Phosphonic acid amide esters

N-Phosphinylhydroxylamines Phosphinyloxylamines Phosphonic acid amide esters P-Aminophosphinic acid - 10... 

Phosphonic acid amide esters. A soln. of ethyl [l-[[(phenylmethoxy)carbonyl]amino]-2-methylpropyl]phosphinate in acetonitrile under argon treated with bis(trimethyl-silyl)acetamide, followed after 1 min by L-alanine hydrochloride methyl ester, CCI4, and Et3N, the soln. stirred at room temp, for 30 min, cooled to 0°, and quenched with methanol N-[ethoxy[ 1 -[[(phenylmethoxy)carbonyl]am no]-2-methylpropyl]-... 

Phosphonic acid amide esters from phosphonodiamidates... 

The hydrolysis of tervalent phosphorus acid derivatives with two P—C bonds leads to secondary phosphine oxides (50) and with one P—C bond to phosphonus acid derivatives (51). Chlorophosphines react rapidly with water, but aminophosphines, phosphinites and phosphonites often survive a short wash with aqueous NaHC03, an effective way to remove contaminating ammonium salts in the crude products. However, aminophosphines with small substituents, e.g. dimethylaminodimethylphosphine, aryl phosphinites and phosphonites and trimethylsilyl phosphinites and phosphonites are hydrolysed too quickly for such a treatment. The hydrolyses are catalysed by acids (the hydrolyses of phosphinites and phosphonites are also catalysed by OH ) and are much faster than hydrolyses of the corresponding phosphoryl compounds [up to a factor of 10 for acid-catalysed hydrolysis of (MeO)3P compared with (MeO)3P=0 ]. Dialkyl phosphonites are rapidly hydrolysed to the monoalkyl esters (51, X = OR) in weakly acidic water, whereas hydrolyses to phosphonous acids require reflux with strong acid or base, e.g. equation 131 Bis-(dialkylamino) phosphines may also be partially hydrolysed to phosphonous acid amides (51, X = NR2). Tervalent phosphorus acid derivatives with hydrogen sulphide give secondary phosphine sulphides or phosphonodithious acids, e.g. equation 156 . ... 

Cationic - quatemary ammonium compounds. Anionic alkyl sulfonates and phosphonates. Nonionic ->Fatty amine ethoxylates or ->fatty alcohol ethoxylates, - fatty acid amides, esters of fatty acids with - glycerol, polyethyleneglycol and - sorbitol. 

Addition of the alcohol 42 to a solution of BF3 Et20/TMSCN in DCM provided the nitrile 43 in 83% yield. Hydrolysis of nitrile 43 then furnished amide 44 in 85% yield. Demethylation of the methoxyindole 44 with BBra in DCM provided the hydroxyindole 45 in 80% yield. This was followed by alkylation of 45 with the bromide 46 under phase transfer conditions to provide the phosphonate ester 47 and subsequent cleavage of the methyl ester by TMS-I furnished trimethylsilyl phosphonic acid 48, which upon alcoholic workup afforded LY311727. 

Surfactants are prepared which contain carboxylic acid ester or amide chains and terminal acid groups selected from phosphoric acid, carboxymethyl, sulfuric acid, sulfonic acid, and phosphonic acid. These surfactants can be obtained by reaction of phosphoric acid or phosphorus pentoxide with polyhydroxystearic acid or polycaprolactone at 180-190°C under an inert gas. They are useful as polymerization catalysts and as dispersing agents for fuel, diesel, and paraffin oils [69]. 

Surfactants which contain carboxylic acid ester or amide chains with terminal phosphonic acid groups are prepared from polyhydroxystearic acid or poly-caprolactone. Such reaction products are useful as dispersants, emulsifiers, and, in some cases, bactericides, disinfectants, and antiseptics see Sec. III.C.9 [69]. 

The reaction of phosphonic acid chloride (254) with (S)-proline ethyl ester afforded a mixture of diasteromeric amides (255) in high diastereoselectivity. The diastereomers (255) can easily be purified by chromatography. The chiral, practically optical pure organophosphorus compound (256) was obtained from purified (255) by acid alcoholysis. 

