6230-68-8

Usage

Main use

Reaction agent in organic synthesis

Structure

Piperidine ring with a phosphoryl group attached to the nitrogen atom

Applications

Conversion of alcohols to alkyl chlorides or bromides
Preparation of phosphonium salts
Synthesis of pharmaceutical compounds
Potential use in drug development
Production of insecticides and herbicides

Hazard

Toxic and hazardous chemical

Safety

Handle with caution

Upstream product

• 110-89-4 piperidine 
• 1499-21-4 Diphenylphosphinic chloride 
• 46346-67-2 N-benzyloxypiperidine 
• 4559-70-0 Diphenylphosphine oxide 
• 75599-76-7 2,4-dinitrophenyl diphenylphosphinate 
• 10259-20-8 4-nitrophenyl diphenylphosphinate 
• 112945-81-0 3,4-dinitrophenyl diphenylphosphinate 
• 66667-06-9 4-formylphenyl diphenylphosphinate 
• 102817-54-9 4-cyanophenyl diphenylphosphinate 
• 21713-55-3 O-4-chlorophenyl diphenylphosphinate 
• 21713-56-4 4-acetylphenyl diphenylphosphinate 
• 912946-27-1 3-acetylphenyl diphenylphosphinate 

Relevant academic research and scientific papers

Practical Synthesis of Phosphinic Amides/Phosphoramidates through Catalytic Oxidative Coupling of Amines and P(O)?H Compounds

Herein, we report a highly efficient ZnI2-triggered oxidative cross-coupling reaction of P(O)?H compounds and amines. This operationally simple protocol provides unprecedented generic access to phosphinic amides/phosphoramidate derivatives in good yields and short reaction time. Besides, the reaction proceeds under mild conditions, which avoids the use of hazardous reagents, and is applicable to scale-up syntheses as well as late-stage functionalization of drug molecules. The stereospecific coupling is also achieved from readily available optically enriched P(O)?H compounds.

Efficient electrosynthesis of phosphinic amides via oxidative cross-coupling between N-H/P-H

A facile and efficient approach to phosphinic amides was developed from diarylphosphine oxides and amines via electrosynthesis. A variety of phosphinic amides were obtained in one step with good to excellent yields under mild and metal-free conditions. Th

Cooperative Effects between Chiral Cpx–Iridium(III) Catalysts and Chiral Carboxylic Acids in Enantioselective C?H Amidations of Phosphine Oxides

An enantioselective C?H amidation of phosphine oxides by using an iridium(III) catalyst bearing an atropchiral cyclopentadienyl (Cpx) ligand is reported. A very strong cooperative effect between the chiral Cpx ligand and a phthaloyl tert-leucine enabled the transformation. Matched–mismatched cases of the different acid enantiomers are shown. The amidated P-chiral arylphosphine oxides are formed in yields of up to 95 % and with excellent enantioselectivities of up to 99:1 er. Enantiospecific reduction provides access to valuable P-chiral phosphorus(III) compounds.

A Catalyst-Free Synthesis of Phosphinic Amides Using O-Benzoylhydroxylamines

A practical approach for the synthesis of phosphinic amides via the coupling of secondary phosphine oxides (SPOs) with O-benzoylhydroxylamines has been reported. Simply heating the mixture of SPOs and O-benzoylhydroxylamines in the presence of K2/su

Synthesis of new organophosphorus compounds using the atherton-todd reaction as a versatile tool

This article discusses the behavior of seven organophosphorus compounds under Atherton-Todd conditions. Therefore, the reactivity and selectivity of different (phen)oxaphosphinines, dioxaphosphinines, dioxaphosphinanes, and diphenylphosphine oxide with three nucleophiles were systematically studied. The results prove the versatility of the Atherton-Todd reaction to a broad range of organophosphorus compounds with different phosphorus environments and reactive Pi-H bonds. The nucleophiles studied in this article were chosen as model substrates for amines and alcohols. Because organophosphorus molecules are important and versatile compounds, for a broad field of applications, novel synthetic approaches are of interest to both academia and industry. As an example, the single-step synthesis of the bridged 1,3-phenylene bis(diphenylphosphinate) with potential flame-retardant properties was added to this study. In addition, the reaction is utilized for the synthesis of a novel organophosphorus anhydride.

Aminolyses of aryl diphenylphosphinates and diphenylphosphinothioates: Effect of modification of electrophilic center from P=O to P=S

(Chemical Equation Presented) A kinetic study is reported for aminolysis of aryl diphenylphosphinothioates (2a-i). The phosphinothioates 2a-i are less reactive than aryl diphenylphosphinates (1a-i), the oxygen analogues of 2a-i, regardless of the basicity

Aminolysis of Y-substituted phenyl diphenylphosphinates and benzoates: Effect of modification of electrophilic center from C=O to P=O

(Chemical Equation Presented) The effect of modification of the electrophilic center from C=O to P=O on reactivity and reaction mechanism has been investigated for aminolysis of Y-substituted phenyl diphenylphosphinates (1a-j) and benzoates (2a-i). The phosphinates 1a-j are less reactive than the benzoates 2a-i. The reactions of 2,4-dinitrophenyl diphenylphosphinate (1a) with alicyclic secondary amines resulted in a linear Bronsted-type plot with a βnuc value of 0.38, while the corresponding reactions of 2,4-dinitrophenyl benzoate (2a) yielded a curved Bronsted-type plot. Similarly, a linear Bronsted-type plot with a β1g value of -0.66 was obtained for the reactions of 1a-j with piperidine, while the corresponding reactions of 2a-i gave a curved Bronsted-type plot. The linear Bronsted-type plots for the reactions of 1a-j have been taken as evidence for a concerted mechanism, while the curved Bronsted-type plots for the reactions of 2a-i have been suggested to indicate a change in the rate-determining step of a stepwise mechanism. The Hammett plot for the reactions of 1b-j exhibited a poor correlation with σ- constants (R2 = 0.962) but slightly better correlation with σo (R2 = 0.986). However, the Yukawa-Tsuno plot for the same reactions resulted in an excellent correlation (R2 = 0.9993) with an r value of 0.30. The aminolysis of 1a-j has been suggested to proceed through a concerted mechanism with an early transition state on the basis of the small βnuc and small r values.

Organic phosphorus compounds 106.1 a 31P-NMR study of phosphinous-, phosphinic-, and thiophosphinic amides

The synthesis, physical, chemical and spectroscopic properties of eight different types of phosphinous-, phosphinic-and thiophosphinic amides are reported. It is shown that the 31P-chem. shifts of tertiary amides are at lower magnetic field than that of secondary amides. As an exception, in the bis(tertiary butyl) series this trend is reversed.

THE AMINOLYSIS OF PHOSPHINATES; THE KINETICS AND MECHANISM OF THE AMINOLYSIS OF PHOSPHINATE ESTERS IN ACETONITRILE

The aminolysis of aryl diphenylphosphinates, p-nitrophenyl diphenylphosphinothionate, -phosphinothioate, and -phosphinodithioate by n-butylamine, by the secondary amines piperidine, pyrrolidine, morpholine, and dipropylamine, as well as by a series of diamines, has been studied in acetonitrile.The general reactivity order is diamines > butylamine > sec-amines.Butylaminolysis follows a two-term rate law, one first order in amine and the other second order in amine.The second order in amine term predominates. sec-Amines and diamines follow a rate law which is first order in amine only.Leaving group effects, solvent effects, and activation parameters support a pathway which involves rate-determining collapse of a zwitterionic pentacoordinate intermediate.In the case of butylamine this collapse is general base catalyzed and for the diamines the reaction is intramolecularly general base catalyzed.