Page 227 - 精细化工2019年第8期

第 36 卷第 8 期 精 细 化 工 Vol.36, No.8
201 9 年 8 月 FINE CHEMICALS Aug. 2019

精细化工中间体
3,6,6-三甲基-2,4-环庚二烯酮的制备

1
1
3
王 婧 1,3 ，曾小静 ，董欢欢 ，徐士超 1,2 ，蒋建新 ，赵振东 1,2*
（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）

摘要：将 CrO 3 通过浸渍法负载于中性 Al 2 O 3 上，制备得到 CrO 3 -Al 2 O 3 ，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：CrO 3 -Al 2 O 3 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。
关键词：3-蒈烯；3,6,6-三甲基-2,4-环庚二烯酮；CrO 3 ；烯丙位氧化；3-蒈烯-5-酮；精细化工中间体
中图分类号：TQ35 文献标识码：A 文章编号：1003-5214 (2019) 08-1715-07

Preparation of 3,6,6-Trimethylcyclohepta-2,4-dienone

1,2
1
1,3
1
WANG Jing , ZENG Xiao-jing , DONG Huan-huan , XU Shi-chao ,
3
JIANG Jian-xin , ZHAO Zhen-dong 1,2*
（1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical
Utilization, Key and Open Lab. of Forest Chemical Engineering, SFA; Key Lab. of Biomass Energy and Material,
Jiangsu Province, Nanjing 210042, Jiangsu, China; 2. Research Institute of Forestry New Technology, CAF, Beijing
100091, China; 3. College of Materials Science and Technology, Beijing Forestry University, Beijing 100083, China）
Abstract: CrO 3-Al 2O 3 was prepared by loading CrO 3 on neutral alumina by impregnation method and used
as catalyst for the oxidation of 3-carene. The oxidation process mainly produced three different
α,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 of α,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.

收稿日期：2018-11-22; 定用日期：2019-03-13; DOI: 10.13550/j.jxhg.20180862
基金项目：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）
作者简介：王 婧（1983—），女，助理研究员，博士生。联系人：赵振东（1960—），男，研究员，E-mail：zdzhao@189.cn。