Synthesis of Functional Perfluorophosphonate Vinyl Ether

doi:10.19894/j.issn.1000-0518.230324

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (4): 512-520.DOI: 10.19894/j.issn.1000-0518.230324

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Synthesis of Functional Perfluorophosphonate Vinyl Ether

Ying-Ying SONG¹, Wei GE¹, Xiang SHI², Gang WEI², Bing LI¹, Chang-Kun LI¹(), Chang-Ming DONG¹(), Xue-Song JIANG¹

^1.School of Chemistry and Chemical Engineering，Shanghai Jiao Tong University，Shanghai 200240，China
^2.State Key Laboratory of Fluorinated Functional Membrane Materials，Shandong Dongyue Future Hydrogen Energy Co. Ltd. ，Zibo 256401，China

Received:2023-10-19 Accepted:2024-02-01 Published:2024-04-01 Online:2024-04-28
Contact: Chang-Kun LI,Chang-Ming DONG
About author:chkli@sjtu.edu.cn
cmdong@sjtu.edu.cn；
Supported by:
the National Key R&D Program of China(2021YFB4001100)

1. Efficient Synthesis of Functional Perfluorophosphonate Vinyl Ethers for Proton Membranes of Fuel Cells.pdf(1580KB)

Abstract

Abstract:

Herein， a new synthesis method of perfluorophosphonate vinyl ether for phosphonic acid-based proton exchange membrane was reported. Perfluorinated sulfonyl vinyl ether was converted to perfluorinated sulfinic acid vinyl ether by sodium borohydride reduction and sulfuric acid acidification， and followed by iodination to obtain perfluorovinyl ether iodide with 58% yield. Based on the metal-halogen exchange reaction， perfluorovinyl ether iodide and halogenated （chlorine/bromine） phosphate ester were dissolved under nitrogen atmosphere， and then n-butyl lithium or Grignard reagent was dropwise added to the reaction at low temperature； according to the Michaelis-Becker reaction， perfluorovinyl ether iodide was mixed with diethyl phosphite， then sodium or lithium bis（trimethylsilyl）amide was slowly added， both methods could successfully produce perfluorophosphonate vinyl ether with yields of 34% and 25%， respectively. This strategy avoids the protection of unsaturated double bonds with highly toxic chlorine gas or liquid bromine， greatly simplifies the synthesis process compared to the reported ones， and provides a new way to synthesize functional perfluorinated vinyl ether monomers.

Key words: Perfluorovinyl ether iodide, Michaelis-Becker reaction, Perfluorophosphonate vinyl ether

CLC Number:

O627.7

Ying-Ying SONG, Wei GE, Xiang SHI, Gang WEI, Bing LI, Chang-Kun LI, Chang-Ming DONG, Xue-Song JIANG. Synthesis of Functional Perfluorophosphonate Vinyl Ether[J]. Chinese Journal of Applied Chemistry, 2024, 41(4): 512-520.

Figures/Tables 6

References 36

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Entry	Reagent	Temperature/℃	Solvent	Yield/%
1	LDA	-78	THF	20
2	LiHMDS	-30	THF	35
3	i-PrMgCl·LiCl	-15	Et₂O	46
4	Mg powder	-15	Et₂O	23

Entry	Reagent	Temperature/℃	Solvent	Yield/%
1	LDA	-78	THF	20
2	LiHMDS	-30	THF	35
3	i-PrMgCl·LiCl	-15	Et₂O	46
4	Mg powder	-15	Et₂O	23

Entry	Reagent 7	R¹M or alkali	Solvent	Yield ^e /% of 6
1 ^a	7a	n-BuLi	THF	NTP
2 ^a	7a	n-BuLi	MTBE	30
3 ^a	7a	n-BuLi	Et₂O	34
4 ^a	7a	i-PrMgCl	Et₂O	11
5 ^a	7a	i-PrMgCl·LiCl	Et₂O	27
6 ^b	7c	NaH	THF	NTP
7 ^b	7c	Cs₂CO₃+TBAI	DMF	NTP
8 ^b	7c	NaOEt	THF	NTP
9 ^c	7c	NaHMDS/LiHMDS	THF	trace
10 ^c	7c	NaHMDS/LiHMDS	Et₂O	25
11 ^c	7c	NaHMDS/LiHMDS	MTBE	12
12 ^d	7c	NaHMDS/LiHMDS	Et₂O	11

Entry	Reagent 7	R¹M or alkali	Solvent	Yield ^e /% of 6
1 ^a	7a	n-BuLi	THF	NTP
2 ^a	7a	n-BuLi	MTBE	30
3 ^a	7a	n-BuLi	Et₂O	34
4 ^a	7a	i-PrMgCl	Et₂O	11
5 ^a	7a	i-PrMgCl·LiCl	Et₂O	27
6 ^b	7c	NaH	THF	NTP
7 ^b	7c	Cs₂CO₃+TBAI	DMF	NTP
8 ^b	7c	NaOEt	THF	NTP
9 ^c	7c	NaHMDS/LiHMDS	THF	trace
10 ^c	7c	NaHMDS/LiHMDS	Et₂O	25
11 ^c	7c	NaHMDS/LiHMDS	MTBE	12
12 ^d	7c	NaHMDS/LiHMDS	Et₂O	11

Synthesis of Functional Perfluorophosphonate Vinyl Ether

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