Facile high yielding synthesis of symmetric esters of methylenebisphosphonic acid

Dominique C. Stepinski; Derek W. Nelson; Peter R. Zalupski; Albert W. Herlinger

doi:10.1016/S0040-4020(01)00846-8

Facile high yielding synthesis of symmetric esters of methylenebisphosphonic acid

Dominique C. Stepinski, Derek W. Nelson, Peter R. Zalupski, Albert W. Herlinger^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

The 1H-tetrazole catalyzed coupling of methylenebis(phosphonic dichloride), CH₂(POCl₂)₂, with primary alkyl, cyclic secondary alkyl, aromatic, and silicon- and fluorine-containing alcohols selectively affords symmetric P,P′-dialkyl partial esters as well as homoleptic and mixed tetraesters. Two partial ester intermediates, methylenebis(2-ethylhexyl phosphonic chloride) and 2-ethylhexyl methylenebisphosphonic trichloride, were observed by ¹H- and ³¹P NMR spectroscopy in the esterification of CH₂(POCl₂)₂ with 2-ethyl-1-hexanol.

Original language	English (US)
Pages (from-to)	8637-8645
Number of pages	9
Journal	Tetrahedron
Volume	57
Issue number	41
DOIs	https://doi.org/10.1016/S0040-4020(01)00846-8
State	Published - Oct 8 2001

Funding

The authors thank Julie A. Dzielawa and Daniel R. McAlister for helpful discussions and suggestions. This work was supported by the PG Research Foundation, Inc., Darien, IL 60561.

Keywords

Aggregation
Esterification
Phosphonic acids and derivatives
Tetrazoles

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/S0040-4020(01)00846-8

Cite this

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title = "Facile high yielding synthesis of symmetric esters of methylenebisphosphonic acid",

abstract = "The 1H-tetrazole catalyzed coupling of methylenebis(phosphonic dichloride), CH2(POCl2)2, with primary alkyl, cyclic secondary alkyl, aromatic, and silicon- and fluorine-containing alcohols selectively affords symmetric P,P′-dialkyl partial esters as well as homoleptic and mixed tetraesters. Two partial ester intermediates, methylenebis(2-ethylhexyl phosphonic chloride) and 2-ethylhexyl methylenebisphosphonic trichloride, were observed by 1H- and 31P NMR spectroscopy in the esterification of CH2(POCl2)2 with 2-ethyl-1-hexanol.",

keywords = "Aggregation, Esterification, Phosphonic acids and derivatives, Tetrazoles",

author = "Stepinski, {Dominique C.} and Nelson, {Derek W.} and Zalupski, {Peter R.} and Herlinger, {Albert W.}",

note = "Funding Information: The authors thank Julie A. Dzielawa and Daniel R. McAlister for helpful discussions and suggestions. This work was supported by the PG Research Foundation, Inc., Darien, IL 60561.",

year = "2001",

month = oct,

day = "8",

doi = "10.1016/S0040-4020(01)00846-8",

language = "English (US)",

volume = "57",

pages = "8637--8645",

journal = "Tetrahedron",

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publisher = "Elsevier Ltd",

number = "41",

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TY - JOUR

T1 - Facile high yielding synthesis of symmetric esters of methylenebisphosphonic acid

AU - Stepinski, Dominique C.

AU - Nelson, Derek W.

AU - Zalupski, Peter R.

AU - Herlinger, Albert W.

N1 - Funding Information: The authors thank Julie A. Dzielawa and Daniel R. McAlister for helpful discussions and suggestions. This work was supported by the PG Research Foundation, Inc., Darien, IL 60561.

PY - 2001/10/8

Y1 - 2001/10/8

N2 - The 1H-tetrazole catalyzed coupling of methylenebis(phosphonic dichloride), CH2(POCl2)2, with primary alkyl, cyclic secondary alkyl, aromatic, and silicon- and fluorine-containing alcohols selectively affords symmetric P,P′-dialkyl partial esters as well as homoleptic and mixed tetraesters. Two partial ester intermediates, methylenebis(2-ethylhexyl phosphonic chloride) and 2-ethylhexyl methylenebisphosphonic trichloride, were observed by 1H- and 31P NMR spectroscopy in the esterification of CH2(POCl2)2 with 2-ethyl-1-hexanol.

AB - The 1H-tetrazole catalyzed coupling of methylenebis(phosphonic dichloride), CH2(POCl2)2, with primary alkyl, cyclic secondary alkyl, aromatic, and silicon- and fluorine-containing alcohols selectively affords symmetric P,P′-dialkyl partial esters as well as homoleptic and mixed tetraesters. Two partial ester intermediates, methylenebis(2-ethylhexyl phosphonic chloride) and 2-ethylhexyl methylenebisphosphonic trichloride, were observed by 1H- and 31P NMR spectroscopy in the esterification of CH2(POCl2)2 with 2-ethyl-1-hexanol.

KW - Aggregation

KW - Esterification

KW - Phosphonic acids and derivatives

KW - Tetrazoles

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U2 - 10.1016/S0040-4020(01)00846-8

DO - 10.1016/S0040-4020(01)00846-8

M3 - Article

AN - SCOPUS:0035828936

SN - 0040-4020

VL - 57

SP - 8637

EP - 8645

JO - Tetrahedron

JF - Tetrahedron

IS - 41

ER -

Facile high yielding synthesis of symmetric esters of methylenebisphosphonic acid

Abstract

Funding

Keywords

ASJC Scopus subject areas

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