有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
シアノ酢酸並びにモノクロル酢酸のエステル化反応
α-シアノアクリル酸エステルの研究(第3報)
米沢 正次鈴木 重成伊藤 博夫伊藤 健治
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1966 年 24 巻 7 号 p. 580-587

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Esterif ication of cyanoacetic acid at 60.. in the absence of catalyst with various alcohols occured in the following order of readiness : methyl>ethyl>n-butyl>2-ethylhexyl>isobutyl>allyl>2-methoxyethyl . The reaction velocities, however, did not vary from each other to a significant extent except those for allyl alcohol and 2-methoxyethyl alcohol. The esterif ication reaction proceeded as a 2 nd order reaction for the cyanoacetic acid concentration, and the apparent activation energies for methyl alcohol, ethyl alcohol, allyl alcohol, isopropyl alcohol, 2-methoxyethyl alcohol, n-butyl alcohol, isobutyl alcohol, and 2-ethylhexyl alcohol were calculated to be 13.6, 14.6, 19.8, 22.8, 17.1, 17.4, 17.0, and 18.6, kcal/mol, respectively. Under the same conditions, esterif ication of monochloroacetic acid occured in the following order of readiness : methyl>n-butyl>ethyl>2-ethylhexyl> allyl> 2-methoxyethyl>isopropyl. The reaction was also of the 2 nd order for the concentration of mono-chloroacetic acid . The apparent activation energies for methyl alcohol, ethyl alcohol, allyl alcohol, isopropyl alcohol, 2-methoxyethyl alcohol, n-butyl alcohol, and 2-ethylhexyl alcohol were calculated to be 14.3, 16.4, 16.6, 22.9, 21.0, 16.3, and 15.6 kcal/mol, respectively. In the presence of sulfuric acid, esterification proceeded with ease and a quantitative yield was attained when benzene was used for the azeotropic removal of water.

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