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本文报告2,2-双羟亚环己基乙酸内酯(Ⅱ)和2-羟基亚环己基乙酸内酯(Ⅲ)中内酯环打开的工作,尤其2-氧代-顺-亚环己基乙酰肼类化合物的制备及其环化和重排的研究结果。Ⅱ与肼作用得5,6,7,8-四氢邻二氮杂萘酮-(3)(Ⅳa),与苯肼作用则得2-氧代-顺-亚环己基乙酰苯肼(Ⅵ)。Ⅵ经热、酸或碱处理易脱水环化,并发生重排而成2-苯基-5,6,7,8-四氢邻二氮杂蓁酮-(3)(ⅩⅥa)。ⅩⅥa的结构式是根据其紫外及杠外吸收光谱和活泼氢的测定而确定。本文中提出重排的可能机理。Ⅱ与1,1-苯甲基苯肼或1,1-二甲基肼作用则分别得2-氧代-顺-亚环己基乙酰苯甲基苯肼(Ⅶ)和2-氧代-顺-亚环己基乙酰二甲基肼(Ⅷ),Ⅷ与氨基脲先形成2-氧代-顺-亚环己基乙酰氨基脲(Ⅸ),进而变成Ⅳa。而2-氧代-反-亚环己基乙酸(Ⅹ)与苯肼反应则生2-氧代-反-亚环己基乙酸苯腙(Ⅺ)。Ⅱ于甲醇中与重氮甲烷生成ⅩⅢ,再与苯肼作用获得2′-氧代-环己烷-(1′-螺-4)-4,5-双氢呲唑-3-甲酰苯肼(ⅩⅣ)。Ⅲ与S-苯甲基硫脲盐酸盐、苯甲胺和甲醇钠的甲醇溶液分别作用都未获得预期的顺烯构型产物,而得到异构化的2-氧代-环己基乙酸的S-苯甲基硫脲盐(ⅩⅩ),2-苯甲亚胺环己基乙酰苯甲胺(ⅩⅪ)和2-氧代-环己基乙酸甲酯(ⅩⅫ)。Ⅲ的开环化合物极易重排为2-氧代-环己基乙酸衍生物,而Ⅱ的开环化合物的酮基极不活泼。
This paper reports the opening of the lactone ring in 2,2-bishydroxycyclohexaneacetolactone (II) and 2-hydroxycyclohexyleneacetolactone (III), especially the 2-oxo-cis-cyclohexylideneacetyl Preparation of hydrazines and their cyclization and rearrangement studies. Hydrochloric acid can react with hydrazine to produce 5,6,7,8-tetrahydrophthalazinone - (3) (Ⅳa). When phenylhydrazide interacts with 2-oxo-cis-cyclohexylideneacetylhydrazide ). Ⅵ by dehydration after acid, acid or alkali dehydration cyclization, and the rearrangement of 2-phenyl-5,6,7,8-tetrahydrophthazantrone - (3) (XVIa). The formula of XVIa is based on its UV and extra-rod absorption spectra and the determination of active hydrogen. In this paper, the possible mechanism of rearrangement is proposed. Ⅱ and 1,1-phenyl-phenyl-phenyl hydrazine or 1,1-dimethyl hydrazine were obtained 2-oxo-cis - cyclohexyl acetophenone phenylhydrazine (Ⅶ) and 2-oxo- cis - cyclohexylidenethyldimethylhydrazine (VIII), VIII and semicarbazide to form 2-oxo-cis-cyclohexylidene semicarbazide (IX), which in turn becomes IVa. The reaction of 2-oxo-trans-cyclohexylideneacetic acid (X) with phenylhydrazine gave the 2-oxo-trans-cyclohexylideneacetic acid hydrazone (XI). Ⅱ in methanol with diazomethane to generate XIII, and then with phenylhydrazine to obtain 2’-oxo-cyclohexane- (1’-spiro-4) -4,5- Hydrazine (XIV). III and S-phenylthiosemicarbazide hydrochloride, and benzylamine and sodium methoxide in methanol respectively did not give the expected cis-isomeric products to give isomerized 2-oxo-cyclohexyl-acetic acid S-benzylthiourea salt (XX), 2-benzimidocyclohexylacetophenylamine (XXI) and methyl 2-oxo-cyclohexyl acetate (XXII). The ring-opened compounds of III are easily rearranged to 2-oxo-cyclohexyl acetic acid derivatives, while the ketone groups of ring-opened compounds of II are extremely inactive.