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2,136,135 UNITED STATES PATENT OFFICE Patented Nov. 8, 1938 2,136,135 PSEUDO-AZllVlIDO-BENZENE-AMINO - ACYL , OAG‘ETIG ACID‘ EST‘ERS ‘Hans Johner ‘and Gerald Bonhote, Basel, Swit zerland, assignors to the ?rm Society of Chem ical Industry in Basle, Basel, Switzerland No Drawing. Application July 12, 1937, Serial No. 153,279. 1 . In Switzerland July 14, 1936 8 Claims. (Cl. 260-308’) 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 ‘ 5 process of producing the same as well as their application for the manufacture of dyestuffs. It has been found that valuable arylides of pi ketone-carboxylic acids may be obtained if amino compounds of the general'formula '10 "15 in which R. stands for an aryl radical of the ben zene 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 - azimi 2 O dobenzene, the 5-amino-2—(4’- ethoxy) - phenyl pseudo-azimidobenzene, the 5-ami'no-6-methy1 2- (4'-methoxy) -phenyl-pseudo - azimidobenzene, the 5-amino-6-methyl - 2 -"(4'- ethox‘y) -p-henyl pseudo-azimidobenzene, the 5-amino-6-methoxy 25 2- (4' -methoxy) -- phenyl-pseudo-azimidobenzene, the 5-amino-6-methoxy-2- (4’ - ethoxy) - phenyl pseudo - azimidobenzene, the 5 - amino - 2 -(1') - naphthyl-pseudo-azimidobenzene, the E-amino 2- (4’-c-‘methoxy-oxyethyl) - phenyl - pseudo-azi 3 O midobenzene, are condensed with esters of B ketone-carboxylic acids, such as ethyl acetoace tate, benzoyl acetic ester, or terephthaloyl acetic ester, These arylides thus correspond to the general formula O 40 \N ~11 in which R stands for a member of the group consisting of aryl nuclei of the benzene and naph thalene series, R1 stands for a member of the 45 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 par ticularly valuable dyestuffs. Among such prod ucts those are again particularly valuable which correspond to the general formula in which y has the signi?cation already indicated 4.60 above and :1,‘ stands for a member of the group 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 ~CO—CH2—CO-— group. In such solutions the alkali salts of the new arylides possess a marked affinity for the Vegetable ?ber, which is entirely surprising, since 10 the similar arylides from the isomeric amino-azi mides do not possess such an a?inity for the vege table ?ber. Since they combine with diazo com pounds to‘ azo-dyestuffs they are inter alia very suitable for the production of azo-dyestuffs on 15 the vegetable ?ber (cotton, ram-ie, ?ax, jute and the like) as well as on regenerated cellulose (vis cose or cuprammonium silk), and also on animal ?bers such as wool, natural silk or loaded silk, according to the methods usual in dyeing with ice 20 colours. Such methods are, for example, padding the ?ber in an alkaline solution of the new arylide and developing with a diazo compound, preferably one containing no hydroxy-, carb'oxy or sulfo-groups. Such diazo-compounds are, for 25 instance, those derived from aniline, ethers or esters of amino-phenols, for ‘example ortho- or para-anisidine, 4-chloro—Z-amino-diphenylether, 4:4'-dichloro-2-aminodiphenylether; those de rived from monoacylated products from 2:5-di aminohydro-quinone-diethyl- or -dimethy1ether and benzoylchlorider or phenoxy-acetic-acid chloride; aminoazoedyestuffs, for instance, 4 amino-5-methoxyazobenzene, methoxyazobenzene, Ll-amin'o - 2:5 - di ortho-amino-azo - toluene; further those derived from chlorotoluidines, for instance tl-chloro-2-methyl-l-aminobenzene, 4 chloro-1-methyl-2-aminobenzene; those from ni-' tranalines such as ortho-nitraniline, 1-amino-2 40 methylA-nitrobenzene, l-amino-2-n'itro-4-chlo robenzene, 1-amino~2-nitro-4-1nethyl- or -meth oxybenzene, or 4-nitro-2-methoxy-1-aminoben— zene; those derived from ortho- or meta-chloran iline, 2:5-dich1oraniline, u- or ,cenaphthylamine and the like. For the purpose of producing fast tints on the ?ber 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. vThese 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 com ponents or the corresponding N—nitramines and alkali salts of the new coupling components on the ?ber and to convert such mixture into dye 2 2,136,135 stu?s by development with nitrous acid, and, if desired, subsequent treatment in alkali. are added gradually 15 parts of ethylacetoacetate. Condensation is continued for 2 hours, during ' The condensation products of the general for which time the alcohol formed and some chloro benzene are distilled. When condensation is complete, the mass is cooled, the chlorobenzene is distilled in steam and the condensation prod not left behind is ?ltered; it is dissolved in dilute caustic alkali lye and, after ?ltration from some mula impurities, the solution is treated with dilute hydrochloric acid to reprecipitate the condensa 10 tion product. 10 in which R, R1 and y have the signi?cation in dicated above, coupled in substance with the same non-sulfonated compounds with which they are used for the production of fast tints on the ?ber, yield pigments which are useful as such or in coloring lacquers, varnishes or the like. 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 pseudo With sulfonated diazo-compounds wool dye 15 azimides and ?-ketone-carboxylic acid esters cited in the introductory paragraphs. The fol stuffs are in particular obtained. Especially valu able are the dyestuffs which are derived from lowing table shows the melting point of some of such condensation products:— ortho-hydroxylated or ortho-carboxylated diazo 20 B-ketone-carboxylic-acid-ester Azimide Melting point from— Ethyl acetoacetate ____________ __ +5-ami_n0-2-(4’-methoxy)-phenyl-pseudo-azimidobenzene.; Do _______________________ __ +5-am1_no-2-(4’-ethoxy)-phenyl-pseudo-azimidobenzene____ Alcohol 191° 0. Do _______________________ ._ Do _______________________ _. +5-am1no-6*methyl-2-phenyl-pseudo-azimidobenzene____ __ Alcohol 205° 0. Do _______________________ __ +5-an_11no~6-methoxy-2-(4’-methoxy)-phenyl-pseudo-azi- Do _______________________ _. +5-ammo-6-methoxy-2-(4’-ethoxy)-phenyl-pseudo-azimi~ +5 -_a!I_1m0 - 6 - methyl - 2 - (4’ - methoxy) - phenyl - pseudoaz1midobenzene. , ' Chlorobenzene 222° 0. 25 ‘ midobenzene. dobenzene. Alcohol 163° 0. Alcohol 168° C. Alcohol 155° C. ' +5-amino-6-ch1oro-2-phenyl-psoudo-azimidobenzene _____ __ Alcohol 185° 0. Do ___________ __ Benzoyl acetic ester. +5-am1n0-6-methy1-2-(1’)mapllthyl-pseudo-azimidobenzene_ Ohlorobenzene 209° C. +5-am1no-2~phenyl-pseudo-azimidobenzene _____________ __ Alcohol 180° C. Terephthaloyl-diacetic ester compounds as these products may be converted in substance or on the ?ber into metalliferous dyestuffs. The dyestuffs which may be prepared accord ing to the present process with aid of the new arylides correspond therefore to the general for mula 30 _-_..do___ 7 ______________________________________________ __ Alcohol 280° 0. ’ r 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‘ prod 35 uct from 5-amino-2-pheny1-pseudo-azimidoben zene and ethylacetoacetate, 100 parts of sodium hydroxide solution of 36° Bé., 175‘. parts sodium acetate and 2000 parts of 'water. The yellow dyestuff formed is precipitated immediately; it l' in which R, R1 and y have the signi?cation in dicated 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 sulfo groups they represent yellow to orange or brown orange pigments which are insoluble in water. Particularly valuable are the dyestuffs of the for mula ~ in which R2 stands for an aromatic radical of the benzene series, if the benzene radical R2 con tains a Intro-group in ortho-position to the -—N=N-group. These dyestuffs when produced on the ?ber dye the same yellow tints of very ' 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 condensa tion product from 5—aminophenyl-pseudo-azi midobenzene 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, 15 parts of sodium chlo ride, and water to make up 1000 parts. The goods are then wrung out and developed in a diazo-solution which has been neutralized with 60 sodium acetate and acidi?ed 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 good fastness properties, particularly excellent properties of fastness. fastness to light. The following examples illustrate the