Phosphonate hydroxymethyl

Uptake of methylphosphonic, aminomelhyl-phosphoniCs hydroxymethyl-phosphonic. l-hydro ycthane-(l, 1-diphosphonic), iminodi-(methylphosphonic). nitnlotris-(methylene-phosphonic). elhylcncdimtnlotetrakis-(methylcnephosphonic), and diethylenetruu-tnlopentakis-(methylenephosphonic) acids was interpreted in terms of formation of 2-9 different surface species whose stability constants are interrelated, namely, log K = (1145 + 7.31 nH2.53 + 0 46n>Z where n is the surface protonation level and Z IS the surface complex charge, and fully deprotonated anions are componenls. Adsorplion isotherms at constant pH were also obtained in the presence of buffers lEP at pH 7 2 in dispersion titrated with Na COj. pristine lEP at pH 8.5. 

The kinetics of deuterium isotope exchange between diphenyl phosphine and t-butylthiol have been studied by H n.m.r. spectroscopy.274 A negative temperature coefficient was observed for the reaction of a perf1uoroalky1 phosphite with a fluorinated aldehyde.275 The kinetics for the reaction of alcohols with phosphoryl trichloride bore strong similarities to those of carboxylic acid derivatives.276 An interesting report desribed the solvolysis of ary 1 hydroxymethyl-phosphonates. It was shown that a phosphoryl group does not prevent carbocation formation on an immediately adjacent carbon atom.277... 

Analysis of the Murchison meteorite led to a completely different type of phosphorus compound the only phosphorus-containing compounds found were alkanephos-phonic acids. Spurred on by these results, de Graaf et al. (1995) irradiated mixtures of o-phosphorous acid in the presence of formaldehyde, primary alcohols or acetone with UV light (low pressure Hg lamp, 254 nm with a 185-nm component) and obtained phosphonic acids, including hydroxymethyl and hydroxyethyl phosphonic acids, which had been found in the Murchison meteorite. Alkanephosphonic acids can be derived from phosphorous acid, with a P-H bond being replaced by a P-C bond. 

Attempted isolation of diethyl hydroxymethyl phosphonate by standard vacuum distillation technique is accompanied by extensive decomposition. The use of Kugelrohr apparatus allows the isolation to be accomplished at a lower temperature, and therefore the product is obtained in higher yield. Alternately, the checkers found that distillation using a 2 wiped-film molecular still (Pope Scientific, Inc.) significantly raised product yields, especially when the reaction was performed on a larger scale (Notes 3 and 6). 

Diethyl [(2-tetrahydropyranyloxy)methyl]phosphonate is useful in the Wlttig-Horner synthesis of enol ethers, which are intermediates in one-carbon homologations of carbonyl compounds. This procedure is an adaptation of a general method for making dialkyl hydroxymethylphosphonates. An 0-tetra-hydropyranyl derivative also has been made from dibutyl hydroxymethyl -phosphonate, and diethyl hydroxymethylphosphonate has been O-silylated with tert-butylchiorodimethylsilane and imidazole. Another useful congener in this series has been prepared by an Arbuzov reaction of methoxyethoxymethyl (HEM) chloride and triethyl phosphite. 

Diethyl [(2-tetrahydropyranyloxy)methyl]phosphonate Phosphonic acid, [[(tetrahydro-2H-pyran-2-yl)oxy]methyl]-, diethyl ester (10) (71885-51-3) Diethyl hydroxymethylphosphonate Phosphonic acid, (hydroxymethyl)-, diethyl ester (8,9) (3084-40-0)... 

Chemical Name Phosphonic acid, ((2-(4-amino-2-oxo-l(2H)-pyrimidinyl)-l-(hydroxymethyl)ethoxy)methyl)-, (1S)-... 

