am1no-2-phenyl-pseudo-azimidobenzene Alcohol 180 C. Terephthaloyl-diacetic ester ..do 7 Alcohol 280 0.
- compounds as these products may be converted in substance or on the fiber into metalliferous dyestuffs.
- Example 1 21 parts of 5-amino-2-phenyl-pseudo azimidobenzene are introduced into 200 parts of chlorobenzene, a few drops of diethylaniline are added and the whole is heated to boiling under reflux.
- Example 2 13.87 parts of ortho-nitraniline are diazotized as usual and the product is introduced into a solution of 29.4 parts of the condensation product from 5-amino-2-pheny1-pseudo-azimidobenzene and ethylacetoacetate, 100 parts of sodium hydroxide solution of 36 B., 1 5 parts sodium acetate and 2000 parts of 'water. The yellow dyestuff formed is precipitated immediately; it is filtered and dried.
- Cotton yarn is impregnated with a grounding prepared by dissolving 3 parts of the condensation product from 5aminophenyl-pseudo-azimidobenzene and ethylacetoacetate in 300 parts of hot water with the addition of 6 parts sodium hydroxide solution of 30 per cent. strength, 10 parts of Turkey red oil, parts of sodium chloride, and water to make up 1000 parts.
- the goods are then wrung out and developed in a diazo-solution which has been neutralized with sodium acetate and acidified with acetic acid, and corresponds with 2 parts of 1-amino-2- methyl-l-nitrobenzene per 1000 parts. There is produced a pure greenish-yellow of very good properties of fastness.
- Similar tints are obtained with other diazocomponents, for instance 1-amino-2-methyl-4- chlorobenzene, 1-amino-2-nitro-4-chlorobenzene, 1-amino-2-nitro-4-methylbenzene.
- Redder tints are obtained for instance with l-amino-Z-nitrol-methoxybenzene or ortho-aminoa'zotoluene.
- the goods may also be grounded at a raised temperature, for instance at 80 C.; such arylides may also be used for printing.
- the following table comprises a number of for the Vegetable fiber, and react with diazo cominvention pounds with formation of azo-dyestufis.
- arylides of the general formula in which the alkyl-group contains not more than 2 carbon atoms and in which :1 stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies; from which solutions they possess afiinity for the vegetable fiber, and react with diazo compounds with formation of azo-dyestuffs.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
Patented Nov. 8, 1938 UNITED STATES 2,136,135 PSEUDO-AZllVlIDO-BENZENE-AMINO ACYL- OAGETIG ACID ESTERS Hans Johner and Gerald Bonhote, Basel, Switzerland, assignors to the firm Society of Chemical Industry in Basle, Basel, Switzerland 1 8 Claims.
The present invention relates to new arylides of Ji-ketone-carboxylic acids which are valuable intermediate products for the manufacture of dyestuffs. It comprises the new arylides, the
process of producing the same as well as their application for the manufacture of dyestuffs.
It has been found that valuable arylides of piketone-carboxylic acids may be obtained if amino compounds of the general'formula in which R. stands for an aryl radical of the benzene or naphthalene series such as the 5-amino- 2-phenyl-pseudo-azimidobenzene, the 5 -'ain'ino 6-methyl-2-phenyl-pseudo azimidobenzene, the 5-amino-2-(4'-methoxy) -phenyl-p'seudo azimidobenzene, the 5-amino-2(4- ethoxy) phenylpseudo-azimidobenzene, the 5-ami'no-6-methy1- 2- (4'-methoxy) -phenyl-pseudo azimidobenzene, the 5-amino-6-methyl 2 -"(4'- ethoxy) -p-henylpseudo-azimidobenzene, the 5-amino-6-methoxy- 2- (4' -methoxy) phenyl-pseudo-azimidobenzene, the 5-amino-6-methoxy-2- (4 ethoxy) phenylpseudo azimidobenzene, the 5 amino 2 -(1') naphthyl-pseudo-azimidobenzene, the E-amino- 2- (4-c-methoxy-oxyethyl) phenyl pseudo-azimidobenzene, are condensed with esters of B- ketone-carboxylic acids, such as ethyl acetoacetate, benzoyl acetic ester, or terephthaloyl acetic ester,
These arylides thus correspond to the general formula in which R stands for a member of the group consisting of aryl nuclei of the benzene and naphthalene series, R1 stands for a member of the group consisting of methyl and phenyl, and y stands for a member of the group consisting of H, CH3 and O-alkyl. Among such products those are valuable in which R represents a nucleus of the benzene series because they lead to particularly valuable dyestuffs. Among such products those are again particularly valuable which correspond to the general formula in which y has the signification already indicated above and :1 stands for a member of the group No Drawing. Application July 12, 1937, Serial In Switzerland July 14, 1936 consisting of H, CH3 and O-alkyl. All these products are light colored powders insoluble in water but soluble in aqueous caustic alkalies.
