油酸甲酯烯烃交叉复分解制备烯烃化学品中底物影响机制探究

doi:10.3969/j.issn.0253-2417.2021.03.002

Abstract

Abstract:

The long-chain terminal olefin compounds 1-decene(CM1) and methyl 9-decenoate(CM2) were prepared through olefin cross-metathesis of methyl oleate(MO) with low olefin substrate. The second-generation Hoveyda-Grubbs catalyst was screened out from 4 typical ruthenium-catalyst through the self-metathesis of methyl oleate. The catalytic mechanism was discussed with 4 substrates, then the proposed mechanism was verified by 6 substrates. The results suggested that the short-chain substrates containing electron-rich and bulk-large group like styrene, eugenol and allyl trimethylsilane were beneficial for the preparation of terminal olefin products, since the property of aromatic group, which could chelate with central metal and formed the key ring intermediate, so that it changed the route of reaction and prepared the highly-selectivity of the aim product yield.

Key words: methyl oleate, olefin cross-metathesis, ruthenium-complex catalyst, α-olefin, methyl 9-decenoate

CLC Number:

TQ35
S216

Hengyi SHU, Zhifeng ZHENG, Shouqing LIU, Hongzhou HE, Yuanbo HUANG. Effect Mechanism of Substrates on Cross-metathesis Reaction for Preparation of Long-chain Terminal Olefin Chemicals from Methyl Oleate[J]. Chemistry and Industry of Forest Products, 2021, 41(3): 11-18.

Figures/Tables 9

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催化剂 catalyst	不同反应时间下MO转化率/% MO conversion of diverse reaction time
催化剂 catalyst	10 min	20 min	40 min
C1	0	0	0
C2	63	56	53
C3	63	68	62
C4	0	0	0

烯烃底物 olefin substrate	MO转化率MO conversion/%			CM1产率CM1 yield/%			CM2产率CM2 yiled/%
烯烃底物 olefin substrate	0 ℃	30 ℃	50 ℃	0 ℃	30 ℃	50 ℃	0 ℃	30 ℃	50 ℃
烯丙基缩水甘油醚 allyl glycidyl ether	30	27	29	3	2	2	2	2	2
2-甲氧基丙烯 2-methoxypropylene	51	59	50	0	0	0	0	0	0
苯乙烯styrene	59	54	54	37	29	26	35	28	24
氯丙烯allyl chloride	67	57	82	17	17	4	18	18	6

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Effect Mechanism of Substrates on Cross-metathesis Reaction for Preparation of Long-chain Terminal Olefin Chemicals from Methyl Oleate

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