有机酸钾盐催化硫醇的β⁃羟乙基化反应

doi:10.3969/j.issn.1672-6952.2022.01.004

辽宁石油化工大学学报 ›› 2022, Vol. 42 ›› Issue (1): 19-23.DOI: 10.3969/j.issn.1672-6952.2022.01.004

有机酸钾盐催化硫醇的β⁃羟乙基化反应

赵敬伟(), 宫红, 李飞, 王锐()

辽宁石油化工大学石油化工学院，辽宁抚顺 113001

收稿日期:2020-05-17 修回日期:2021-03-01 出版日期:2022-02-28 发布日期:2022-03-07
通讯作者: 王锐
作者简介:赵敬伟（1994⁃），女，硕士研究生，从事功能材料设计、合成及应用研究；E⁃mail：1297952153@qq.com。
基金资助:
辽宁省自然科学基金项目(20180550246)

Organic Acid Potassium Salt Catalyzed β⁃Hydroxyethylation of Thiols

Jingwei Zhao(), Hong Gong, Fei Li, Rui Wang()

School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China

Received:2020-05-17 Revised:2021-03-01 Published:2022-02-28 Online:2022-03-07
Contact: Rui Wang

摘要/Abstract

摘要：

研究了一种有机酸钾盐(KA)催化硫醇与碳酸乙烯酯反应合成β?羟乙基硫醚的方法。结果表明，在常压、无溶剂条件下，KOAc、KSAc和HCOOK具有较高的催化活性，多元有机酸钾盐的催化活性相对较低，而CF₃SO₃K和CH₃SO₃K无催化活性。以KOAc为催化剂，各种硫醇的反应活性顺序为苯硫酚>2?巯基乙醇>糠硫醇>正构脂肪族硫醇。根据软硬酸碱理论，探讨了钾盐活化-S-H的反应机理。

关键词: β?羟乙基化, 有机酸钾盐, 硫醇, β?羟乙基硫醚

Abstract:

A method for synthesizing β?hydroxyethyl sulfide by reacting a thiol with ethylene carbonate by an organic acid potassium salt (KA) was reported. The results show that under normal pressure and solvent?free conditions, KOAc, KSAc and HCOOK have higher catalytic activity, and the catalytic activity of multi?organic potassium salt is relatively lower, while CF₃SO₃K and CH₃SO₃K have no catalytic activity. With KOAc as a catalyst, the order of reaction of various thiols is thiophenol>2?mercaptoethanol>hydrazine thiol>normal aliphatic thiol. According to the theory of soft and hard acid and base, the activation mechanism of -S-H by potassium salt was discussed.

Key words: β?Hydroxyethylation, Organic acid potassium salt, Thiols, β?Hydroxyethyl sulfide

中图分类号:

TQ227.1

赵敬伟, 宫红, 李飞, 王锐. 有机酸钾盐催化硫醇的β⁃羟乙基化反应[J]. 辽宁石油化工大学学报, 2022, 42(1): 19-23.

Jingwei Zhao, Hong Gong, Fei Li, Rui Wang. Organic Acid Potassium Salt Catalyzed β⁃Hydroxyethylation of Thiols[J]. Journal of Liaoning Petrochemical University, 2022, 42(1): 19-23.