In many examples, it is not necessary to prepare the phosphorane. Instead, the dicarbonyl compound is heated with a trialkyl or triaryl ester of phosphorus acid or, less commonly, with a diester of a phosphonous acid (RP(OH)2, where R is an organic group). For example, when the thioester 301 is heated with dipropyl ethylphosphonite the 2-substituted carbapenem 302 is produced in 80% yield (Equation 32) <1997CPB1439>. This general method has been used to prepare 2-sulfide-substituted 1/3-methylcarbapenems <2000CPB126, 2001SC587> and O-protected 2-hydroxymethyl derivatives < 1999JA11261 >. 

Quantitative risk assessments have been performed on a variety of flame-retardants used both in upholstered furniture fabric and foam. The National Research Council performed a quantitative risk assessment on 16 chemicals (or chemical classes) identified by the U.S. Consumer Product Safety Commission (CPSC). The results were published in 2000.88 The 16 flame-retardants included in this NRC study were HBCD, deca-BDE, alumina trihydrate, magnesium hydroxide, zinc borate, calcium and zinc molybdates, antimony trioxide, antimony pentoxide and sodium antimonate, ammonium polyphosphates, phosphonic acid, (3- [hydroxymethyl]amino -3-oxopropyl)-dimethylester, organic phosphonates, tris (monochloropropyl) phosphate, tris (l,3-dichloropropyl-2) phosphate, aromatic phosphate plasticisers, tetrakis (hydroxymethyl) hydronium salts, and chlorinated paraffins. The conclusions of the assessment was that the following flame-retardants can be used on residential furniture with minimal risk, even under worst-case assumptions ... 

The CPSC staff performed quantitative risk assessments on various flame-retardants for both upholstered residential furniture fabrics and foam.89 CPSC addresses chemical hazards under the Federal Hazardous Substances Act (FHSA), which is risk based. For fabrics, five flame-retardants were evaluated, that include antimony trioxide, deca-BDE, HBCD, phosphonic acid, (3- [hydroxymethyl]amino)-3-oxopropyl)-, dimethyl ester (PA), and tetrakis (hydroxymethyl) phosphonium chloride (THPC). These flame-retardants were selected for study because they are used to comply with the U.K. upholstered furniture flammability standard (except THPC) and fabric samples were available for testing. The staff concluded in 2006 that deca-BDE, HBCD, and PA would not present a hazard to consumers and that additional data would be needed to assess antimony trioxide and THPC. 

Also phosphorus- and nitrogen-containing polyols are shown to be effective in flame retardancy of PU foams24 such as polyols based on phosphonic acid ester or obtained by partial or full substitution of methylol groups of tetrakis(hydroxymethyl)phosphonium chloride with amine several examples of such polyols were reported by Levchik and Weil.15 Rigid PU foam modified with these polyols showed improved oxygen index values moreover better results were achieved with higher functionality polyols. 

Phosphonic acid, (phthalimidomethyl)-, diethyl ester, 65, 119 Phosphorazidic acid, diphenyl ester (26386-88-9), 68,1 Phosphoric triamide, hexamethyl- (680-31-9), 66, 51, 94 Phosphorodichloridic acid, 2-chloroethyl ester, 65, 68 Phosphorous acid, triethyl ester, 65, 108.119 Phosphorus oxychloride, 66,173, 176 67,1 68, 41,162 Phosphorus tribromide (7789-60-8), 67, 210 Phthalimide, N-(bromoethyl)-, 65, 119 Phthalimide, N-(hydroxymethyl)-, 65,119 Pig liver esterase, 69, 20... 

The procedure 1n the present reaction sequence for the preparation of N-bromomethylphthalimide (2) is a modification of that reported by Pucher and Johnson. N-Bromomethylphthallmide has also been prepared by treatment of 11-hydroxymethyl phthali mi de with phosphorus tri bromide. The procedures for the syntheses of the phosphonates 3 and 4 represent modifications of those described by Yatnauchi and co-workers. Two other routes to 4 have recently been reported by Gross and co-workers. Ratcliffe and Christensen have also recorded the preparation of diethyl N-benzylldeneaminomethylphosphonate (5) by the condensation of benzaldehyde with 4 under virtually identical conditions as detailed herein, but their route to 4 was completely different. The submitters have found that the present method for the syntheses of 2-5 gives reproducibly higher yields and is more reliable and convenient than those alternative procedures. 