inven components,’ for instance 1-amino-2-methyl-4~ tion, the parts being by weight: Example 1 70 21 parts of 5-amino-2-phenyl-pseudoeazimido benzene are introduced into 200 parts of chloro benzene, a few drops of diethylaniline are added and the whole is heated to boiling under re?ux. 75 is ?ltered and dried. The chlorobenzene is then distilled and. there Similar tints are obtained with other diazo chlorobenzene, 1-amino-2-nitro-4-chlorobenzene, 1-amino-2-nitro-4-methylbenzene. Redder tints are obtained for instance with l-amino-Z-nitro 70 ‘l-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 75 3 2,136,135 other dyeing colors which may be made by this invention :— DiaZo-component for the Vegetable ?ber, and react with diazo com pounds with formation of azo-dyestu?s. Condensation product from ethyl-aceto-acetate with- Ortho-nitraniline _________________ __ 5-amino-2-(4’-methoxy)-phenyl-pseudo-azimidobenzene ____ _- Color Yellow. l-amino-Z-nitro-4»methyl-benzene_ __ -.___do-_ _ 1-amino-2-nitro-4—methoxybenzene-_ _ Do. .____do _ _ _ _ _ . _ _ . _ _ _ _ ._ 5-amino-2-(4’-etl1oxy)~phenyl-pseudo-azimidobenzene _______ __ Ortho-nitramline ______ _ Para-mtraniline. _ _-___ 10 ___ . _ _____do ____________________________________________________ __ 5-smino-6-methyl-2-phenyl-pseudo-azimidobenzene ________ __ Ortho-aminoaZo-toluene_ _ -_ _. _ l-amino-2-nitro-4-chlorbenzene ____ __ ?-amino-S-methoxy-Z-(4’-metl1oxy)-phenyl~pseudo-azimidobenzene. 4:4’-dichlor~2-aminodipl1enyletl1er--_ 1~amino-2-nitr0~4-chlorbenzene ____ _. 15 Ortho-nitraniline _________________ ._ Greenish-yellow. Reddish-yellow. 10 Gold-orange. 5-%mino~6-methyl-2- (4’ -mcthoxy) ~phenyl-pseudo-azimido- Reddish-yellow. enzene. 2:5-dichlotaniline _________________ __ Do. D o. Yellow. , _____do _ _ _ _ _ _ . _ . . _ . . -_ Greenish-yellow. _____do ____________________________________________________ __ Reddish-yellow. _._-_do ____________________________________________________ __ Yellow. What we claim is:— 1. As new products the arylides of the general 15 4. As new products the arylides of the general formula i‘ ‘i formula i’ N-C-OHrC-CHB 20 in which y stands for a member of the group con in which R stands for a member of the group con sisting of nuclei of the benzene and naphthalene series, R1 stands for a member, of the group con sisting 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 pow ders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the 35 vegetable ?ber, and react with diazo compounds sisting of H, CH3 and O-alkyl, which products 25 are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they pos sess af?nity for the vegetable ?ber, and react with diazo compounds with formation of a20 30 dyestuffs. 5. As new products the arylides of the general formula 35 with formation of azo-dyestuffs. 2. As new products the arylides of the general formula Ill 0 40 @Ncl, 45 , 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 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 40 O-alkyl, which products are light colored pow ders, dissolving in aqueous caustic alkalies; from which solutions they possess a?inity for the vege table ?ber, and react with diazo compounds with 45 formation of azo-dyestuffs. 6. As a new product the arylide of the for mula O-alkyl, and it stands for a member of the group consisting of H, CH3 and O-alkyl, which products 50 are light colored powders, dissolving in aqueous caustic alkalies, from which solutions they possess affinity for the vegetable ?ber, and react with diazo compounds with formation of azo-dyestuifs. 3 As new products the arylides of the general 55 formula ]ll I o N-C-CHr- —OH; 60 7. As a new product the arylide of the for mula /N CQHF-O-GN\Nl H (II) I 1l1'—C——CH2-C—-CHa OCH: 8. As a new product the arylide of the for mula H 0 I ll ll in which :1] stands for a member of the group con 65 sisting 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 col ored powders, dissolving in aqueous caustic alka lies, from which solutions they possess a?inity /N onto-Oat | ' \N 55 a0 —N—-C—CH2—-C—CHa 65 —CH3 HANS JOI-INER. A GERALD BONHOTE.