In an earlier investigation by the author [2] di-amides, (I) and (II), were prepared and used in dental adhesive composites. Materials based on acrylic-ester phosphonic acids, (III) and (IV), and used in dental cements were also prepared by the author [3]. 

The exact composition of marine DOM is unknown. It has, as of early 2000s, been shown to contain carbohydrates, which consist largely of polysaccharides, and amino acids, amides (such as chitin), phosphorus esters, and phosphonates (Benner et al., 1992 McCarthy et al., 1997 Clark et ai, 1998 Amon et ai, 2001). Microbial degradation could play a role in setting the composition of DOM in the ocean (Amon et ai, 2001). 

PNOCi2H,2, Phosphinic amide, diphenyl-lanthanoid complexes, 23 180 PNOSiCi2Hi Phosphinimidic acid, P-methyl-P-phenyl-N-(trimethylsilyl)-2,2,2-trifluoroethyI ester, 25 72 PN04CsH,g, Phosphonic acid, [(N,N-di-diethyIcarbamoyl)methylJ-, dimethyl ester, 24 101... 

The prototypical representatives of the group are the carboxylic acids. However, a huge number of bioisosteres such as sulfonic or phosphonic acids, tetrazoles or 3-hydrox-yisoxazoles are available (see Chapter 15). In addition functions like esters, amides, peptides, aldehydes, primary alcohols and related functions can work as prodrugs or bioprecursors (see Chapter 36). 

Firestone, R.A.. Esters and amides of (diazomethyl)phosphonic acid, Merck, U.S. Patent Appl. US 3668197, 1972 Chem. Abstr. 77. 114560, 1972. 

From a synthetic viewpoint, the significant feature of the classical Michaelis-Arbuzov reaction of an alkyl halide with a P(III) ester is the formation of a carbon-phosphorus bond. Since its discovery by Michaelis and Kaehne (222) in 1898, it has been the principle synthetic route to the phosphonic acids, which, with their esters and amides, probably outnumber all other compounds containing the carbon-phosphorus bond (105). 

Michaelis-Arbuzov reactions are not restricted to the use of the alkyl halide but may also be carried out with a corresponding ester or alcohol. On reaction with triethyl phosphite or a phosphorus(III) amide, the ester NCCH2CH2Z (Z = OAc) and ethers (with Z = OPh or OEt) afford the corresponding derivatives of (2-cyanoethyl)phosphonic acid [3-(dialkoxyphosphinyl)propanenitrile]. The same products are obtainable from 2-cyanoethanol. These reactions, and the conversion of406 into 408 and of407 into 409 , are reminiscent of those which take place between phosphorus(III) esters and 2-hydroxy-benzyl alcohols, and indeed they may be formulated in a similar manner (Chapter 2, Section II.A). Yet a further variation in reaction 22 is the involvement of substrates in... 

The monoaminomonophosphonic acids, either in the free state or, very often, as their diethyl esters, have been resolved by the usual techniques of repeated crystallization of appropriate salts those of L-(+)-tartaric acid (2,3-dihydroxybutanedioic acid) or its mono-or di-benzoyl derivativesor of D-(-)-mandelic acid, have been widely employed the use of di-O-benzoylated L-tartaric anhydride, which is based on the separation of diastereoisomeric amides (111), has also been employed to a limited extent. In selected cases, such as the monoaminomonophosphonocarboxylic acids or A -acylated (aminoalkyl)phosphonic acids, resolution following salt formation with organic bases has also been carried out ephedrine, quinine and both enantiomers of l-phenylethylamine have all been used. In many cases, only one enantiomer of the (aminoalkyl)phosphonic acid (or diester) has been isolated in optically pure form. Sometimes, the acidity of the substrate, and hence choice of base for resolution, can be modified by using a mono- (as opposed to di-) ester or (or even in addition to) protection of the amino group as, for example, the phthalimido, benzyloxycarbonyl (cbz) or r r -butyloxycarbonyl (boc) derivative. Resolved di- and mono-esters can be hydrolysed to the free acids under acidic conditions, and A -protection can also be removed through the customary procedures. 

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