{"title":"次氯酸盐与硝基乙烷反应对氢氧化物的反动力学依赖","authors":"R. Lii, Sidney I. Miller","doi":"10.1039/J29710002271","DOIUrl":null,"url":null,"abstract":"In strong aqueous base, pH > 11, the catalysed chlorination of nitroethane (N) obeys the rate law, v=k[N]0[ClO–][OH–]–1. These kinetics are consistent with a rate-determining attack of either hypochlorite on the nitronic acid (A)kA= 1·8 × 108 l mol–1 s–1, or hypochlorous acid on nitronate (C–)k8≃ 1·5 × 105 l mol–1 s–1, at 25°C. A rationale is provided for the fact that the usual second-order kinetics for deprotonation of N do not apply to this halogenation of a nitro-alkane.","PeriodicalId":17268,"journal":{"name":"Journal of The Chemical Society B: Physical Organic","volume":"7 1","pages":"2271-2272"},"PeriodicalIF":0.0000,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":"{\"title\":\"Inverse kinetic dependence on hydroxide in the reaction of hypochlorite with nitroethane\",\"authors\":\"R. Lii, Sidney I. Miller\",\"doi\":\"10.1039/J29710002271\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"In strong aqueous base, pH > 11, the catalysed chlorination of nitroethane (N) obeys the rate law, v=k[N]0[ClO–][OH–]–1. These kinetics are consistent with a rate-determining attack of either hypochlorite on the nitronic acid (A)kA= 1·8 × 108 l mol–1 s–1, or hypochlorous acid on nitronate (C–)k8≃ 1·5 × 105 l mol–1 s–1, at 25°C. A rationale is provided for the fact that the usual second-order kinetics for deprotonation of N do not apply to this halogenation of a nitro-alkane.\",\"PeriodicalId\":17268,\"journal\":{\"name\":\"Journal of The Chemical Society B: Physical Organic\",\"volume\":\"7 1\",\"pages\":\"2271-2272\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1971-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"1\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of The Chemical Society B: Physical Organic\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1039/J29710002271\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of The Chemical Society B: Physical Organic","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1039/J29710002271","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 1
摘要
在pH为bbbb11的强水中，硝基乙烷(N)的催化氯化反应遵循v=k[N]0[ClO -][OH -] - 1的速率规律。这些动力学与25℃下次氯酸对硝酸(a)kA= 1·8 × 108 l mol-1 s-1或次氯酸对硝酸(C -)k8≃1·5 × 105 l mol-1 s-1的速率决定作用相一致。通常的N去质子化的二级动力学不适用于硝基烷烃的卤化，这一事实提供了一个基本原理。
Inverse kinetic dependence on hydroxide in the reaction of hypochlorite with nitroethane
In strong aqueous base, pH > 11, the catalysed chlorination of nitroethane (N) obeys the rate law, v=k[N]0[ClO–][OH–]–1. These kinetics are consistent with a rate-determining attack of either hypochlorite on the nitronic acid (A)kA= 1·8 × 108 l mol–1 s–1, or hypochlorous acid on nitronate (C–)k8≃ 1·5 × 105 l mol–1 s–1, at 25°C. A rationale is provided for the fact that the usual second-order kinetics for deprotonation of N do not apply to this halogenation of a nitro-alkane.
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