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The title compounds 3 were prepared in low yields from the carbylamine reaction of amino-1,3,5-triazines 1 under phase-transfer conditions. Isocyanotriazine 3a readily reacted with amines in the presence of copper salts to afford triazinylformamidines 4, and also with active methylene compounds in the presence of base to afford addition products 5 and 6, indicating the high electrophilicity of 3. The reactions of isocyanotriazine with electrophiles such as carbonyl compounds and bromine are also described.

The azo coupling reaction of p-dimethylaminobenzenediazonium tetrafluoroborate with mphenylenediamine has been investigated in a water-1, 2-dichloroethane two-phase system. It has been found that, among the organic acids examined, dipicrylamine and thiols such as pentachlorobenzenethiol and 2, 4-dinitrobenzenethiol acted as efficient anionic phase-transfer catalysts.

The nucleophilic substitution reactions of 2-methoxy- and 2-diethylamino-4-chloro-6-(2-hydroxy-1-naphthyl)-1,3,5-triazines (1) with aniline, diethylamine, sodium azide, and sodium methoxide were carried out and compared with the reactions of the corresponding derivatives of 4-chloro-6-(4-hydroxy-1-naphthyl)-1,3,5-triazine (2) and 4-chloro-6-(1-naphthyl)-1,3,5-triazine (3). Compound 1 was found to be more reactive than the corresponding (2) and (3), not only in the reactions of a neutral molecule, but also in those of anionic species. The results of the reactions of neutral species are interpreted in terms of the difference in solvation toward the substrates; however, the loss of coplanarity between the naphthalene and triazine nuclei may be responsible for the high reactivity of Compound 1 in the reactions of anionic species.

2-Azido-4,6-dimethoxy-1,3,5-triazine (1a) gave an adduct with pyridine in a molar ratio of 1 : 1. On the contrary, 2-azido-4,6-bis(dimethylamino)-1,3,5-triazine (1b) did not react with pyridine. Similarly, 1a gave an adduct with 3-methylpyridine, whereas in the reactions of 1a with 2-methyl-, 4-methyl-, and 2,6-dimethylpyridines, 2-amino-4,6-dimethoxy-1,3,5-triazine was obtained instead of the adduct. On the other hand, 1a and 1b gave the corresponding triazinyliminophosphoranes with triphenylphosphine.

液一液二相系,相間移動触媒条件下におけるジアゾブミノ化合物〔1〕といくつかの親電子剤との反応を検討した。1-(4-トリル)-3-メチルトリアゼンは臭化プロピル,臭化アリル,および2,4-ジニトロクPtpaベンゼンなどのハロゲン化アルキル(またはアリール)と容易に反応し,3-位のN-アルキル(まぞたはアリール)化物を与えた。また,活性なアルケンに対してMichael型付加反応も起こることがわかった。さらにイソチオシアン酸エステルとの反応では,チオキソ誘導体〔4〕が,チオシアン酸エステルとの反応からは,基質が2分子付加したイミン誘導体〔5〕が得られた。一方,ジフェニルトリアゼンは,同様にアルキル化されるが,塩化ベンゾィルとの反応ではベンズアニリドのみが得られ,その生成過程について考察した。

The diazonio group of arenediazonium salts derived from weakly basic amines were efficiently substituted by hydrogen with alkylbenzenes in sulfuric acid. Several types of evidence, including kinetic results and experiments to trap an intermediate, indicated that the reduction occurs via an aryl radical intermediate. In the reduction with toluene, analyses of by-products suggested a radical chain mechanism, which would involve a propagation cycle caused by electron transfer from the benzyl radical to the diazonio group.

Phenylhydrazine gave o-phenylenediamines as the major product upon heating in a molten mixture of AlCl3–NaCl–KCl. In the molten mixture, some aromatic compounds gave the corresponding aromatic amines in good yields in the presence of phenylhydrazine, suggesting that the method provides a novel direct process for the preparation of aromatic amines.

Photo-Fries rearrangements of N-acyl-2,3-dihydrobenzoxazol-2-ones are described. Irradiation of N-acyl-2-3-dihydrobenzoxazol-2-ones in acetonitrile afforded a mixture of 2-acyl-2,3-dihydrobenzoxazol-2-one and 6-acyl-2,3-dihydrobenzoxazol-2-one together with other minor products. However, 2,3-dihydrobenzoxazol-2-one and N-methyl-2,3-dihydrobenzoxazol-2-one were very photostable. The reaction scheme involving Norrish type I dissociation has been discussed.

