Bis(hydroxymethyl)phosphine oxides and hydroxymethyl phosphinic acids as phosphonic acid analogs

Full text of DOI:10.1080/10426500213342

This article was downloaded by: [University of Bristol]
On: 05 March 2015, At: 08:00
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the Related
Elements
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/gpss20
Bis(hydroxymethyl)phosphine Oxides and
Hydroxymethyl Phosphinic Acids as Phosphonic Acid
Analogs
J. L. Pirat a , C. Brahic a , C. Ciptadi a , H. J. Cristau a , A. Hervé a & D. Virieux a
a Laboratoire de Chimie Organique , France
Published online: 27 Oct 2010.
To cite this article: J. L. Pirat , C. Brahic , C. Ciptadi , H. J. Cristau , A. Hervé & D. Virieux (2002)
Bis(hydroxymethyl)phosphine Oxides and Hydroxymethyl Phosphinic Acids as Phosphonic Acid Analogs, Phosphorus, Sulfur, and
Silicon and the Related Elements, 177:8-9, 2221-2222, DOI: 10.1080/10426500213342
To link to this article: http://dx.doi.org/10.1080/10426500213342
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2221–2222
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290095241
BIS(HYDROXYMETHYL)PHOSPHINE OXIDES AND
HYDROXYMETHYL PHOSPHINIC ACIDS AS
PHOSPHONIC ACID ANALOGS
J. L. Pirat, C. Brahic, C. Ciptadi, H. J. Cristau, A. Herve´,
and D. Virieux
Laboratoire de Chimie Organique, France
(Received July 29, 2001; accepted December 25, 2001)
Very active phosphonate or phosphinate compounds have been recently
synthesized. However, their high ionic character can sometimes slow
down their transport trough cell membranes. New phosphorus phar-
macophores constituted by bis(hydroxymethyl) phosphine oxide and
hydroxymethylphosphinic acid groups were introduced in biologically
active phosphorus compounds to evaluate their potential activity.
SCHEME 1
The construction of such compounds requires the synthesis of
new building blocks bearing these two groups. One of them,
bis(benzyloxymethyl)phosphinic chloride 2, was obtained in five steps
from hypophosphorous acid in a good overall yield. Its reactivity toward
C-nucleophiles was also studied.
SCHEME 2
Bis(benzyloxymethyl)chloromethylphosphine oxide
3
was ob-
tained from tetrakis(hydroxymethyl)phosphonium chloride by double
Address correspondence to J. L. Pirat, Laboratoire de Chimie Organique - UMR 5076
du CNRS, 8, Rue de l’Ecole Normale 34 296 Montpellier Cedex 5, France.
E-mail: pirat@cit.enscm.fr
2221

2222
J. L. Pirat et al.
protection of two hydroxy groups and was used further in reaction
with heteroatomic nucleophiles. Benzyloxymethylphosphinate was
synthesized from hypophosphorous acid and its reactivity is still under
investigation.
SCHEME 3
Using these reagents, we were able to synthesize some biologically
active phosphonic acids analogs of aminophosphonates and geminal
bisphosphonates.1
REFERENCE
[1] H.-J. Cristau, C. Brahic, and J.-L. Pirat, Tetrahedron, 57, 9149–9156 (2001).