Development of an Efficient Method for the Synthesis of Compounds Containing P—O—P Bonds: Pyrophosphonates, Tetraalkyl Pyrophosphates and Pyrophosphonamidates

doi:10.6023/cjoc202201050

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (7): 2214-2221.DOI: 10.6023/cjoc202201050 Previous Articles Next Articles

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高效合成含P—O—P键化合物: 焦膦酸酯、四烷基焦膦酸酯和焦膦酰胺的方法

张子璇, 高润利, 胡慧娟, 卢晓刚, 王瑾陈霄^*(), 王红梅^*()

国民核生化灾害防护国家重点实验室北京 102205

收稿日期:2022-02-07 修回日期:2022-03-05 发布日期:2022-08-09
通讯作者: 王瑾陈霄, 王红梅
基金资助:
国民核生化灾害防护国家重点实验室(SKLNBC2021-09)

Development of an Efficient Method for the Synthesis of Compounds Containing P—O—P Bonds: Pyrophosphonates, Tetraalkyl Pyrophosphates and Pyrophosphonamidates

Zixuan Zhang, Runli Gao, Huijuan Hu, Xiaogang Lu, Jin,Chen,Xiao Wang(), Hongmei Wang()

State Key Laboratory of NBC Protection for Civilian, Beijing 102205

Received:2022-02-07 Revised:2022-03-05 Published:2022-08-09
Contact: Jin,Chen,Xiao Wang, Hongmei Wang
Supported by:
State Key Laboratory of Nuclear Biological and Chemical Protection for Civilian(SKLNBC2021-09)

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Abstract

This work describes a method of synthesizing pyrophosphonates, tetraalkyl pyrophosphates and pyrophosphonamidates. Pyrophosphonates can be synthesized by the reaction of alkyl dichlorophosphonate, triethylamine (Et₃N), and water, in a molar ratio of 1∶1.2∶0.5 (dichlorophosphonate∶Et₃N∶water). When the reaction was allowed to proceed for 15 min in acetone, the maximum yield recorded for the pyrophosphonates was 95%. Et₃N was the solvent, with an acid-binding agent. Following this method, the achieved rate of production of tetraalkyl pyrophosphate and pyrophosphonamidate was faster than the rate of production of the compounds reached using traditional methods.

Key words: pyrophosphonates, tetraalkyl pyrophosphates, pyrophosphonamidates, P—O—P bond

Cite this article

Zixuan Zhang, Runli Gao, Huijuan Hu, Xiaogang Lu, Jin,Chen,Xiao Wang, Hongmei Wang. Development of an Efficient Method for the Synthesis of Compounds Containing P—O—P Bonds: Pyrophosphonates, Tetraalkyl Pyrophosphates and Pyrophosphonamidates[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2214-2221.

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References 14

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Entry	R¹	R²	Solvent	T/℃	Base (equiv.)	Yield^a/%
1^b	Me	OⁱPr	Acetone	Reflux	DMAP (1.0)	84
2^b			MeCN	Reflux		73
3^b			THF	Reflux		65
4^b			DCM	Reflux		62
5^b			Toluene	Reflux		31
6^b			Acetone	Reflux	Et₃N (1.0)	90
7^b					Et₃N (1.1)	90
8^b					Et₃N (1.2)	95
9^b					Et₃N (1.3)	85
10^b					DBU (1.0)	62
11^b					NaHCO₃ (1.0)	35
12^b			—	80	Et₃N	—
13^b			—	90	DBU	—
14^b			—	80	Pyridine	56
15	OⁱPr	OⁱPr	Acetone	Reflux	Et₃N (1.2)	98^c
16			Toluene	Reflux	Et₃N (1.2)	58
17			MeCN	Reflux	Et₃N (1.2)	63
18			THF	Reflux	Et₃N (1.2)	89^d
19			—	Reflux	Pyridine	56
20			—	80	Et₃N	89
21			—	Reflux	Et₃N	90
22			—	95	DBU	—
23	Me	N(Et)₂	Acetone	Reflux	Et₃N (1.2)	—
24			Toluene	Reflux	Et₃N (1.2)	—
25			Et₃N	80	Et₃N	95
26			DBU	90	DBU	50

Entry	R¹	R²	Solvent	T/℃	Base (equiv.)	Yield^a/%
1^b	Me	OⁱPr	Acetone	Reflux	DMAP (1.0)	84
2^b			MeCN	Reflux		73
3^b			THF	Reflux		65
4^b			DCM	Reflux		62
5^b			Toluene	Reflux		31
6^b			Acetone	Reflux	Et₃N (1.0)	90
7^b					Et₃N (1.1)	90
8^b					Et₃N (1.2)	95
9^b					Et₃N (1.3)	85
10^b					DBU (1.0)	62
11^b					NaHCO₃ (1.0)	35
12^b			—	80	Et₃N	—
13^b			—	90	DBU	—
14^b			—	80	Pyridine	56
15	OⁱPr	OⁱPr	Acetone	Reflux	Et₃N (1.2)	98^c
16			Toluene	Reflux	Et₃N (1.2)	58
17			MeCN	Reflux	Et₃N (1.2)	63
18			THF	Reflux	Et₃N (1.2)	89^d
19			—	Reflux	Pyridine	56
20			—	80	Et₃N	89
21			—	Reflux	Et₃N	90
22			—	95	DBU	—
23	Me	N(Et)₂	Acetone	Reflux	Et₃N (1.2)	—
24			Toluene	Reflux	Et₃N (1.2)	—
25			Et₃N	80	Et₃N	95
26			DBU	90	DBU	50

Entry	Compd.	e/hartree	μ/debye	P—O—P/(kJ•mol^–1)
1	2a	–1369.4128	4.7446	369.69
2	2d	–1684.0591	5.0677	409.72
3	1c	–1376.2258	4.7091	400.03
4	3a	–1415.0741	10.5770	282.35

Entry	Compd.	e/hartree	μ/debye	P—O—P/(kJ•mol^–1)
1	2a	–1369.4128	4.7446	369.69
2	2d	–1684.0591	5.0677	409.72
3	1c	–1376.2258	4.7091	400.03
4	3a	–1415.0741	10.5770	282.35

高效合成含P—O—P键化合物: 焦膦酸酯、四烷基焦膦酸酯和焦膦酰胺的方法

Development of an Efficient Method for the Synthesis of Compounds Containing P—O—P Bonds: Pyrophosphonates, Tetraalkyl Pyrophosphates and Pyrophosphonamidates

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