The new arylides, which represent valuable intermediate products for the manufacture of dyestuffs, dissolve in aqueous caustic alkalies owing to the presence of the -COCH2CO- group. In such solutions the alkali salts of the new arylides possess a marked affinity for the Vegetable fiber, which is entirely surprising, since the similar arylides from the isomeric amino-azimides do not possess such an afiinity for the vegetable fiber. Since they combine with diazo compounds to azo-dyestuffs they are inter alia very suitable for the production of azo-dyestuffs on the vegetable fiber (cotton, ram-ie, flax, jute and the like) as well as on regenerated cellulose (viscose or cuprammonium silk), and also on animal fibers such as wool, natural silk or loaded silk, according to the methods usual in dyeing with ice colours. Such methods are, for example, padding the fiber in an alkaline solution of the new arylide and developing with a diazo compound, preferably one containing no hydroxy-, carb'oxyor sulfo-groups. Such diazo-compounds are, for instance, those derived from aniline, ethers or esters of amino-phenols, for example orthoor para-anisidine, 4-chloroZ-amino-diphenylether, 4:4'-dichloro-2-aminodiphenylether; those derived from monoacylated products from 2:5-diaminohydro-quinone-diethylor -dimethy1ether and benzoylchloride or phenoxy-acetic-acidchloride; aminoazo dyestuffs, for instance, 4- amino-5-methoxyazobenzene, l-amin'o 2:5 dimethoxyazobenzene, ortho-amino-azo toluene; further those derived from chlorotoluidines, for instance l-chloro-2-methyl-l-aminobenzene, 4- chloro-1-methyl-2-aminobenzene; those from ni-' tranalines such as ortho-nitraniline, 1-amino-2- methylA-nitrobenzene, l-amino-2-n'itro-4-chlorobenzene, 1-amino-2-nitro-4-1nethylor -methoxybenzene, or 4-nitro-2-methoxy-1-aminoben zene; those derived from orthoor meta-chloraniline, 2:5-dich1oraniline, uor ,c naphthylamine and the like.
For the purpose of producing fast tints on the fiber preparations or printing colors containing them may also be prepared which contain an alkali salt of the new derivatives and a stabilized diam-compound in the form of a nitrosamine or of a diazoamino-compound. These preparations may be printed on the fiber and then developed to dyestuifs by suitable treatment, for example by passage through an acid. It is also possible to print mixtures of the free diazotizing components or the corresponding Nnitramines and alkali salts of the new coupling components on the fiber and to convert such mixture into dyestufis by development with nitrous acid, and, if desired, subsequent treatment in alkali.
The condensation products of the general formula in which R, R1 and y have the signification indicated above, coupled in substance with the same non-sulfonated compounds with which they are used for the production of fast tints on the fiber, yield pigments which are useful as such or in coloring lacquers, varnishes or the like.
With sulfonated diazo-compounds wool dyestuffs are in particular obtained. Especially valuable are the dyestuffs which are derived from ortho-hydroxylated or ortho-carboxylated diazoare added gradually 15 parts of ethylacetoacetate. Condensation is continued for 2 hours, during which time the alcohol formed and some chlorobenzene are distilled. When condensation is complete, the mass is cooled, the chlorobenzene is distilled in steam and the condensation prodnot left behind is filtered; it is dissolved in dilute caustic alkali lye and, after filtration from some impurities, the solution is treated with dilute hydrochloric acid to reprecipitate the condensation product.
