The R-A reactions have been carried out on carbonyl compounds, such as glyoxal, pyruvaldehyde (methylglyoxal), acetoin, and acetol acetate, in the presence of ammonia yielded 85% of imidazole (mp 88-90°C) as a main product from glyoxal and large amount of ethylene glycol as a neutral by-product. About the same yield of imidazole was obtained by mere heating of a mixture of glyoxal and aqueous ammonia. The velocity of formation of imidazole is considered to be faster than the reduction of glyoxal itself. In case of methylglyoxal, there, was no formation of such imidazole derivatives and the wain reaction was the formation of dialkanolamine which was considered to be produced from deamination of 2-aminopropanol and isopropanolamine in the first step of reaction and the yield was 36% and the yield of propyleneglycol as a neutral substance was 33%. In case of using acetoin as a raw material, the main product was butyldiamine-2, 3 with 44% yield, followed by 24% yield of 2, 3, 5, 6-tetramethylpiperazine, and 10% of 2-amino-3-hydroxybutane. In case of using acetol acetate as a raw material, the yield of products were 45% dipropanolamine-O-acetate, NH[CH(CH₃)-CH₂0Ac]₂, 19% 2, 6-dimethylpiperazine. and a high boiling polymer.

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Bromination of 1-amino-4-hydroxyanthraquinone yielded 1-amino-2-bromo-4-hydroxyanthraquinone. Reaction of bromine on 1-amino-4-methoxyanthraquinone in glacial acetic acid gave 1-amino-2-bromo-4-hydroxyanthraquinone with good yield. Absorption spectra of 1-amino-2-bromo-4-hydroxyanthraquinone and 1-amino-3-bromo-4-hydroxyanthraquinone and their affinity towards acetate have been investigated and found that the effect of position of bromine is remarkable, also, the considerable differences in fastness of dye are noted.

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A new fact of synthesis of 1-amino-3-methylanthraquinone has been found through the route of 1-amino-2-methylanthraquinone, 1-amino-2-methy1-4-bromoanthraquinone, its diazotation and reduction to 1-bromo-3-methylanthraquinone, and treating this with p-toluenesulfonamide and subsquent hydrolysis of the product. Also, p-toluenesulfonamide was reacted with 1-chloro-4-methylanthraquinone to obtain 1-(p-toluenesulfonyl) amino-4-methylanthraquinone and this was hydrolyzed in sulfuric acid to 1-amino-4-methylanthraquinone. Absorption spectra of 1-amino-2-methylanthraquinone, 1-amino-3-methylanthraquinone, and 1-amino-4-methylanthraquinone were determined.

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The following 7 kinds of new dialkyldinaththylurea type compounds were synthesized as a series of compotmds effective for preventing the fading of dyes for cellulose acetate by acidic gas:_??_

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In the Previous papers, we have reported on a manufacturing method of Na-monochloro-, and -1, 4-dichloroanthraquinone-7-sulfonates from Na-anthraquinone-sulfonate (Silver salt).
In the present papers, we report on the synthesis of some acid anthraquinone dyes, from Na-1, 4-dichloroanthraquinone-7-sulfonate (I).
1). Condensation of I with 2 moles of aniline, to obtain Na-1, 4-dianilino anthraquinone-7-sulfonate. 5g. I, 60g. aniline, and 2g. NaOAc. were stirred at 183-5°, for 8hr. The product was greenish black powder. Yield, 6.3g.(96.9% of the calc. amount). It showed no mp., and dyed wool, as well as nylon, bluish green hue of excellent light fastness. Dyeing and testing methods are outlined. In water solution, absorption maxima were found at 200mg, and 640mμ
2). Amination of condensation product of I with 1 mole of aniline, to obtain Na-amino-anilino-anthraquinone-sulfonate. A mixture of 40g. I, 38.4g. aniline, 18g. Na₂CO₃ and 440cc. water was stirred at 95°, in the presence of freshly prepared cuprous oxide, for 4hr., until the condensation was complete (reaction end point was detected by paper chromatographical method). The product (11) was reddish violet powder. Yield, 38-40g.(83-86% of calc. amount). It showed no mp., and dyed wool bluish red. In water solution, absorption maxima were found at 259.0mμ., 332.5mμ., and 535mμ.
Amination of II.5g. II (as Na salt), 180cc. 28% ammonia, and 2g. p-toluene sulfamide were taken in an autoclave, and heated at 125° and 20 atm. for 4hr. The product was deep blue powder. It showed no mp. Yield, 2.9-3.0g.(64-66% of calc. amount). It dyed wool navy blue of excellent light fastness. In water solution, absorption maxima were found at 255mμ., 550mμ., and 590mμ. The presence of amino group in the dye was identified by its diazotisation and coupling with β-naphtol, to obtain a brown acid azo dye.
3). Condensation of I, with 1 mole of monomethylamine, and 1 mole of aniline, to obtain Na-methylamino-anilino-anthraquinone-sulfonate. 5g. I and 3g. Na₂CO₃ were dissolved in 150cc. water at 95°. To the solution, 0.9g. CH₃NH₂·HCl, dissolved in 20cc. water, was added, and stirred at 95° for 4-5hr. The product was reddish violet powder (III). Yield, 4.6g.(93.5% of calc. amount). It showed no mp., and dyed wool clear bluish red hue, but of little value as dye. In water solution, absorption maxima were found at 255.5mμ., and 535mμ.
Condensation of III with 1 mole of aniline. 4 g. III (as Na salt), 50g. aniline, and 2g NaOAc were stirred at 183-5° for 25hr. The product was greenish black powder. Yield, 4.1g.(89.1% of calc. amount). It showed no mp., and dyed wool blue-black hue, similar to Acid Blue Black. 10 B.(C. I. 246). Dyeing and fastness properties were studied in details (See Table 3-5). In water solution. absorption maxima were found at 254mμ. and 620mμ.