The title compounds 3 were prepared in low yields from the carbylamine reaction of amino-1,3,5-triazines 1 under phase-transfer conditions. Isocyanotriazine 3a readily reacted with amines in the presence of copper salts to afford triazinylformamidines 4, and also with active methylene compounds in the presence of base to afford addition products 5 and 6, indicating the high electrophilicity of 3. The reactions of isocyanotriazine with electrophiles such as carbonyl compounds and bromine are also described.

非対称型ジスアゾ染料合成のための基礎資料と,二つの別々な芳香環にある二つの官能基間の相互作用についての知見を得るため,各種のテトラゾ化ジアミンとR酸(2-ナフトール-3,6-ジスルホン酸)とのアゾカップリング反応の第1段反応の速度定数(k1),第2段反応の速度定数(K2)を分光光度計を用いて測定した。テトラゾ化ベンジジンの場合,K1/K2が約650であるが,ベンジジンの二つのべンゼン環の間に-O-,-S-,-SO-,-SO2-,-CH2-,-CO-などの架橋基を導入すると,K1/K2はかなり小さくなる。しかし,O-トリジン,O-ジアニシジンのテトラゾ化物の場合には大きなK1/K2の値が観測されることがわかった。以上の結果の理由について分光学的資料とも関連して考察を行なった。

17種のジアゾ化複素環式アミンとR酸 (2-ナフトール-3, 6-ジスルホン酸) とのカップリング反応速度を分光光度計を用いて測定し, これらの結果よりピリジル-, キノリル-, チアゾリル-, ベンゾチアゾリル-, トリアゾリル-, テトラゾリル-基などの複素環の置換基定数 (σ-値) を算出した。一般に, 複素環式ジアゾ化合物はベンゼンジアゾニウム塩に比べ速かに反応し, 特に大きな反応性がメチルピリジニウム塩からのジアゾ化合物の場合に認められた。一方, ジアゾ化複素環式アミンとR酸から得られるいくつかの複素環式アゾ化合物について, その解離定数 (pKa) を測定した。そして解離定数におよぼす複素環の効果を, 動力学的結果より得られたσ値と比較し考察した。

オルトあるいはパラ置換ベンゼンジアゾニウム塩 (置換基 : H ,o-, p-CH3, o-, p-C2H5, o-, p-i-C3H7, p-t-C4H9, o-p-Cl, o-, p-NO2, o-, p-OCH3) と R 酸(2-ナフトール-3,6-ジスルホン酸) とのカップリング反応速度を, いくつかの温度で測定し, これら反応の活性化パラメーターを求めた。一連のオルトあるいはパラアルキル置換体において類似の値の速度定数が認められたが, 一連のオルトあるいはバラ置換体において活性化パラメーターはそれぞれかなり変化し, そしてオルト位に置換基を持つジアゾニウム塩は, 対応するパラアルキル置換体より活性化エネルギー, log A 値, ともに低い。これらの結果を溶媒和および補償効果と関連させて考察した。一方, 自由エネルギーの直線関係が適合しうる p-NO2, p-OCH3, p-Cl, p-CH3, H などの置換基を持つベンゼンジアゾニウム塩の場合, 活性化エネルギーと頻度因子間に補償効果は認められなかった。

パラ- (OCH3, CH3, NHCOCH3, Br, Cl, COOCH3, CHO, NO2) あるいはオルトー (OCH3, CH3, COOH, NHCOCH3, Br, Cl, CONH2, CHO, 2,6-(OCH3)2) 置換フェノールとジアゾ化スルファニル酸とのアゾカップリング反応速度を, 分光光度計を用い, 緩衝水溶液中, 20℃ で測定し, 置換基が反応速度におよぼす影響について考察した。一連のパラ-置換フェノールにおいて,log pk と Hammett の σm 値との間の相関関係は得られなかったが, 一方反応速度はフェノール類の pKa 値の増大に伴い増加し, log pk を pKa いわば σp- 値に対してプロットしたところ直線関係が得られた。同様な関係は,一連のオルト-置換フェノール類の場合にも認められた。しかしながら, O-COOH や O-CHO などを置換基とする場合, この関係が成立しない。これは水酸基とこれら置換基間の分子内水素結合のためと推定される。