图/表 7

参考文献 20

1	Clements J H. Reactive applications of cyclic alkylene carbonates［J］. Industrial & Engineering Chemistry Research， 2003， 42（4）： 663⁃674.
2	Orhan B， Ziba C A， Morcali M H， et al. Synthesis of hydroxyethyl cellulose from industrial waste using microwave irradiation［J］. Sustainable Environment Research， 2018， 28（6）： 403⁃411.
3	Shivarkar A B， Gupte S P， Chaudhari R V. Synthesis of β⁃amino alcohols from aromatic amines and alkylene carbonates using Na⁃Y zeolite catalyst［J］. Synlett， 2006（9）： 1374⁃1378.
4	Molleti J， Yadav G D. Selectivity engineering in hydroxyalkoxylation of phenol by ethylene carbonate using calcined hydrotalcite［J］. Clean Technologies and Environmental Policy， 2017， 19（5）： 1413⁃1422.
5	Yamada M， Tanaka Y. Pest control composition： US9265256［P］.2016⁃02⁃23.
6	Carlson D A. Kirk⁃othmer encyclopedia of chemical technology［M］. New Jersey： John Wiley & Sons， 2000： 112⁃124．
7	Mansueto M， Kres K C， Laschat S， et al. Sulfur makes the difference： Synthesis and mesomorphic properties of novel thioether⁃functionalized imidazolium ionic liquid crystals［J］. Tetrahedron， 2014， 70（36）： 6258⁃6264.
8	Kirres J， Schmitt K， Wurzbach I， et al. Tuning liquid crystalline phase behaviour in columnar crown ethers by sulfur substituents［J］. Organic Chemistry Frontiers， 2017， 4（5）： 790⁃803.
9	唐海燕，章亚东.无溶剂条件下相转移催化制备2⁃羟乙基正辛基硫醚［J］. 高校化学工程学报， 2010， 24（6）： 1017⁃1021.
10	唐海燕，章亚东，王振兴.避虫醇的合成及表征［J］. 精细石油化工， 2010， 27（3）： 23⁃26.
11	Hiroaki K， Izumi T. Method for producing sulfide derivative： JP2002121182［P］.2002⁃04⁃23.
12	Malievskii A D. Mechanism of the unusual substituent exchange in the reactions of alkylene oxides with organic compounds bearing β⁃hydroxyalkyl groups at heteroatoms S， Se， N， and P［J］. Russian Chemical Bulletin， 2017， 66（8）： 1357⁃1377.
13	Malievskii A D. Exchange reaction of oxiranes with β⁃hydroxyalkyl sulfides， selenides，⁃amines， and⁃phosphines［J］. Russian Chemical Bulletin， 2000， 49（4）： 579⁃587.
14	Malievskii A D. Exchange of substituents in the reaction of alkylene oxides with β⁃hydroxyalkyl sulfides［J］. Russian Journal of Physical Chemistry B， 2015， 9（4）： 601⁃614.
15	Frederickson S， Watson R. Process for producing a mono⁃condensation product of an alkylene oxide and a mercaptan： US3775483［P］. 1973⁃11⁃27.
16	Liu L， Cho M， Sathitsuksanoh N， et al. Uniform chemical functionality of technical lignin using ethylene carbonate for hydroxyethylation and subsequent greener esterification［J］. ACS Sustainable Chemistry & Engineering， 2018， 6（9）： 12251⁃12260.
17	Carlson W W. Process of hydroxyethylation： US2448767［P］.1948⁃09⁃07.
18	Upare P P， Kinage A K， Shingote S K， et al. Environmentally benign synthesis of β⁃hydroxy sulfides using cyclic carbonates catalyzed by large⁃pore zeolites［J］. Green Chemistry Letters and Reviews， 2012， 5（1）： 19⁃26.
19	Speight J G. Lange's handbook of chemistry［M］. New York： McGraw⁃Hill， Inc.， 2005： 2620⁃2669.
20	Tundo P， Rossi L I， Loris A， et al. Dimethyl carbonate as an ambident electrophile［J］. Journal of Organic Chemistry， 2005， 70（6）： 2219⁃2224.

KA	HA对应的pKa^a	t/min	V(CO₂)/mL	n⁃C₈H₁₇SH转化率/%	2b选择性/%
KOAc	4.76	61.03	2 410	96.4	100.0
HCOOK	3.75	103.65	2 249	90.0	100.0
KSAc	3.33	32.58	2 220	88.8	100.0
K₂C₂O₄∙H₂O	1.27	153.95	1 640	65.6	100.0
CF₃COOK	0.50	144.08	1 940	77.6	100.0
CF₃SO₃K	-14.00	120.00	0	—	—
CH₃SO₃K	-1.90	120.00	0	—	—
C₆H₅O₇K₃∙H₂O	3.13	157.60	1 730	69.2	100.0
C₄H₄O₆K₂∙0.5H₂O	3.22	164.43	1 725	69.0	100.0
C₄H₄O₆KNa∙4H₂O	3.22	211.47	1 710	68.4	100.0

