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柠檬腈的光氧化和酯化得到二个新的香料化合物:2,6-二甲基-7-氰基-3,6-二烯庚醇-2和2-甲基-6-甲酰基-1,5-二烯庚醇-3的乙酸酯(6,7)。发现在柠檬腈的烯型反应产物中,叔醇异构体2的含量特别低。化合物7的前体α-甲醛基四氢呋喃4可能经2的烯酮氧化机理生成。为肯定所提机理,经与2,3-二苯基-对已二氧烯-2的光氧化速率常数比较,测定柠檬腈、乙酸芳樟酯的消失反应速率常数,并利用顺、反柠檬腈中C-1双键光氧化的四翼相关图解释了所观察的现象,顺、反柠檬腈反应速率常数的差异为单重态氧烯型反应的分步机理提供了一个新的佐证。
Photo-oxidation and esterification of lemonitrile resulted in two new perfume compounds: 2,6-dimethyl-7-cyano-3,6-dienoheptan-2 and 2-methyl-6-formyl- 1,5-dienol-3 acetate (6,7). It was found that the content of tertiary alcohol isomer 2 is particularly low in the olefinic reaction product of limonitrile. The precursor of compound 7, α-carboxyphenyltetrahydrofuran 4, may be generated via the 2 ketene oxidation mechanism. To affirm the proposed mechanism, the rate constants of the disappearance of citric acid and linalyl acetate were determined by comparison with the photooxidation rate constants of 2,3-diphenyl-p-dioxole-2. The four-wing correlation diagram for photooxidation of the C-1 double bond in the nitrile explains the phenomenon observed, and the difference in cis- and anti-limonitrile reaction rate constants provides a new evidence for the step-by-step mechanism of the singlet oxygenation reaction.