SYNS BIS(HYDROXYMETHYL)PHOSPHINE OXIDE DIMETHOXYPHOSPHINE OXIDE DIMETHYL ACID PHOSPHITE DIMETHYLESTER KYSEUNY FOSFORITE (CZECH) DIMETHYLFOSFIT DIMETHYLFOSFONAT DLMETHYLHYDRO-GENPHOSPHITE DLMETHYL PHOSPHITE DIMETHYL PHOSPHONATE DIMETHYL PHOSPHOROUS ACID HYDROGEN DIMETHYL PHOSPHITE METHYL PHOSPHONATE NCI-C54773 PHOSPHOROUS ACID DIMETHYL ESTER... 

It is known that low-molecular-weight esters of phosphorous acid react, in the presence of alkali catalysts, with formaldehyde to give the corresponding hydroxymethyl phosphonates. This reaction was used to synthesize cellulose hydroxymethylphosphonates (V). The structure of these compounds has been confirmed by hydrolysis to hydroxymethyl-phosphonic acid, which was identified by paper chromatography. 

Bis(hydroxymethyl)phosphonic acid esters that incorporated thymine were employed as a backbone to prepare short oligonucleotide chains. This chain was prepared by condensation of the bis(4,4 -dimethoxytrityl) protected phosphonic acid and iV or N -(2-hydroxyethyl)thymine in the presence of l-(2-mesitylenesul-fonyl)-3-nitro-l,2,4-triazole or by an Appel reaction with or N -(2-aminoethyl)thymine (89a-h). Selective removal of one DMT-group and phos-phitylation yielded the building blocks for solid supported synthesis of the short oligomers by the phosphoramidite approach. Holy has reported the synthesis of 8-amino and 8-substituted amino derivatives of acyclic purine nucleotide analogues. The 8-amino, 8-methylamino- and 8-dimethylamino-adenine and -guanine analogues of iV-(2-phosphonomethoxyethyl) and (S)-iV-(3-hydroxy-2-phosphono-methoxy-propyl) derivatives of purines (90a-i), were prepared by... 

The Stille cross-coupling reaction between various heteroarylstannanes and ring-brominated benzylphosphonates (107) has been used to prepare heterobiaryl phosphonates 108. A key step in the synthesis of individual optical isomers of 2-hydroxymethyl-4-[3-(diethoxyphosphinyl)propyl]-5-alkylpiperazines 109 as CPP analogues is the alkylation of protected 5-alkyl-2-hydroxymethylpiperazines with (3-bromopropyl)phosphonate (Scheme 5). Compound 110, a new member... 

Hydroxyalkylphosphonates have been prepared by reduction of the corresponding ketones. These include phosphonomalate esters by highly diastereose-lective reduction of 3-phosphonopyruvates with NHs.BHa and both 2-hydroxyalkyl-phosphonates, e.g. 178, and thiophosphonates by asymmetric hydrogenation using chiral ruthenium catalysts. An enantioselective synthesis, from 179, of both enantiomers of phosphonothrixin 180 and their absolute stereochemistry have been reported.The epoxide 179 was prepared from 2-methy -3-hydroxymethyl-1,3-butadiene via a Sharpless epoxidation. 

BICYCLOPROPYLIDENE possesses unique reactivity toward a wide range of electrophiles and nucleophilic carbenes. (E)-I-DIMETH YLAMINO-3-tert-BUTYLDIMETHYL-SILOXY-1,3-BUTADIENE is a highly reactive diene for Diels-Alder reactions, as described in an accompanying procedure for the synthesis of 4-HYDROXYMETHYL-2-CYCLOHEXEN-1-ONE via the Diels-Alder reaction with methyl acrylate. Finally, this section concludes with the preparation of DIETHYL [(PHENYLSULFONYL)METHYL]PHOSPHONATE, a reagent that is very useful for synthesis of [Pg.285]

