38938-31-7

Upstream product

• 67-56-1 methanol 
• 75-18-3 dimethylsulfide 
• 4129-17-3 diphenylphosphoranyl azide 
• 105584-85-8 N-(diphenylphosphinoyl)-O-(p-nitrophenylsulphonyl)-hydroxylamine 
• 73452-22-9 N-(Diphenylphosphinyl)-hydroxylamin-methylsulfonat 
• 124-41-4 sodium methylate 
• 84718-90-1 t-butyl(phenyl)phosphinic azide 
• 186581-53-3 diazomethane 
• 193346-75-7 C₂₆H₂₅NO₃P₂ 
• 1499-21-4 Diphenylphosphinic chloride 
• 824-72-6 P,P-dichlorophenylphosphine oxide 
• 1779-48-2 phenylphosphinic acid 
• 7162-15-4 methyl phenylphosphinate 
• 622-37-7 Phenyl azide 

Relevant academic research and scientific papers

Ligand-free copper-catalyzed denitrogenative arylation of phosphorylamides with arylhydrazines

A straightforward arylation of phosphorylamides with arylhydrazines hydrochloride was herein demonstrated. The protocol proceeded in the presence of a catalytic loading of Cu(OAc)2 as the catalyst, DTBP as the external oxidant and Cs2CO3 as the base, but without any ligands. And a series of N-aryl phosphorylamides were successfully obtained in high efficiency (up to 93% yields) with good substituents compatibility (up to 30 examples). Free radical mechanism was proposed for the facile methodology based on the results of control reactions and literature explorations.

Synthesis of phosphonamidate peptides by Staudinger reactions of silylated phosphinic acids and esters

The Staudinger reaction of unprotected azido-peptides with silylated phosphinic acids and esters on the solid support offers a straightforward acid-free entry to different phosphonamidate peptide esters or acids under mild conditions in high purity and yield.

Transposition of the phosphinoyl groups in the base-induced rearrangements of N,O-bis(diarylphosphinoyl)hydroxylamines

Because the N- and O-phosphinoyl groups can change places prior to rearrangement, Ph2P(O)NHOP(O)Ar2 and Ar2P(O)NHOP(O)Ph2 (Ar = p-tolyl) both give mixtures of two phosphonamidic-phosphimic anhydrides, Ph(PhNH)P(O)OP(O)Ar2 and Ar(ArNH)P(O)OP(O)Ph2, on treatment with KOBu(t) in Bu(t)OH. The transposition of the phosphinoyl groups may involve phosphorane intermediates (7 and 9) having the P atom contained within a three-membered ring.

N,O-bis(diphenylphosphinoyl)hydroxylamine base-induced rearrangement to a phosphonamidic-phosphinic mixed anhydride

The hydroxylamine derivative Ph2P(O)NHOP(O)Ph2 rearranges on treatment with Bu(t)OK-Bu(t)OH; the product contains two dissimilar P atoms (δ(p) 24.2 and 7.9, J(pp) 34 Hz) and is rapidly hydrolysed to a phosphonamidate and a phosphinate, consistent with it being the mixed anhydride Ph(PhNH)P(O)OP(O)Ph2.

O-Sulphonyl-N-phosphoylhydroxylamines: Nucleophilic Attack at Nitrogen by Dimethyl Sulphide and Allyl Methyl Sulphide Leading to N-Phosphoyl Sulphilimines

The O-sulphonyl-N-phosphoylhydroxylamines RR'P(O)NHX 6H4O; X=OMs or ONs> generally react with dimethyl sulphide and allyl methyl sulphide at room temperature in the absence of base.Nucleophilic attack at nitrogen, with displacement of the sulphonate anion, gives the protonated N-phosphoyl sulphilimines which is converted into the free sulphilimine on treatment with base.The allylic sulphilimines are labile, undergoing -sigmatropic rearrangement to N-phosphoyl-N-allylsulphenamides .In the light of these results, the formation of some sulphilimine when the base-induced rearrangement of Ph2P(O)NHOMs is carried out in dimethyl sulphide need not be seen as evidence for a nitrene mechanism.

Migration of the Amino Group in the Base-induced Rearrangements of N-(Aminophosphinoyl)-O-sulphonylhydroxylamines

The N-phosphinoylhydroxylamines R1R2P(O)NHOH having R1 = R2 = PhNH; R1 = Ph, R2 = PhNH; and R1 = Ph, R2 = Me2N have been prepared and converted into their O-methylsulp

Photolysis of Diphenyl- and t-Butyl(phenyl)-phosphinic Azides: Dimethyl Sulphide as a Nitrene Trap, and Its Influence on the Curtius-like Rearrangement

Photolysis of Ph2P(O)N3 in benzene containing MeOH gives a high yield (72percent) of the phosphonamidate PhP(O)(OMe)NHPh (3) resulting from Curtius-like rearrangement.When some of the benzene solvent is replaced by Me2S the yield of the rearrangement prod

Preparation and Characterisation of N-(Diphenylphosphinoyl)hydroxylamine, and Conversion into O-Sulphonyl Derivatives that undergo Lossen-like Rearrangement

Having previously shown that diphenylphosphinic chloride (1a) forms O-(diphenylphosphinoyl)hydroxylamine (3a) with hydroxylamine, we have now established that N-(diphenylphosphinoyl)hydroxylamine (2a) can be obtained in good yield by reaction of (1a) with O-trimethylsilylhydroxylamine followed by methanolytic removal of the silyl blocking group.The di-p-tolyl (2b) and bis-p-methoxyphenyl (2c) analogues can be prepared in a similar way.N-(Diphenylphosphinoyl)hydroxylamine is acetylated at the O atom with acetic anhydride, and is sulphonylated at O with methanesulphonyl chloride and toluene-p-sulphonyl chloride.The N-(diphenylphosphinoyl)-O-sulphonylhydroxylamines (8) and (12a) undergo rapid and quantitative Lossen-like rearrangement with methanol-sodium methoxide to give methyl N,P-diphenylphosphonamidate (11).Comparable rearrangement are observed with t-butylamine, aniline-triethylamine, and phenol-triethylamine.

DIARYLPHOSPHINIC AZIDES. PHOTOCHEMICAL REACTIONS INCLUDING REARRANGEMENT IN METHANOL

On photolysis in methanol the diarylphosphinic azides Ar2P(O)N3 (Ar=phenyl, p-tolyl, p-anisyl, p-chlorophenyl) rearrange with loss of nitrogen to form (monomeric) metaphosphonimidates which are trapped by the solvent to give methyl NP-diarylphosphonamidates (7) (41-53percent).Diarylphosphinic amides (18-42percent) are also usually formed, presumably from (triplet) nitrenes.The limited evidence available suggests that the rearrangements take place directly from the photo-excited azides rather than via (singlet) nitrene intermediates.One of the products of rearrangement, methyl NP-di(p-chlorophenyl)phosphonamidate, suffers extensive photochemical dechlorination giving methyl N-phenyl-P-p-chlorophenylphosphonamidate.

DIMETHYLSULPHIDE AS A NITRENE TRAP IN THE PHOTOLYSIS OF SOME PHOSPHINIC AZIDES

When PhRP(O)N3 (R=Ph or t-Bu) is photolysed in dimethylsulphide substantial amounts (22-32percent) of PhRP(O)N:SMe2 and PhRP(O)NHCH2SMe are produced and rearrangement is less important than in benzene.