In the preceeding report, it was clarified that anthraquinone-oxazole ring showed electron-attractive property. This report deals with syntheses of new dyes having anthraquinone-oxazole ring, such as 2-(4-anthraquinone-oxazolylanilino) anthraquinone (2), 1-(4-anthraquinone-oxazolylanilino)-4-benzoylaminoanthraquinone (3b), and 10-(anthraquinone-oxazolyl) anthraquinonebenzacridone (4), and their dyeing properties. Synthesis of (2) was made by Ullman reaction of 2-(4-bromophenyl) anth - raquinone-oxazole (5) and 2-aminoanthraquinone but its yield and purity were extremely low. Chromatographic purification gave orange colored product (brown vat dye). (3b) was synthesized by condensation of (5) and 1-amino-4-nitroanthraquinone, followed by reduction and benzoylatlon. This dyed cotton green fromm green vat and the fastness against light was 5th grade. 1-(4-Anthraquinoneoxazolylanilino)-4-aminoanthraquinone (3a) was overreduced by alkali hydroxide but it gave no original compound by oxidation. (4) was synthesized by condensation of 1-nitroanthraquinone-2-carboxylic acid and 4-aminobenzoic acid, the condensation product was derived to its acidd chloride by use of thionyl chloride, it was cyclized to acridone, then it was further condensed with 2-amino-3-hydroxyanthraquinone and cyclized to oxazole. It dyed cotton orange coloration from vat dyeing. The fastness against the light was 5?`6 th grade. An attempt for synthesis of (4) by condensation of 1-aminoanthraquinone-2-carboxylic acid and (5), followed by cyclizatioa with sulfuric acid, was unsuccessful.
Anthraquinone-azole type dyes having anthraquinone (2:3) oxazole (1a), :anthraquinone (1:2) oxazole (1b), anthraquinone (2:1) oxazole (1c), anthraquinone (2:3) thiazole (1d), and anthraquinone (2:1) thiazole (1e) in 2-position of 1-aminoanthraquinone were synthesized. The dye having anthraquinone-(1:2) thiazole could not be obtained in a pure form. From the N-H stretching-vibration range in infrared absorption spectra, it was indicated the presence of intramolecular hydrogen bonding between amino group and oxazole or thiazole and it was clarified that the intensity was in the order of (1b) > (1c) > (1a), and (1e) > (1d). There was no simple regularity between oxazole and thiazole. The visible spectra of dyes in trichlorobenzene were investigated and it was found that anthraquinone-azole ring had electron-attractive property and λmax shifted to longer wave length side by the extension of conjugated system and intramolecular hydrogen bonding. The λmax was in order of (1b) > (1a) > (1a), .and (1e) > (1d). Following results were obtained from dyed cloths dyed with IW method: kind of dye (vat color, fastnesses against chlorine and light, respectively, given) :1a (brown, 5, 7-8) ; 1b (red, 5, 7-8): 1e (red, 5, 5-6) ; 1d (red, 5, 5-6) ; 1e (red, 5, 7-8). Good fastnesses shown by the dye in spite of having amino group was attributed to the protection of the amino group by the intramolecular hydrogen bonding. However, the fastness against the light cannot be explained from hydrogen bonding alone. Vat color of oxazole type was red brown and that of thiazole type was reddish purple.
N-Sulfonylethylenimide (1) and N-(β-chloroethyl)sulfonamide (2) are easily convertible to each other by the action of hydrochloric acid and alkali as follows:(2) Also, (1) gives β-alkoxyethylsulfonamide (3) in the presence of alcohol and alkali;(3) Therefore, the dye having (2) in the molecule can be converted into (1) by the action of alkali and this is expectable to have chemical binding with cellulose fibers. As the diazo component of (2) type azo dyes, N1-Q-chloroethyl-sulfanilamide (4), 4-methoxy-3-aminobenzenesulfonyl-β-chloroethylamide (5), 4-methyl-3-aminobenzenesulfonyl-β-chloroethylamide (6), 6-methyl-3-aminoben-zenesulfonyl-p-chloroethylamide (7), and 6-ethoxy-3-aminobenzenesulfonyl-β-chloroethylamide (8), respectively, were syntnesized as given in the following order:(A=H, CH3, OCH3, OC2H5) Then, a series of dye were synthesized, using (4) as a diazo component, and G acid, R acid, H acid, J acid, and r acid as azo component. The dyes thus obtained combined with cellulose fibers in the presence of alkali (sodium hydroxide, sodium carbonate and sodium bicarbonate) with heating and confirmed that the (2) is useful as a functional group of the reactive dye.
Aromatic primary amines having sulfonyl-β-chloroethylamide group, N1-β-chloroethylsulfanilamide (1), 4-methyl-3-aminobenzenesulfonyl-β-chloroethyl-amide (2), 6-methyl-3-aminobenzenesulfonyl-β-chloroethylamide (3), 4-methoxy-3-aminobenzenesulfonyl-β-chloroethylamide (4), 6-ethoxy-3-aminobenzenesul-fonyl-β-chloroethylamide (5), and 4-amino-l-naphthalenesulfonyl-β-chloroethyl-amide (6) were synthesized, and a series of azo dyes were synthesized by use of each of these as a diazo component and acetyl-Hacid, acetyl-J acid, acetyl-γ acid, phenyl-J acid, phenyl-γ- acid, carbonyl-J acid, and di-J acid, as an azo component. Respectively, the dyes thus obtained were used for dyeing of cotton fibers by heating in the presence of alkali and the dyed colors, dyeing proper-ties, and f astnesses have been investigated. Each of these dyes combine with cotton fibers, and dyed cotton were fast to the extraction by pyridine and boiling tese with aqueous solution of citric acid or sodium carbonate. Dyed colors were in the range of orange-red-brown purple. Dyeing properties and fastness against washing depend much on its solubility, and easily soluble dyes showed better dyeing properties and fastness. Condensation of 3-hydroxy 2-naphthoic acid and (1), (4), and (5), respectively, in the presence of phosphorus trichloride gave Naphthol AS having active group After fixing of A on cotton by heating in the presence of alkali, and developing by treating with commercial salts we obtained dyed cotton lacking in clearness, and the wet-fastness was unsatisfactory due to the presence of residual uncombined dye. The results of naphthol dyeing of cotton by use of usual Naphthol AS as the grounder and (1), (4), and (5) as the developer were nearly the same as thore obtaned by the abovementioned way.