The a proton of a substituted cyclopropane is also rendered acidic if the substituent is attached to the ring by C-P bonds. A few reports have appeared on a-substitution in such compounds.(Cyclopropyl)triphenylphosphonium bromide was converted to a (1-ethoxy-carbonylcyclopropyl)triphenylphosphonium salt 18 in 80% yield by sequential treatment with lithium diisopropylamide and ethyl chloroformate. Furthermore, some diethyl cyclopropyl-phosphonates were converted, in some cases in excellent yield, to diethyl (1-hydroxymethyl-cyclopropyl)phosphonates by treatment with lithium diisopropylamide followed by addition of an aldehyde." Thus, typically, diethyl 2-hexylcyclopropylphosphonate gave diethyl 2-hexyl-l-[hydroxy(phenyl)methyl] cyclopropylphosphonate (19b) in 90% yield on reaction with benzaldehyde. ° Other electrophiles such as acetone, acetyl chloride, acetic anhydride, and ethyl acetate, were not sufficiently reactive to undergo addition to the anion. 

Out own research indicates, however, that the reaction product from CH2 0 and P4 consists actually of equal amounts ( 30% each) of hydroxyme-thyl-phosphonic acid (75), bis (hydroxymethyl)phosphinic acid (74), and me-thyl-hydroxymethyl-phosphinic acid (75). Small amounts of methyl-phosphonic acid and tris (hydroxymethyl)phosphine oxide were also detected... 

A quite similar method is employed in the one-carbon chain extension of a 5 -phosphonate isostere of pyridoxal 5 -phosphate (Scheme 5.50) The a , 3-O-isopropylideneisopyridoxal is converted into an oc,P-unsaturated phosphonate in yields up to 65% by condensation with sodium tetraethyl methylenediphosphonate. Selective hydrolysis with 10% HCOjH at reflux gives the key diethyl 2-(3-hydroxy-4-hydroxymethyl-2-methyl-5-pyridyl)vinylphosphonate intermediate in 98% yield. After catalytic hydrogenation of the double bond using 5% Pd/C in EtOH, a comparison of methods for the oxidation of the alcohol has been made, including use of MnOi in water, CrO, Py, and DMSO-DCC. Finally, oxidation with activated MnO2 in CHCl, was found to proceed smoothly to give the diethyl 2-(4-formyl-3-hydroxy-2-methyl-5-pyridyl)cthylphosphonate. ... 

Costisella, B., and Gross, H., a-Substituted phosphonates. Part 14. Phosphoryl derivatives of 2,2-hri(hydroxymethyl)-5-norbomene, J. Prakt. Chem., 314, 532, 1972. 

Distorted octahedral structures have been proposed for the 1 1 neutral complexes formed between bivalent transition-metal ions and hydroxymethyl-phosphonic acid, H0CH2P03H2. A series of new dialkylaminomethylenedi-phosphonic acids (H0)2P(0)CH(NR R )2P(0)(0H)2 has been prepared from phosphorus trihalides and NN-dialkylformamides. Acid dissociation constants and the complex behaviour toward Cu " for the phosphinyl-propionic acid Ph(H0)P(0)CMe(0H)(C02H) have been evaluated. ... 

Addition of phosphorus trichloride to aldehydes or ketones occurs with deoxygenation of the carbonyl compound. It thus provides a simple entry to the phosphonic acid series. After phosphorus trichloride has reacted with 3 moles of a carbonyl compound hydrolytic working up affords ac-hydroxy phosphonic acids, often in good yield. Directions for the preparation of the hydroxymethyl compound from paraformaldehyde have been given by Bannard and his co-workers.104... 

Dialkyl phosphites react with (hydroxymethyl)amines, giving a-amino phosphonic esters the same products can often be obtained by reaction of the phosphite with aminals, Schiff bases, or an aldehyde plus an amine321 (cf. page 708). Free phosphorous acid can itself be a-aminoalkylated in an acid medium, when according to the amine selected (ammonia can also be used) up to three methylenephosphonic acid groups can be attached to one nitrogen atom 322... 

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