KA	HA对应的pKa^a	t/min	V(CO₂)/mL	n⁃C₈H₁₇SH转化率/%	2b选择性/%
KOAc	4.76	61.03	2 410	96.4	100.0
HCOOK	3.75	103.65	2 249	90.0	100.0
KSAc	3.33	32.58	2 220	88.8	100.0
K₂C₂O₄∙H₂O	1.27	153.95	1 640	65.6	100.0
CF₃COOK	0.50	144.08	1 940	77.6	100.0
CF₃SO₃K	-14.00	120.00	0	—	—
CH₃SO₃K	-1.90	120.00	0	—	—
C₆H₅O₇K₃∙H₂O	3.13	157.60	1 730	69.2	100.0
C₄H₄O₆K₂∙0.5H₂O	3.22	164.43	1 725	69.0	100.0
C₄H₄O₆KNa∙4H₂O	3.22	211.47	1 710	68.4	100.0

催化剂	x/%	t/min	V(CO₂) /mL	n⁃C₈H₁₇SH转化率/%	2b选择性 /%
KOAc	1.00	61.03	2 410	96.4	100.0
	0.20	111.20	2 200	88.0	99.9
	0.10	110.75	2 080	83.2	99.4
	0.01	148.12	1 550	62.0	100.0
KSAc	1.00	32.58	2 220	88.8	100.0
	0.20	77.55	2 100	84.0	100.0
	0.10	88.33	1 940	77.6	100.0
	0.01	50.38	160	6.4	100.0

催化剂	x/%	t/min	V(CO₂) /mL	n⁃C₈H₁₇SH转化率/%	2b选择性 /%
KOAc	1.00	61.03	2 410	96.4	100.0
	0.20	111.20	2 200	88.0	99.9
	0.10	110.75	2 080	83.2	99.4
	0.01	148.12	1 550	62.0	100.0
KSAc	1.00	32.58	2 220	88.8	100.0
	0.20	77.55	2 100	84.0	100.0
	0.10	88.33	1 940	77.6	100.0
	0.01	50.38	160	6.4	100.0

催化剂	反应温度 /℃	t/min	V(CO₂) /mL	n⁃C₈H₁₇SH转化率/%	2b选择性 /%
KOAc	120	61.03	2 410	96.4	100.0
	110	102.22	2 230	89.2	100.0
	100	136.55	2 090	83.6	100.0
	90	172.90	1 670	66.8	100.0
KSAc	120	32.58	2 220	88.8	100.0
	110	42.12	1 910	76.4	100.0
	100	99.25	1 910	76.4	100.0
	90	105.52	1 610	64.4	100.0

有机酸钾盐催化硫醇的β⁃羟乙基化反应

Organic Acid Potassium Salt Catalyzed β⁃Hydroxyethylation of Thiols

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Metrics

R	反应温度/℃	t/min	V(CO₂)/mL	转化率/%	选择性/%
n⁃C₆H₁₃-	120	47.42	2 195	87.8	100.0
n⁃C₆H₁₃-	110	69.78	2 100	84.0	100.0
n⁃C₈H₁₇-	120	61.03	2 410	96.4	100.0
n⁃C₈H₁₇-	110	102.22	2 230	89.2	100.0
n⁃C₁₂H₂₅-	120	102.68	2 200	88.0	100.0
C₆H₅-	90	49.16	2 360	94.4	100.0
C₆H₅-	70	108.68	2 125	85.0	100.0
HOCH₂CH₂-	120	27.50	2 500	100.0	100.0
HOCH₂CH₂-	100	60.68	2 360	94.4	100.0
C₅H₅O-	120	23.00	2 340	93.6	100.0
C₅H₅O-	100	52.30	2 260	90.4	100.0