Phosphinic acid amides esters

Amidophosphonous acid esters Iminophosphites Phosphinic acid amides... 

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]-... 

In a similar way to the aminolysis of the P-N bond mentioned above (Scheme 9), alcoholysis of phosphinous amides leads to the alkyl esters of the respective phosphinous acids [30, 121]. This reaction occurs with inversion of the absolute configuration of the phosphorus atom, and has been used in a synthetic sequence leading to optically active tertiary phosphanes 22 [122] (Scheme 23). 

A variety of compounds have been examined which are in the phosphinic acid class. They include a phenyl cyclopentyl ester,184 a phosphinothioic anhydride,185 a dipheny1phosphinamide, 86 a red bis(di-t-buty1thiophosphinamide) and its selenide analogue,187 the anisylphosphor inane (67),1 88 the thioamide (68),1 89 and the phospholenium amide (69, Y = i-Pr2N).190... 

The reaction of alcohols with CO was catalyzed by Pd compounds, iodides and/or bromides, and amides (or thioamides). Thus, MeOH was carbonylated in the presence of Pd acetate, NiCl2, tV-methylpyrrolidone, Mel, and Lil to give HOAc. AcOH is prepared by the reaction of MeOH with CO in the presence of a catalyst system comprising a Pd compound, an ionic Br or I compound other than HBr or HI, a sulfone or sulfoxide, and, in some cases, a Ni compound and a phosphine oxide or a phosphinic acid.60 Palladium(II) salts catalyze the carbonylation of methyl iodide in methanol to methyl acetate in the presence of an excess of iodide, even without amine or phosphine co-ligands platinum(II) salts are less effective.61 A novel Pd11 complex (13) is a highly efficient catalyst for the carbonylation of organic alcohols and alkenes to carboxylic acids/esters.62... 

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 . ... 

The only comprehensive and readily-available surveys of thio- and seleno-phosphonic and -phosphinic acids appear to be those in the compilation by Kosolapoff and Maier which appeared during the 1970s, and those in the Houben-Weyl volumes. Some further information relevant to heterocyclic systems which possess endo- or exo-cyclic phosphorus-sulphur bonds has been surveyed by Mann Gefter has also provided a useful compilation of syntheses and data for unsaturated thiophosphonates and related compounds. As in the preceding chapters concerned with the synthesis of the various classes of phosphonic and phosphinic acids, literature surveys have been presented for individual compounds and the field, as a whole, is surveyed annually". In addition. Hall and Inch reviewed the mechanistic implications of changes in stereochemistry following displacement reactions at phosphorus in cyclic phosphorus(V) esters and amides, and in so doing discussed the reaction s of many such thiophosphoryl compounds. 

Esters of orthophosphoric acid have been used extensively as plasticizers and lubricant additives. Others have been used as flame retardants. Many sulfur analogues find use as insecticides, while the introduction of P—C bonds give phosphonic and phosphinic acids. Esters of pyrophosphoric acid (H4P2O7) are also of interest as are amide derivatives. 

Thereafter, the cleavage of the benzyl group followed by acetylation and amide coupling or esterification gave amide 134 or methyl ester 135. Deprotection of the methyl ester and acidification gave phosphinic acids 128 and 130, each as a mixture of two diastereomers. 

With dilute aqueous HCl, phosphinic acids are obtained, or esters from amidous esters. 

Squaric acid forms salts with aluminium, gallium, and indium. Amidation of squaric acid gives not only the 1,3- but also, the 1,2-diamides, which can be further acylated on the nitrogen. The amides, esters, and chlorides can be transformed into thiosquarates by the action of HS and cyclobutene dications can be obtained from the l,2-dithio-3,4-diamide. Neuse and Green have examined further arylation reactions of squaryl chlorides from which a variety of substituted cyclo-butenones may be obtained. Phosphine derivatives of the squarate system have also been reported. ... 

Thio) phosphoric acid ester (Thio) phosphonic (fhio) phosphinic acid ester acid ester Sulfonic acid ester Sulfonic acid amide... 

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