70795-79-8

Upstream product

• 109-89-7 diethylamine 
• 15849-83-9 ethylphenylphosphinous chloride 
• 74-96-4 ethyl bromide 
• 3376-52-1 pentaphenylcyclopentaphosphane 
• 70795-79-8 ethyl-phenyl-phosphinous acid diethylamide 
• 70795-79-8 R(-)-Ethylphenyl-phosphinigsaere-diethylamid 

Downstream Products

• 70795-80-1 1-(diethylamino)-1-ethoxy-2-ethyl-2-phenyldiphosphine 1-oxide 
• 1069-08-5 diethylphosphoramidous dichloride 
• 15849-83-9 ethylphenylphosphinous chloride 
• 660-68-4 diethyl amine hydrochloride 
• 77599-09-8 1-(2-chloroethoxy)-1-(diethylamino)-2-ethyl-2-phenyldiphosphine 1-oxide 
• 70795-79-8 Ethyl-phenyl-phosphingsaere-diethylamid 
• 360-92-9 N,N-diethyl-2,2,2-trifluoroacetamide 
• 20337-70-6 methyl ester of ethylphenylphosphonous acid 
• 109-89-7 diethylamine 
• 70795-79-8 ethyl-phenyl-phosphinous acid diethylamide 
• 26515-05-9 (-)-(S_P)-ethylmethylphenylphosphine oxide 
• 17045-47-5 (R)-ethyl(methyl)(phenyl)phosphane oxide 
• 685-91-6 diethylacetamide 
• 74607-57-1 C₁₄H₁₅PS 

Relevant academic research and scientific papers

Dialkylamino-phenyldi- and -triphosphides from the Degradation of (PhP)5 by Alkali Amides

(PhP)5 and lithium dialkylamides in tetrahydrofuran form equilibrium mixtures of lithium aminophenylphosphides (PhP)nNR2(-) with n = 3 and (mainly) 2.The monophosphides (n = 1) are not formed; it is concluded that they are generally unstable, decomposing to aminodiphosphides and cyclophosphines.Alkylation of an equilibrium mixture gives 1-alkyl-2-dialkylamino-diphenyldiphosphines which, however, are thermally unstable. (PhP)5 degradation equilibria using different anionic nucleophiles are compared. - Key words: Cyclophosphines, Nucleophilic Degradation Equilibria, Aminophosphides, Diphosphines, 13C NMR Spectra

PHOSPHORORGANISCHE VERBINDUNGEN 92 Zur Stereochemie und zum chemischen Verhalten optisch aktiver Amidophosphoniumsalze und optisch aktiver Phosphinigsaereamide

Optically active amides of phosphinous acids R1R2PNR2 4 (R1 = Ph, R2 = Me, R = Et) may be obtained in high yield from the corresponding chiral amidophosphonium salts 1R2R3PNR2>X(R1 = Ph, R2 = CH3, Et, R3 = Bz or allyl, R = Et) via cathodic fassion or cyanolysis, both processes proceeding under retention of configuration at phosphorus.The optically active amidophosphonium salts (e.g. ethyl-methyl-phenyl-diethylamidophosphonium iodide 10 or benzyl-ethyl-phenyl-diethylamidophosphonium bromide 12 were prepared: a.) from the optically active tertiary phosphines (e.g.R-(+)-benzyl-methyl-phenyl-phosphine 6 or S-(-)-ethyl-methyl-phenyl-phosphine 13 on treatment with aryl or alkyl azides and subsequent alkylation of the ensueing phosphine imine 7. b.) from the chiral phosphinous acid amide 4 on alkylation.Methods a) and b) proceed under retention of configuration at phosphorus. c.) treatment of chiral phosphines with N-haloamines results in racemic amidophosphonium salts. Optically active amidophosphonium salts (eg.S-(+)-benzyl-methyl-phenyl-diethylamidophosphonium bromide 8 or R-(-) 10) are converted to the corresponding phosphine oxides 9 or 11 under inversion of configuration on treatment with aqueous alkali.LiAlH4 removes the amino ligand, converting amidophosphonium salts (eg.S-(+) 12) to the optically active phosphine under retention of configuration.Treatment of S(+)-ethyl-phenyl-diethylamidophosphonium bromide 5 with benzaldehyde gives stilbene and chiral ethyl-phenyl-phosphinic acid diethylamide 17 under retention of configuration; 7 is also obtained from R-(-) 4 on oxidation with H2O2.R-(-) 4 gives optically active ethyl-phenyl-thiophosphine acid diethylamide 18 on treatment with sulphur.Optically active 4 undergoes spontaneous racemization at 130 deg either in the neat phase or dissolved in hydrocarbons, zero order kinetics being observed.The racemization is proposed to occur through a cyclic bimolecular association, since compounds with different groups at phosphorus and nitrogen exchange ligands (forming crossed the phosphinous acid amides in approximately equal quantities) after three hours at 200 deg C.Phosphinous acid amides (eg. 4) form chiral charge-transfer complexes with nitrobenzene, which undergo racemization quickly even at room temperature.Optically active 4. when used as co-catalyst with (RhCl-hexa-1,5-diene), enables the homogeneous hydrogenation of α-ethylstyrene to 2-phenylbutane to be carried out with an optical yield of 34percent.

PHOSPHORORGANISCHE VERBINDUNGEN 90 Methodische Ausgestaltung der P-C und P-S-Cyanolyse am Beispiel einiger Heterophosphoniumsalze

Treatment of allylamido-phosphonium salts with dry tetrabutylammonium cyanide in methylenechloride delivers after removal of the allyl group phosphinous acid amides with retention of configuration (P-C-cyanolysis).Allyl-O-alkylphosphonium salts undergo the Arbosov reaction under the above conditions, while allyl-S-alkyl phosphonium salts undergo fission of the P-S bond (P-S cyanolysis).Equally good results were obtained using KCN in methylene chloride accompained by catalytic amounts of 18-crown-6 ether; thus optically active benzyl-methyl-phenyl-phosphine-sulfid gave the corresponding phosphine with retention of configuration.Dithiophosphinic acid esters and thiophosphinic acid amides, after conversion to the corresponding quasiphosphonium salts via S-alkylation and subsequent treatment with tetrabutylammonium cyanide in methylenechloride, also give the corresponding thiophosphinous acid ester and phosphinous acid amide respectively.Thiophosphinic acid O-alkyl esters (R2P(S)OR') give however the thiophosphinic S-alkyl ester (R2P(O)SR') via an Arbusov reaction.The P-C cyanolysis of allyl-triphenylphosphoniumbromide using KCN/18-crown-6 or tetrabutylammonium cyanide in aprotic medium stops at the stage of the intermediary red-coloured ylide; addition of a proton-donor then results in the subsequent rearrangement to the corresponding propenyl-phosphonium salt.