Tetrakis(trimethysilyl)hypophosphate P2O2(OTMS)4: Synthesis, reactivity and application as flame retardant

The preparation of tetrakis(trimethy- silyl)hypophosphate, P2O2(OTMS)4 (TMS = SiMe3), which is easily obtained from cheap starting materials, is reported. Reaction with protic substrates (H2O, alcohols) proceeds under stepwise cleavage of silylethers, ROTMS, and formation of hypophosphoric acid, P2O2(OH)4. Amines in the presence of molecular sieves lead to desilylation and formation of ammonium salts of the [P2O2(OTMS)2(O−)2] dianion. On cotton fabrics, P2O2(OTMS)4 hydrolyzes to give P2O2(OH)4 within about 1 h when exposed to air, and this compound acts as an efficient flame retardant (limiting oxygen index >26%) even at low loadings (P content <3%). © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:721–731, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20373

[1]  M. Tsafack,et al.  Towards multifunctional surfaces using the plasma-induced graft-polymerization (PIGP) process: Flame and waterproof cotton textiles , 2007 .

[2]  M. Tsafack,et al.  Plasma-induced graft-polymerization of flame retardant monomers onto PAN fabrics , 2006 .

[3]  M. Kukhanova,et al.  Hypophosphoric acid is a unique substrate of pyrophosphorolysis catalyzed by HIV-1 reverse transcriptase. , 2005, Biochemical and biophysical research communications.

[4]  B. Twamley,et al.  Room temperature synthesis and solid-state structure of Ni2P2O6·12H2O , 2005 .

[5]  M. Tsafack,et al.  Polymerization and surface modification by low pressure plasma technique , 2004 .

[6]  H. Remy,et al.  Über das Verhalten der Unterphosphorsäure , 2004, Naturwissenschaften.

[7]  P. Granger,et al.  NMR nomenclature. Nuclear spin properties and conventions for chemical shifts(IUPAC Recommendations 2001) , 2001 .

[8]  Ian D. Williams,et al.  The First Examples of Enantiomerically Pure Diphosphane Dioxides—(RP,RP)‐ and (SP,SP)‐1,2‐Di‐ter‐butyl‐1,2‐diphenyldiphosphane 1,2‐Dioxides, and (RP)‐ and (SP)‐1‐tert‐Butyl‐1,2,2‐triphenyldiphosphane 1,2‐Dioxides , 1997 .

[9]  T. Winkler,et al.  A NOVEL REARRANGEMENT IN THE SERIES OF GEM-BISPHOSPHONIC ACIDS , 1990 .

[10]  L. Maier.  ORGANIC PHOSPHORUS COMPOUNDS 89.1 A NEW METHOD FOR THE PREPARATION OF AMINOMETHYLPHOSPHONIC ACID AND DERIVATIVES , 1990 .

[11]  M. Regitz,et al.  Salts of α-Diazo “Phosphorus Acids” - Starting Compounds for Phosphonate and Phosphate Transfer Reagents , 1983 .

[12]  H. Schnering,et al.  Struktur und NMR‐Spektren des (R,R/S,S)‐1,2‐Di‐tert‐butyl‐1,2‐bis(2,2‐dimethylpropyl)diphosphan‐1,2‐dioxids , 1982 .

[13]  C. McKenna,et al.  The facile dealkylation of phosphonic acid dialkyl esters by bromotrimethylsilane , 1977 .

[14]  R. Collin,et al.  The crystal structure of disodium dihydrogen hypophosphate hexahydrate (Na2H2P2O6.6H2O) and disodium dihydrogen pyrophosphate hexahydrate (Na2H2P2O7.6H2O) , 1971 .

[15]  W. Stec,et al.  Cyclic organophosphorus compounds. II. Some sterically hindered cyclic hypophosphate systems and related compounds , 1967 .

[16]  J. W. Emsley,et al.  High Resolution Nuclear Magnetic Resonance Spectroscopy , 1965 .

[17]  A. Wilson,et al.  The crystal structure of diammonium dihydrogen hypophosphate (NH4)2H2P2O6 , 1964 .

[18]  J. R. Wazer,et al.  Principles of Phosphorus Chemistry. III. Structure Proofs by Nuclear Magnetic Resonance1 , 1957 .

[19]  E. Leininger,et al.  A New Method for the Preparation of Disodium Dihydrogen Hypophosphate , 1949 .

[20]  M. Hunter,et al.  Organosilicon polymers; infrared spectra of the methylpolysiloxanes. , 1947, Journal of the American Chemical Society.

[21]  T. Salzer.  Ueber die Unterphosphorsäure , 1877 .

[22]  J. Schiel.  Ueber die chlorige Säure , 1859 .