甲基柏木酮O-取代肟类化合物的合成与表征

doi:10.3969/j.issn.0253-2417.2019.06.005

Abstract

Abstract:

Six novel methyl cedrone O-substituted oximes were synthesized by the alkylation reaction using methyl cedrone oxime (16-methyl-2, 6, 6, 8-tetramethyl tricyclic-8-enone oxime) and halides as raw materials:16-methyl-2, 6, 6, 8-tetramethyltricyclo-8-enone O-benzyl oxime (2a), 16-methyl-2, 6, 6, 8-tetramethyltricyclo-8-enone O-(4-chlorobenzyl) oxime (2b), 16-methyl-2, 6, 6, 8-tetramethyltricyclo-8-enone O-(4-cyanobenzyl) oxime (2c), 16-methyl-2, 6, 6, 8-tetramethyltricyclo-8-enone O-(2, 6-dichlorobenzyl) oxime (2d), 16-methyl-2, 6, 6, 8-tetramethyltricyclo-8-enone O-(4-tert-butylbenzyl) oxime (2e), 16-methyl-2, 6, 6, 8-tetramethyltricyclo-8-enone O-(o-fluorobenzyl) oxime (2f). The structures of the products were identified by FT-IR, GC-MS, ¹H NMR and ¹³C NMR. Taking benzyl chloride as an example, the effects of solvents, the amount of tetrabutyl ammonium bromide(TBAB) and benzyl chloride, the reaction temperature and reaction time on the conversion and yield of 2a were discussed. The optimum condition was obtained as follows:toluene as solvent, n(methyl cedrone oxime):n(TBAB):n(benzyl chloride)=1.0:0.12:1.4, the reaction temperature was 70℃, the reaction time was 24 h. Under the optimal condition, the yield of product 2a was 78.10%, the yield of 2b-2f ranged from 58.91% to 71.36%.

Key words: methyl cedrone oxime, alkylation reaction, oxime ether, structure characterization

CLC Number:

TQ35
O621

Xia ZHANG,Yiming LUO,Jing HUANG,Chenjing LIU,Jinyue LUO. Synthesis and Characterization of Methyl Cedrone O-substituted Oximes[J]. Chemistry and Industry of Forest Products, 2019, 39(6): 37-43.

Figures/Tables 3

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Table 1

Table 2

References 13

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项目 items		反应转化率/% reaction conversion	反应选择性/% reaction selectivity	得率/% yield
溶剂种类 solvent type	N, N-二甲基甲酰胺DMF	53.32	81.51	43.46
	二甲亚砜DMSO	92.61	72.94	67.55
	乙腈acetonitrile	95.44	64.63	61.68
	甲苯toluene	96.33	73.92	71.21
	丙酮acetone	99.12	65.25	64.68
n(甲基柏木酮肟):n(四丁基溴化铵) n(methyl cedrone oxime):n(TBAB)	1.0:0.06	61.71	56.36	34.77
	1.0:0.08	79.90	61.06	48.78
	1.0:0.10	96.39	73.92	71.25
	1.0:0.12	97.83	78.72	77.01
	1.0:0.14	98.17	74.73	73.36
	1.0:0.16	98.42	69.21	68.12
n(甲基柏木酮肟):n(苄基氯) n(methyl cedrone oxime): n(benzyl chloride)	1.0:1.0	70.82	63.69	45.11
	1.0:1.2	84.60	70.52	59.66
	1.0:1.4	95.92	75.47	72.39
	1.0:1.6	97.83	78.72	77.01
	1.0:1.8	98.27	77.64	76.30
	1.0:2.0	97.59	76.30	74.46
反应温度 reaction temperature	40 ℃	52.67	43.58	22.95
	50 ℃	89.73	71.39	64.06
	60 ℃	97.30	77.42	75.33
	70 ℃	97.83	78.72	77.01
	80 ℃	98.23	76.01	74.66
反应时间 reaction time	16 h	61.44	43.26	26.57
	18 h	82.31	64.73	53.28
	20 h	94.62	73.21	69.27
	22 h	97.30	77.42	75.33
	24 h	98.10	79.08	77.58
	26 h	98.51	75.22	74.10

序号 No.	A n(甲基柏木酮肟):n(四丁基溴化铵) n(methyl cedrone oxime): n(TBAB)	B n(甲基柏木酮肟):n(苄基氯) n(methyl cedrone oxime): n(benzyl chloride)	C 反应温度/℃ reaction temperature	D 反应时间/h reaction time	得率/% yield
1	1.0:0.10	1.0:1.4	50	22	65.81
2	1.0:0.10	1.0:1.6	60	24	70.85
3	1.0:0.10	1.0:1.8	70	26	69.17
4	1.0:0.12	1.0:1.4	60	26	74.93
5	1.0:0.12	1.0:1.6	70	22	74.21
6	1.0:0.12	1.0:1.8	50	24	72.46
7	1.0:0.14	1.0:1.4	70	24	76.32
8	1.0:0.14	1.0:1.6	50	26	70.13
9	1.0:0.14	1.0:1.8	60	22	73.25
k₁	68.61	72.35	69.47	71.09
k₂	73.87	71.73	73.01	73.21
k₃	73.23	71.63	73.23	71.41
R	5.26	0.72	3.76	2.12

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Synthesis and Characterization of Methyl Cedrone O-substituted Oximes

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