取代-2-羟甲基苯甲酰胺和-1 亚氨基-1,3-二氢异苯并呋喃的合成(英文)

Synthesis of the substituted 2-hydroxymethylbenzamide and 1-imino-1,3-dihydro isobenzofuran

取代苯酞在三乙胺 /三氯化铝存在下氨解生成取代 2 羟甲基苯甲酰胺 (3)和 1 亚氨基 1 ,3 二氢异苯并呋喃 (4)。苯酞 3 位以环状 /非环状基团取代可能影响反应过程和产物的生成 ,当回流反应时只生成产物 4 ,不生成产物 3,且 4的收率很低。 1 苄亚氨基 3,3 二取代 1 ,3 二氢异苯并呋喃在空气中能缓慢氧化为相应氢过氧化物。氢过氧化物结构用光谱法、化学分析法和单晶X 射线衍射确证 ,并推测了生成氢过氧化物的机理。化合物 7m的1H NMR表明δ 6 34处有一单峰 ,归属为PhCHOOH氢质子 ,HMBC表明δ 92 81处有吸收峰 ,归属为NCH(OOH)Ph碳质子 ,IR表明 84 5cm-1有吸收峰 。

Substituted 2 hydroxymethylbenzamides(3)and 1 imino 1,3 dihydro isobenzofurans(4)have been obtained by aminolysis of phthalides in the presence of triethylamine/aluminium chloride.The disposition of the groups at 3 position of phthalides may affect the reaction course and the formation of products.When the reaction was carried out under reflux products 4 rather than 3 were obtained in comparatively low yields.1 Benzylimino 3,3 disubstituted 1,3 dihydro isobenzofurans can be slowly peroxidized to the corresponding hydroperoxides on exposure to air.The structures were characterized by spectral and chemical analyses and a single crystal X ray diffraction.A possible mechanism was suggested.For compound 7m one singlet was at δ=6 34,corresponding to the proton of PhCHOOH. 13 C COSY(HMBC)revealed that the proton signal at 92 81 belonged to the carbon atom of NCH(OOH)Ph.The IR spectrum of 7m,showed one band of —O—O— at 845 cm -1 .