アリルアゾ基の性質について明らかにするため, 各種のアリルアゾ基を持つベンゼンジアゾニウム塩とR酸 (2-ナフトール-3,6-ジスルホン酸) との反応速度を分光分析により測定し, 各アリルアゾ基の置換基定数を求めた。その結果フェニルアゾ基が +M, -I 効果を呈すること, また置換基効果の伝達に対して大きな絶縁作用を持つことが明らかとなった。また 1-ナフチルアゾ基はフェニルアゾ基に比べてかなりの電子供与性を示し, アゾ結合のオルト位の水酸基は電子吸引基として働くことがわかった。

Triazinylnitrenes were found to be inert towards nitro compounds. They afforded the products derived from the combination of two molecules of the starting materials.

Die pH-Abhangigkeit der Kinetik der Kupplungsreaktionen z.B. von N,N-Dimethyl-N′-acetyl- und -N′-(p-toluol-sulfonyl)-m-phenylendiamin mit p-Methylbenzoldiazoniumsalz sowie von N,N-Dimethyl-N′-benzoyl- und -N′-athoxycarbonyl-m-phenylendiamin mit p-Methoxybenzoldiazoniumsalz wird untersucht.

The diazonio group of arenediazonium salts derived from weakly basic amines were efficiently substituted by hydrogen with alkylbenzenes in sulfuric acid. Several types of evidence, including kinetic results and experiments to trap an intermediate, indicated that the reduction occurs via an aryl radical intermediate. In the reduction with toluene, analyses of by-products suggested a radical chain mechanism, which would involve a propagation cycle caused by electron transfer from the benzyl radical to the diazonio group.

The nucleophilic substitution reactions of 2-methoxy- and 2-diethylamino-4-chloro-6-(2-hydroxy-1-naphthyl)-1,3,5-triazines (1) with aniline, diethylamine, sodium azide, and sodium methoxide were carried out and compared with the reactions of the corresponding derivatives of 4-chloro-6-(4-hydroxy-1-naphthyl)-1,3,5-triazine (2) and 4-chloro-6-(1-naphthyl)-1,3,5-triazine (3). Compound 1 was found to be more reactive than the corresponding (2) and (3), not only in the reactions of a neutral molecule, but also in those of anionic species. The results of the reactions of neutral species are interpreted in terms of the difference in solvation toward the substrates; however, the loss of coplanarity between the naphthalene and triazine nuclei may be responsible for the high reactivity of Compound 1 in the reactions of anionic species.

2-Azido-4,6-dimethoxy-1,3,5-triazine (1a) gave an adduct with pyridine in a molar ratio of 1 : 1. On the contrary, 2-azido-4,6-bis(dimethylamino)-1,3,5-triazine (1b) did not react with pyridine. Similarly, 1a gave an adduct with 3-methylpyridine, whereas in the reactions of 1a with 2-methyl-, 4-methyl-, and 2,6-dimethylpyridines, 2-amino-4,6-dimethoxy-1,3,5-triazine was obtained instead of the adduct. On the other hand, 1a and 1b gave the corresponding triazinyliminophosphoranes with triphenylphosphine.

Triazinylnitrene generated photochemically from 2-azido-4,6-dimethoxy-1,3,5-triazine adds to the aromatic ring of alkylbenzenes and halobenzenes to give N-triazinylazepines.

Di-1,3,5-triazinyl ethers have been prepared by the condensation of 2-chloro-1,3,5-triazines with potassium 1,3,5-triazin-2-olate in acetonitrile in the presence of a small amount of cyclic polyether. Di-1,3,5-triazinyl ether was also prepared by the reaction of 2-chloro-1,3,5-triazine with potassium nitrite.

The stability constants for 18-crown-6 complexes with arenediazonium salts have been determined spectrophotometrically. The Hammett plot for m- and p-substituted benzenediazonium salts showed good correlation with a reaction constant 0.98 in methanol. The solvent effect on the stability of the complexes has been discussed.

Triazinylnitrene generated photochemically from 2-azido-4,6-dimethoxy-1,3,5-triazine adds to the aromatic ring of alkylbenzenes and halobenzenes to give N-triazinylazepines.

Triazinylnitrenes were found to be inert towards nitro compounds. They afforded the products derived from the combination of two molecules of the starting materials.