文献类型：期刊文献

中文题名：3,6,6-三甲基-2,4-环庚二烯酮的制备

英文题名：Preparation of 3,6,6-Trimethylcyclohepta-2,4-dienone

作者：王婧[1,3] 曾小静[1] 董欢欢[1] 徐士超[1,2] 蒋建新[3] 赵振东[1,2]

第一作者：王婧

通信作者：Zhao, Zhen-Dong

机构：[1]中国林业科学研究院林产化学工业研究所生物质化学利用国家工程实验室国家林业局林产化学工程重点开放性实验室江苏省生物质能源与材料重点实验室,江苏南京210042;[2]中国林业科学研究院林业新技术研究所,北京100091;[3]北京林业大学材料科学与技术学院,北京100083

年份：2019

卷号：0

期号：8

起止页码：1715-1721

中文期刊名：精细化工

外文期刊名：Fine Chemicals

收录：CSTPCD;;EI(收录号：20193807451391);Scopus;北大核心:【北大核心2017】；CSCD:【CSCD2019_2020】；

基金：江苏省生物质能源与材料重点实验室基本科研业务费项目(JSBEM-S-201709)

语种：中文

中文关键词：3-蒈烯;3,6,6-三甲基-2,4-环庚二烯酮;CrO3;烯丙位氧化;3-蒈烯-5-酮;精细化工中间体

外文关键词：3-carene;3,6,6-trimethylcyclohepta-2,4-dienone;CrO3;allylic oxidization;car-3-ene-5-one;fine chemical intermediates

分类号：TQ651.1

摘要：将CrO3通过浸渍法负载于中性Al2O3上,制备得到CrO3-Al2O3,利用其催化3-蒈烯的氧化反应。反应主要生成3种α,β-不饱和酮。考察了催化剂用量、温度、时间以及氧气流量对氧化反应的影响,得到最佳氧化工艺为:CrO3-Al2O3用量为3-蒈烯质量的3%、温度25℃、时间10 h以及氧气流量25 mL/min,对应原料转化率58.72%,α,β-不饱和酮类化合物总选择性86.07%(3-蒈烯-2-酮19.83%、2-蒈烯-4-酮4.61%、3-蒈烯-5-酮61.63%)。在减压精馏分离氧化产物过程中,3-蒈烯-5-酮极易异构转化为3,6,6-三甲基-2,4-环庚二烯酮,一步实现了该产物的制备与提纯,但是3-蒈烯-2-酮和2-蒈烯-4-酮不发生类似异构。结果证明,减压是异构发生的必要条件,压力越小,反应越容易进行且效果越好。0.5 kPa压力下,120℃反应4 h,3-蒈烯-5-酮转化率99.62%,3,6,6-三甲基-2,4-环庚二烯酮选择性98.15%,表明压力达到0.5 kPa即可满足反应要求。
CrO3-Al2O3 was prepared by loading CrO3 on neutral alumina by impregnation method and used as catalyst for the oxidation of 3-carene.The oxidation process mainly produced three differentα,β-unsaturated ketones.The effects of catalyst amount,temperature,time and oxygen flux on the oxidation were investigated.The optimum oxidation process was established as that catalyst amount was 3%of the mass of 3-carene,temperature was 25℃,time was 10 h and oxygen flux was 25 mL/min.Under the optimum process,the raw material conversion was 58.72%,and the total selectivity ofα,β-unsaturated ketones was 86.07%(car-3-ene-2-one 19.83%,car-2-ene-4-one 4.61%and car-3-ene-5-one 61.63%).During the separation of the oxidation product by vacuum rectification,car-3-ene-5-one was very easily isomerized and converted into 3,6,6-trimethylcyclohepta-2,4-dienone and the product was prepared and purified in one step.However,similar isomerization reactions did not happened for car-3-ene-2-one and car-2-ene-4-one in this process.The results showed that reduced pressure was a necessary condition for isomerization,and the lower the pressure,the easier the reaction would occur,and the better the effect would be.A conversion of 99.62%for car-3-ene-5-one and a selectivity of 98.15%for 3,6,6-trimethylcyclohepta-2,4-dienone were obtained when the pressure was 0.5 kPa,temperature was 120℃and time was 4 h,which indicated that a pressure of 0.5 kPa completely satisfied the reaction requirement.