诺蒎酮的合成工艺研究

doi:10.3969/j.issn.0253-2417.2020.02.017

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (2): 125-130.doi: 10.3969/j.issn.0253-2417.2020.02.017

• 研究报告 • 上一篇

诺蒎酮的合成工艺研究

石云飞¹,张桧²,钟旭阳¹,段欣颖¹,陈淑兰¹,廖圣良^1,*()

1. 江西农业大学林学院; 国家林业和草原局木本香料(华东)工程技术研究中心; 国家林业和草原局/江西省樟树工程技术研究中心; 江西特色林木资源培育与利用协同创新中心, 江西南昌 330045
2. 江西省林业科技推广总站, 江西南昌 330038

收稿日期:2019-07-29 出版日期:2020-04-28 发布日期:2020-04-27
通讯作者: 廖圣良 E-mail:alexliao24@163.com
作者简介:石云飞(1993—),女,河南鹿邑人,硕士生,主要从事植物精油衍生物合成研究
基金资助:
国家自然科学基金青年基金项目(31800493);江西省林业科技创新项目(201807);江西省教育厅科学技术研究项目(GJJ170255)

The Optimization of Synthesis Process of Nopinone

Yunfei SHI¹,Hui ZHANG²,Xuyang ZHONG¹,Xinying DUAN¹,Shulan CHEN¹,Shengliang LIAO^1,*()

1. College of Forestry, Jiangxi Agricultural University; East China Woody Fragrance and Flavor Engineering Research Center of National Forestry and Grassland Administration; Camphor Engineering Research Center of National Forestry and Grassland Administration, Jiangxi Province; Collaborative Innovation Center of Jiangxi Typical Trees Cultivation and Utilization, Nanchang 330045
2. Jiangxi Forestry Science and Technology Extension Station, Nanchang 330038, China

Received:2019-07-29 Online:2020-04-28 Published:2020-04-27
Contact: Shengliang LIAO E-mail:alexliao24@163.com

摘要/Abstract

摘要：

对β-蒎烯氧化制备诺蒎酮的合成工艺进行优化，探讨了反应时间、反应温度、催化剂类型及用量、氧化剂类型及用量和溶剂种类等因素对反应转化率和选择性的影响。研究结果显示：5.00 g β-蒎烯，3 mL 2 mol/L H₂SO₄，反应时间为3 h，反应温度为21~24 ℃，催化剂为十六烷基三甲基溴化铵（CTAB），用量0.20 g，氧化剂为高锰酸钾，n（高锰酸钾）:n（β-蒎烯）为3.2:1，溶剂为丙酮，在机械搅拌条件下，诺蒎酮合成反应的转化率达99.5%，选择性高达92.2%。

关键词: β-蒎烯, 氧化, 诺蒎酮, 相转移催化剂

Abstract:

Nopinone is an important forest derivative derived from the oxidation reaction of β-pinene, which is of great significance for further deep processing and utilization of naloxone.In this paper, the optimization for the synthesis process of nopinone from β-pinene was studied.The effects of reaction time, reaction temperature, type and amount of catalyst, n(potassium permanganate):n(β-pinene), type of oxidant, solvent type on reaction conversion and selectivity were discussed.The results showed that when the reaction time was 3 h, the reaction temperature was 21-24℃, the catalyst was cetyltrimethylammonium bromide (CTAB), the amount of catalyst was 0.20 g, the molar ratio of potassium permanganate to β-pinene was 3.2:1, using potassium permanganate as oxidant, acetone as solvent, the conversion rate of the synthesis reaction of nopinone is 99.5%, and the selectivity is 92.2%.

Key words: β-pinene, oxidation, nopinone, phase transfer catalyst

中图分类号:

TQ35
TQ463.2

石云飞,张桧,钟旭阳,段欣颖,陈淑兰,廖圣良. 诺蒎酮的合成工艺研究[J]. 林产化学与工业, 2020, 40(2): 125-130.

Yunfei SHI,Hui ZHANG,Xuyang ZHONG,Xinying DUAN,Shulan CHEN,Shengliang LIAO. The Optimization of Synthesis Process of Nopinone[J]. Chemistry and Industry of Forest Products, 2020, 40(2): 125-130.

图/表 5

图1

表1

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表3

图2

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β-蒎烯/g β-pinene	氧化体系oxidation system¹⁾		催化剂²⁾/g catalyst	溶剂³⁾/ mL solvent	反应时间/h reaction time	温度/℃ temp.	转化率% conversion rate	选择性/% selectivity
β-蒎烯/g β-pinene	氧化剂 oxidant	用量/g dosage	催化剂²⁾/g catalyst	溶剂³⁾/ mL solvent	反应时间/h reaction time	温度/℃ temp.	转化率% conversion rate	选择性/% selectivity
5.14	KMnO₄	17.32	0	25	6	8~15	87.4	82.7
5.08	KMnO₄	15.02	1.05	25	22	6~15	84.2	27.2
5.13	KMnO₄	13.83	1.05	50	7	12~15	92.3	68.3
5.04	KMnO₄	14.60	1.10	50	24	5~10	86.6	85.7
4.94	K₂CrO₇	13.27	0	50	24	11~15	28.1	42.3
5.02	K₂CrO₇	13.57	1.24	50	22	11~15	14.4	50.2
5.10	KMnO₄	13.63	0	0	22	11~15	32.7	26.8

反应条件¹⁾ condations		转化率/% conversion rate	选择性/% selectivity
温度 temperature	6~10 ℃	94.5	89.0
	15~17 ℃	98.8	86.8
	21~24 ℃	98.5	87.7
	36~38 ℃	95.1	85.4
反应时间 reaction time	2 h	98.8	84.5
	3 h	98.9	87.9
	4 h	98.9	84.2
	5 h	98.9	79.4
	6 h	99.0	71.3
	7 h	99.2	83.9
催化剂类型 catalysttype	DTAB	98.9	85.2
	CTAB	96.4	89.6
	BETAB	98.3	89.3
	TBAB	93.2	86.7
	18-冠醚-6 18-crown ether-6	90.2	88.1
催化剂用量 dosage of catalyst	0.2 g	96.4	89.6
	0.4 g	94.6	88.7
	0.6 g	96.4	89.8
	0.8 g	94.6	88.1
	1.0 g	97.3	88.6
1) DTAB:十二烷基三甲基溴化铵dodecyl trimethyl ammonium bromides; CTAB:十六烷基三甲基溴化铵cetyl trimethyl ammonium bromide; BETAB:2-溴乙基三甲基溴化铵(2-bromoethyl)trimethylammonium bromide; TBAB:四丁基溴化铵tetrabutyl ammonium bromide

n(KMnO₄): n(β-蒎烯) n(KMnO₄): n(β-pinene)	转化率/% conversion rate	选择性/% selectivity
2.7:1	95.3	88.3
2.9:1	98.5	87.7
3.0:1	98.8	89.3
3.2:1	99.6	91.2

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诺蒎酮的合成工艺研究

The Optimization of Synthesis Process of Nopinone

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