Diphenylphosphinyl chloride

Electrophiles, which lead to high yields, are methyl iodide, trialkyltin- and trialkylsUyl chlorides, diphenylphosphinyl chloride, acid chlorides, aldehydes and carbon dioxide. Remarkably, though highly acidic ketones are formed on acylation, no deprotonation or racemization by excess of carbanionic species occurs. Other alkyl halides than methyl iodide react very sluggishly with low yields. Benzylic and aUylic halides lead to partial racemization, presumably due to single-electron transfer (SET) in the alkylation step. As very recently found by Papillon and Taylor, racemization of 42 can be suppressed by copper-zinc-lithium exchange before alkylation to 43 via the Knochel cuprates (equation 7) °. 

The only symmetric phosphorus peroxide reported is bis(diphenylphosphonyl) peroxide 8. It is prepared by condensation of diphenylphosphinyl chloride with sodium peroxide (equation 94). When the same procedure was applied for substituted arenephosphinyl chlorides, no peroxide was observed. Peroxide 8 is stable at —80 °C and decomposes at room temperature. 

A. O-Diphenylphosphinylhydi oxylamine. A 5ilO-mL, round-bottomed flask, equipped with a reflux condenser, drying tube, an efficient mechanical stirrer, a dropping funnel and a nitrogen-inlet tube, 1s charged with 300 mL of anhydrous methylene chloride, 16.5 g (0.5 mol) of hydroxylamine base (Note 1), and 1,0 g of dry sodium bicarbonate. While the suspension 1s stirred vigorously at -30°C (bath temperature), a solution of 52.06 g (0.22 mol) of diphenylphosphinyl chloride (Note 2) in 70 mL of anhydrous methylene chloride... 

Diphenylphosphinyl chloride can be purchased from Aldrich Chemical Company, Inc. or from EGA-Chem1e, D-7924 Steinheim, West Germany (an Aldrich Chemical Company). Diphenylphosphinyl chloride can also be prepared by oxygen-mediated oxidation of dlphenylchlorophosphlne5 (purchased from Fluka AG, CH-9470 Buchs, Switzerland). 

The recovered and dried diphenylphosphinic acid, 19.6 g (90%), is ready to be recycled to diphenylphosphinyl chloride. ... 

Diphenylphosphinyl chloride Phospinic chloride, diphenyl- (8,9) (1499-21-4) 7-Benzylideneaminotheophyl1ine lH-Purine-2,6-dione, 3,7-dihydro-1,3-dimethyl -7-r(phenylmethylene)amino]- (11) (81281-59-6)... 

Mol. wt. 340.27, m.p. 125-127°. The phosphinic ester is prepared by reaction of diphenylphosphinyl chloride and 2-hydroxy-5-nitropyridine in the presence of triethylamine. 

Tetrahydrothiopyran 1-oxide is readily metallated at C-2 with -BuLi quenching the reaction mixture with diphenylphosphinyl chloride and subsequent oxidation affords the /ra r-diphenylphoshine oxide 307 (Scheme 50)... 

Tris(morpholine)selenonium fluoride (33), easily prepared by the reaction of JV-trimethylsilylmorpholine (34) with selenium tetrafluoride (35), is a very useful reagent for chloride/fluoride exchange reactions (121. Thus, benzenesulfonyl chloride (36) and diphenylphosphinyl chloride (37) gave upon treatment with 33 the corresponding fluorides 38 and 39 in good yields (Scheme 5). 

Commercial reagent grade diphenylphosphinyl chloride from Aldrich Chemical Company, Inc. was used as obtained. This compound can be prepared either by oxidation of diphenylphosphinous chloride with dimethyl sulfoxide or by the treatment of diphenylphosphinic acid with phosphorus pentachlorlde. ... 

Diphenylphosphinyl chlorides and simple ylides yield 1-diphenylphosphinylalkylidenephosphoranes in a transylidation reaction the introduction of the thiophosphinyl group may be carried out analogously (equation 32). Synthesis of diethoxy- and diphenoxy-phosphinomethylenetriphenylphosphoranes may be achieved with the corresponding phosphoro chloridates (equation 33). 

Sample preparation 500 jjlL Plasma or serum or 200 p,L urine + 1 mL pH 7 buffer + 2 mL dichloromethane, shake, centrifuge at 2500 g for 5 min. Remove 1 mL organic layer and add it to 1 mL dichloromethane containing 20 p,L diphenylphosphinyl chloride and 20 p,L triethylamine, vortex for 10 s, add 500 p,L L-leucinamide solution, shake for 10 min, extract with 200 p.L 1 M HCl (500 p,L 0.5 M HCl for urine samples), inject 100 p,L of aqueous supernatant. (Prepare L-leucinamide solution by adding 10 mL dichloromethane and 1 mL 5 M NaOH to 500 mg L-leucinamide hydrochloride, shake, discard upper aqueous layer, store dichloromethane layer over anhydrous sodium sulfate.)... 

Preparation. - The reaction of diphenylphosphinyl chloride with dicyclopentadienylsamarium (or samarium diiodide), followed by an alkyl halide (or alkyl tosylate, epoxide, or a,P-unsaturated ketone), provides a route to a... 

PROTECTION OF AMINO GROUPS 2-BenzoyloxymethylbenzoyI chloride. Di-t-butyl-dicarbonate. Diphenylphosphinyl chloride. p-Phcnylbcnzoyl chloride. Phcnyl-[2-p-phenylazophenyDisopropyl]-carbonate. p-Toluenesulfonyl isocyanate. 

PEPTIDES Benzotriazolyloxytris(dimethylamino)-phosphonium hexafluorophosphate. Diethyl phosphorocyanidate. Diphenylphosphinyl chloride. 4,6-Diphenylthienol3,4-dJ-dioxol-2-one-5,S-dioxide. Thioglycolic add. 

Figure 3. Reactions of racemic adds with alkyl chloroformates and diphenylphosphinyl chloride.

Diphenylphosphinyl chloride N-methylmorpholineltriethylamine Phenol ring from 3,5-dienecarboxylic acids m-Hydroxycarboxylic acid esters... 

A soln. of 3-methoxycarbonyl-5-methylhexa-3,5-dienoic acid in dichloromethane treated sequentially under N2 with a soln. of N-methylmorpholine and diphenylphosphinyl chloride in dichloromethane at —23°, stirred for 28 min, triethylamine in the same solvent added, and stirred for 10 min at —23°, 10 min at 0°, and 1.5 h at ambient temp. methyl 3-hydroxy-5-methylbenzoate. Y 50%. F.e. and tetrahydro-pyridines s. K. Clinch et al.. Tetrahedron 45, 239-58 (1989). 

Thiosemicarbazides that are not substituted at the 4-position have been obtained by the action of ammonium rhodanide, or potassium rhodanide in the presence of hydrochloric acid, on hydrazines. A thio-semicarbazide of the type (210) was the only product obtained by the treatment of a 4-substituted thiosemicarbazide with diphenylphosphinyl chloride. ... 

Preparation.—Modifications of the standard procedure (R COjH + R SH) employ 4-(dimethylamino)pyridine and dicyclohexylcarbodi-imide, diphenylphosphinyl chloride, or Me2NP(0)Cl2 as coupling reagents. Related methods e,g. acyl... 

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