Organic Acid Potassium Salt Catalyzed β⁃Hydroxyethylation of Thiols

doi:10.3969/j.issn.1672-6952.2022.01.004

Abstract

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

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

CLC Number:

TQ227.1

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.

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.

Figures/Tables 7

References 20

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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