It is a white powder freely soluble in dilute alkalies and melting after recrystallization from alcohol at 152 C.
The process is similar with the other pseudoazimides and fi-ketone-carboxylic acid esters cited in the introductory paragraphs. The following table shows the melting point of some of such condensation products:
B-ketone-carboxylic-acid-ester Azimide Melting point from- Ethyl acetoacetate +5-ami n0-2-(4-methoxy)-phenyl-pseudo-azimidobenzene.; Alcohol 163 0. Do +5-am1 no-2-(4-ethoxy)-phenyl-pseudo-azimidobenzene Alcohol 191 0. Do +5-am1no-6*methyl-2-phenyl-pseudo-azimidobenzene Alcohol 205 0. Do +5 a 6 methyl 2 (4 methoxy) phenyl pseudo- Chlorobenzene 222 0. az1m dobenzene. Do +-an 11no-6-methoxy-2-(4-methoxy)-phenyl-pseudo-azi- Alcohol 168 C.
midobenzene. Do +5-ammo-6-methoxy-2-(4-ethoxy)-phenyl-pseudo-azimi- Alcohol 155 C.
dobenzene. +5-amino-6-ch1oro-2-phenyl-psoudo-azimidobenzene Alcohol 185 0. Do +5-am1n0-6-met y1- )mapllthyl-pseudo-azimidobenzene Ohlorobenzene 209 C. Benzoyl acetic ester. +5-am1no-2-phenyl-pseudo-azimidobenzene Alcohol 180 C. Terephthaloyl-diacetic ester ..do 7 Alcohol 280 0.
compounds as these products may be converted in substance or on the fiber into metalliferous dyestuffs.
The dyestuffs which may be prepared according to the present process with aid of the new arylides correspond therefore to the general formula r in which R, R1 and y have the signification indicated above, and R2 stands for an aromatic radical selected from the group consisting of aromatic nuclei of the benzene and naphthalene series. If these dyestuffs do not contain sulfogroups they represent yellow to orange or brownorange pigments which are insoluble in water. Particularly valuable are the dyestuffs of the formula in which R2 stands for an aromatic radical of the benzene series, if the benzene radical R2 contains a Intro-group in ortho-position to the -N=N-group. These dyestuffs when produced on the fiber dye the same yellow tints of very good fastness properties, particularly excellent fastness to light.
The following examples illustrate the invention, the parts being by weight:-
Example 1 21 parts of 5-amino-2-phenyl-pseudo azimidobenzene are introduced into 200 parts of chlorobenzene, a few drops of diethylaniline are added and the whole is heated to boiling under reflux.
The chlorobenzene is then distilled and. there Example 2 13.87 parts of ortho-nitraniline are diazotized as usual and the product is introduced into a solution of 29.4 parts of the condensation product from 5-amino-2-pheny1-pseudo-azimidobenzene and ethylacetoacetate, 100 parts of sodium hydroxide solution of 36 B., 1 5 parts sodium acetate and 2000 parts of 'water. The yellow dyestuff formed is precipitated immediately; it is filtered and dried.
If a sulfonic acid, for instance sulfanilic acid, is substituted for the ortho-nitraniline, there is obtained a dyestuif soluble in water.-
Ewample 3 Cotton yarn is impregnated with a grounding prepared by dissolving 3 parts of the condensation product from 5aminophenyl-pseudo-azimidobenzene and ethylacetoacetate in 300 parts of hot water with the addition of 6 parts sodium hydroxide solution of 30 per cent. strength, 10 parts of Turkey red oil, parts of sodium chloride, and water to make up 1000 parts. The goods are then wrung out and developed in a diazo-solution which has been neutralized with sodium acetate and acidified with acetic acid, and corresponds with 2 parts of 1-amino-2- methyl-l-nitrobenzene per 1000 parts. There is produced a pure greenish-yellow of very good properties of fastness.
Similar tints are obtained with other diazocomponents, for instance 1-amino-2-methyl-4- chlorobenzene, 1-amino-2-nitro-4-chlorobenzene, 1-amino-2-nitro-4-methylbenzene. Redder tints are obtained for instance with l-amino-Z-nitrol-methoxybenzene or ortho-aminoa'zotoluene.