p-Aminoazobenze ne, 4-amino-1, 1'-azonaphthalene, 1-amino-4-cyclohexyl-aminoanthraquinone, and 1-amino-4-hydroxyanthraquinone, respectively, is made to react with cyanuric chloride to give a dichloro-s-triazine type pigment, (F=residual group of the pigment). Reaction of this with monoethanolamine, diethanolamine, N, N-diethylethyl-enediamine, and ethylenimine, respectively yielded dyes with general formula, where R=H or R'; R'=-CH2CHZOH, -CH2CH2N(C2H5)2 or The dyeing properties of these pigments with substituent groups, such as -N(CH2CH2OH)2 and -NHCH2CH2OH were considerably selective, and Nylon. Vinylon and acetate fibers were dyed well, but cotton, rayon. Tetron and acrylonitrile type fibers were not dyed by these pigments. The basic pigments having a substituent group, -NHCH2CH2N(C2H5)2, showed the characteristics of basic pigment and had less selective property, they dye silk well, and the dyeing properties to rayon, wool and acrylonitrile type fibers was increased, while that of to Nylon, Vinylon and acetate fibers decreased. The quarternary salt also showed the same dyeing property. The products containing ethyle-nimino group as substituent had a charcteristic of reactive or polymerizable pigment, they were fixed on cotton by a mere heating at 110-30°c without condensation agent such as alkali, and the dyed materials were fast against the extraction test with pyridine.
For the purpose of obtaining superior gas-fading inhibitor, 5 kinds of diaminochloro-s-triazines and 15 kinds of aromatic amines were reacted by ref luxing 2 hrs. on a water bath and neutralized to obtain 21 kinds of mono-arylmelamines with above 9O% yield., among which mono-p-ethoxyphenylmela-mine, mp 217-8°c., mono-p-biphenylylmelamine, mp 248-9°c, mono-p-acet amino-pheneylmelamine, mp 256-7°c (reaction for 10 min), N-β-hydroxy-ethyl-N-phenylmelamine, mp 168-9°c, N-methyl-p-toluylmelamine, mp 262-3°c, N-methyl-N-p-chlorophenylmelamine, mp 243°c, N, N'-bismethyl-N-phenyl-melamine, mp 138-9°c, N, N'-bismethyl-N" -phenylmelamine, (picrate, mp 269-270°c), N, N', N"-trismethyl-N-phenylmelamine (picrate, mp 207-8°c) (yield 85%), and N, N', N"-pentamethyl-N-phenylmelamine, mp 89-90°c (yield 40%) are new compounds.
New dyes were synthesized from condensation of 2, 4, 6-trichloro-s-triazine and aminoazo dye or with hydroxyalkyalmine or bis(hydroxyalkyl)amine, having alcoholic hydroxyl as a functional group other than amino group, such as 2-aminoethanol or 2, 2′-iminodiethanol. Dyeing and fastness characteristics of dyes obtained by urein binding of the same aminoazo dyes were compared. As aminoazo dyes, 4-amino-2 2′-dimethY1-1 4′-1′, 4′′-1′′ 4′′′-trisazobenzene-1′′′, 3′′-disulfonic acid, 2-(4′-amino-2′-methylphenylazo)naphthalene-4, 8-disulfonic acid, 4-amino-3-methoxy-1, 1′-azobe nze-3′-sulfonic acid, and 1-amino-4, 1′-azo-4′-hydroxybenzene-3′-earboxylic acid, have been used. Dyes having 2, 4-dichloro-6-alkanolamino-s-triazine nucleus showed higher solubility in water due to the presence of hydrophilic residual alkanolamine group and showed better fastness against various tests than those of dyes from urein binding, especially, it showed no discoloration by the dyeing at high temperature.
N4-Benzilidene-N1-(3, 4-dimethyl-5-isoxazolyl)sulfanilamide was obtained by the condensation of N1-(3, 4-dimethyl-5-isoxazolyl)sulf anilamide (1) (sulf isox azole) and benzaldehyde. This in toluene was acetylated with acetic anhydride for synthesis of N4-benzilidene-N1-acetyl-N1-(3, 4-dymethyl-5-isoxazolyl)sulf anilamide. This was hydrolyzed easily at room temperature and gave N1-acetyl-N1-(3, 4-dimethyl-5-isoxazolyl) sulf anilamide by the liberation of benzaldehyde. By a similar way, an attempt was made for synthesis of N1-acetyl substitunet of N1-(2, 6-dimethoxy-4-pyrimidinyl)-sulf anilamide (2) (sulf adimethoxine), but the separation of N4-benzilidene derivative of (2) was impossible. Therefore, acetylation of N4-(2-carboxybenzilidene) derivative of (2) was attempted but the acetylation of N1-position was impossible. In connection with this work, N4-acetyl and N1, N4-diacetyl substituents of (1), and N4-acetyl and N1, N4-diacetyl substituents of (2) were obtained. Succinylation of (1) and (2) gave N4-succinyl substituent only in each case.