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Differences in colors and their fastness have been investigated by changing the alkyl group to methyl, ethyl, n-propyl and n-butyl in Fast Blue RR type developing agent (2-benzoylamino-5-aminohydroguinone dialkyl ether) or by changing the alkyl group of Violet Base Chiba III type (having 2-p-cresoxyacetamino group in Fast Blue RR type).
The result indicated that the coloration was in order of n-propyl<n-butyl<methyl<ethyl in Fast Blue RR type. In Violet Base III type, metyl derivative only showed the development of light purple coloration while all others showed blue coloration of the same intensity and an increase in numbers of carbon atoms in alkyl group was not accompanied with deep coloration. In all cases, there were no great differences in fastness, being 5-6 grade for light and 4-5 grade for washing and rubbing.

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Fast Blue RR type developing agent (3-benzoylamino-6-aminohydroquinone dialkyl ether) and Violet Base Chiba III type developing agent (having 3-pcresoxyacetamino group in Fast Blue RR) were converted into their 1-CH₃O and 4-RO groups (R=ethyl, n-propyl, and n-butyl), respectively, and their colorations have been investigated.
The result indicated that only ethyl ether in Fast Blue RR type showed the development of blue color, others showed reddish blue coloration as in methyl ether and the higher alkyl ethers were not always effective for development of deeper coloration. Violet Base Chiba I type compound showed development of purple coloration, in which ethyl ether showed coloration near to blue while butyl ether showed darker coloration.

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Dimetyl-, diethyl-, and ethylene ethers of aminocatechol were synthesized. Those were condensed with β-hydroxynaphthoic acid to give azoic coupling components. p-Nitroaniline and 2-chloro-4-nitroaniline were diazotized and coupled with aminocatechol dimethyl- and -diethyl ether to give aminoazo compounds as azoic diazo components, and their coloration and fastness have been invb-stigated.
The coupling components synthesized gave nearly the same coloration as that of Naphthol AS-BG, among which ethylene derivative gave a clear blue coloration when combined with Fast Blue BB and its fastness was about the same as that of Naphthol AS-BG. The diazo components generally colored in brownolive green, their fastness was 6 grade for light and superior for washing and rubbing.

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1-Cyano-l-methylethyl radicals produced by the decomposition of α, α'-azobisisobutyronitrile attacked the semipolar N→0 bond of azoxybenzene and dimethylaniline-N-oxide yielding hydrogen cyanide, acetone, azobenzene, and dimethylaniline. Sulphone, sulphoxide, triethyl phosphate, and phosphorus oxychloride did not react with this radical. There was a rough parallelism between the amounts of acetone produced and the reductive half-wave potentials of nitro compounds, azoxybenzene, and dimethylaniline-N-oxide.
Oxygen combined with 1-cyano-1-methylethyl radicals in solutions to yield the corresponding peroxy radicals which decompose giving hydrogen cyanide and acetone.

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1-Cyano-l-methylethyl radicals produced by the decomposition of α, α'-azobisisobutyronitrile attacked dimethylaniline yielding 2, 4-bis-(1-cyano-1-methyl ethyl)-dimethylaniline. 1-Cyano-1-methylethyl radicals, however, did not react with aniline, diethylaniline, acetanilide, pyridine, anisole, acetophenone, benzonitrile, azobenzene, and benzoin. The reaction mechanism is discussed in terms of electron transfer. a, N-Diphenylnitrone combined with two 1-cyano-1-methylethyl radicals to produce N-phenyl-N-[α-(1-cyano-1-methylethyl)-benzy1]-O-(1- cyano-1-methylethyl)-hydroxylamine in 63% yield. This reaction is a new type of addition. 1-Cyano-1-methylethyl radicals did not add to a C=N bond.

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