3-对䓝烯-1-胺的合成工艺研究

doi:10.3969/j.issn.0253-2417.2019.05.009

Chemistry and Industry of Forest Products ›› 2019, Vol. 39 ›› Issue (5): 67-72.doi: 10.3969/j.issn.0253-2417.2019.05.009

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Synthetic Technology of p-Menth-3-en-1-amine

Huanhuan DONG^1,²,Shichao XU^1,^2,³,Jing WANG^1,^2,^3,⁴,Hongmei ZHANG^1,²,Xiaojing ZENG^1,²,Yuxiang CHEN^1,^2,³,Zhendong ZHAO^1,^2,^3,*()

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China
3. Research Institute of Forestry New Technology, CAF, Beijing 100091, China
4. College of Materials Science and Technology, Beijing Forestry University, Beijing 100083, China

Received:2019-06-24 Online:2019-10-25 Published:2019-11-01
Contact: Zhendong ZHAO E-mail:zdzhao@189.cn
Supported by:
国家自然科学基金资助项目(31870557);国家自然科学基金资助项目(31600466);中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2018SZ012)

Abstract

Abstract:

p-Menth-3-en-1-amine was synthesized from p-menthane diacetylamide by two steps as an acid-catalyzed elimination and an alkaline-catalyzed hydrolysis. The effects of different conditions on these reactions were studied by single-factor and orthogonal tests. The optimal reaction conditions of the acid-catalyzed elimination are shown as 20 mmol p-menthane diacetylamide, 35 mL 12.5% H₂SO₄ solution (24 mmol) and reaction time 8 h, under which the yield is 41.6%; And the optimized technological parameters of the alkaline-catalyzed hydrolysis are shown as n(N-diacetyl-3-en-1-amine):n(NaOH) 1:7, 30 mL ethylene glycol as the solvent, reaction time 11 h and reaction temperature 170 ℃, to give N-diacetyl-3-en-1-amine in a yield of 82.2%, total yield is 34.2%, purified to 97% by vacuum rectification. The structure of the compound was determined by ESI-MS, FT-IR, ¹H NMR and ¹³C HMR spectroscopic analyses.

Key words: monoterpene derivative, 1, 8-p-menthanediacetylamide, p-menth-3-en-1-amine

CLC Number:

TQ35

Huanhuan DONG,Shichao XU,Jing WANG,Hongmei ZHANG,Xiaojing ZENG,Yuxiang CHEN,Zhendong ZHAO. Synthetic Technology of p-Menth-3-en-1-amine[J]. Chemistry and Industry of Forest Products, 2019, 39(5): 67-72.

Figures/Tables 8

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项目 items		转化率/% transformation rate	产率/% yield
催化剂种类 catalyst type	20%CH₃COOH	痕量tr.	痕量tr.
	10%HCl	76.2	26.7
	10%H₂SO₄	85.6	38.2
反应温度 temperature	40 ℃	痕量tr.	痕量tr.
	60 ℃	痕量tr.	痕量tr.
	80 ℃	60.8	8.0
	105~110 ℃	93.6	41.6

序号 No.	A n(单酰胺): n(氢氧化钠) n(N-diacetyl-3-en-1-amine): n(NaOH)	B 反应时间/h time	C 反应温度/℃ temp.	产率/% yield
1	1:5	11	160	59.4
2	1:5	13	170	68.2
3	1:5	15	180	58.3
4	1:7	15	160	65.2
5	1:7	11	170	89.9
6	1:7	13	180	76.2
7	1:9	13	160	62.2
8	1:9	15	170	69.1
9	1:9	11	180	72.6
k₁	62.0	74.0	62.3
k₂	77.1	68.9	75.7
k₃	68.0	64.2	69.0
R	15.1	9.8	13.4

Synthetic Technology of p-Menth-3-en-1-amine

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