The goods may also be grounded at a raised temperature, for instance at 80 C.; such arylides may also be used for printing.
The following table comprises a number of for the Vegetable fiber, and react with diazo cominvention pounds with formation of azo-dyestufis.
DiaZo-component Condensation product from ethyl-aceto-acetate with- Color Ortho-nitraniline 5-amino-2-(4-methoxy)-phenyl-pseudo-azimidobenzene Yellow. l-amino-Z-nitro-4methyl-benzene do- Do. 1-amino-2-nitro-4methoxybenzenedo Do.
5-amino-2-(4-etl1oxy)-phenyl-pseudo-azimidobenzene D Ortho-nitramline Para-mtraniline.
Ortho-aminoaZo-toluene l-amino-2-nitro-4-chlorbenzene 2:5-dichlotaniline 4:4-dichlor-2-aminodipl1enyletl1er-- 1-amino-2-nitr0-4-chlorbenzene Ortho-nitraniline o. Greenish-yellow. Reddish-yellow.
5-smino-6-methyl-2-phenyl-pseudo-azimidobenzene Gold-orange. 5-%mino-6-methyl-2- (4 -mcthoxy) -phenyl-pseudo-azimido- Reddish-yellow.
enzene. fi-amino-S-methoxy-Z-(4-metl1oxy)-phenyl-pseudo-azimido- Yellow.
benzene. do Greenish-yellow. do Reddish-yellow. do Yellow.
What we claim is: 1. As new products the arylides of the general formula in which R stands for a member of the group consisting of nuclei of the benzene and naphthalene series, R1 stands for a member of the group consisting of methyl and phenyl, and 3 stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the vegetable fiber, and react with diazo compounds with formation of azo-dyestuffs.
2. As new products the arylides of the general formula in which R1 stands for a member of the group consisting of methyl and phenyl, y stands for a member of the group consisting of H, CH3 and O-alkyl, and it stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the vegetable fiber, and react with diazo compounds with formation of azo-dyestuifs.
3 As new products the arylides of the general formula in which :1] stands for a member of the group consisting of H, CH3 and O-alkyl, and :0 stands for a member of the group consisting of H, CH3, 0'- alkyl and halogen, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess aflinity l II o N-C-CHr- OH;
4. As new products the arylides of the general formula i i i N-C-OHrC-CHB in which y stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the vegetable fiber, and react with diazo compounds with formation of a20- dyestuffs.
5. As new products the arylides of the general formula in which the alkyl-group contains not more than 2 carbon atoms, and in which :1 stands for a member of the group consisting of H, CH3 and O-alkyl, which products are light colored powders, dissolving in aqueous caustic alkalies; from which solutions they possess afiinity for the vegetable fiber, and react with diazo compounds with formation of azo-dyestuffs.
6. As a new product the arylide of the formula HANS JOI-INER. A GERALD BONHOTE.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US184277A US2136136A (en) | 1937-07-12 | 1938-01-10 | Dyestuffs |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CH2136135X | 1936-07-14 |
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Publication Number | Publication Date |
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US2136135A true US2136135A (en) | 1938-11-08 |
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ID=4567648
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Application Number | Title | Priority Date | Filing Date |
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US153279A Expired - Lifetime US2136135A (en) | 1936-07-14 | 1937-07-12 | Pseudo-azimido-benzene-amino-acyloacetic acid esters |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4573639A (en) * | 1982-05-24 | 1986-03-04 | Logue Murl F | Shower head |
US5132429A (en) * | 1988-05-31 | 1992-07-21 | Shionogi & Co., Ltd. | Benzotriazole derivatives and fluorescence-emitting reagents thereof |
-
1937
- 1937-07-12 US US153279A patent/US2136135A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4573639A (en) * | 1982-05-24 | 1986-03-04 | Logue Murl F | Shower head |
US5132429A (en) * | 1988-05-31 | 1992-07-21 | Shionogi & Co., Ltd. | Benzotriazole derivatives and fluorescence-emitting reagents thereof |
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