O-Diphenylphosphinylhydroxylamine Chemical Properties

Melting point:

>140℃ (decomposition)

Boiling point:

368.0±25.0 °C(Predicted)

Density 

1.25±0.1 g/cm3(Predicted)

storage temp. 

2-8°C

solubility 

DMSO (Slightly), Methanol (Very Slightly, Sonicated)

pka

-1.65±0.70(Predicted)

form 

solid

color 

white

InChI

InChI=1S/C12H12NO2P/c13-15-16(14,11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H,13H2

InChIKey

SJECIYLGISUNRO-UHFFFAOYSA-N

SMILES

P(C1=CC=CC=C1)(C1=CC=CC=C1)(ON)=O

Safety Information

WGK Germany 

3

O-Diphenylphosphinylhydroxylamine Usage And Synthesis

Chemical Properties

Light yellow or white powder solid

Uses

Efficient reagent for direct conversion of aldehydes to nitriles in the presence of alcohol, ketone, ester, or amine functionality.

Uses

O-Diphenylphosphinylhydroxylamine is a versatile reactant used in the synthetic preparation of various products such as trans-acylaziridines and aldohydrazones.

Synthesis Reference(s)

Tetrahedron Letters, 23, p. 3835, 1982 DOI: 10.1016/S0040-4039(00)87720-5

Description

O-Diphenylphosphinylhydroxylamine (DPPH) is a versatile electrophilic amination reagent that has been used widely for the amination of stable carbanions, Grignard reagents, and π-electron-rich nitrogen heterocycles. Researchers have used DPPH for the aziridination of enones. Compared to other hydroxylamine derivatives typically stored as hydrochloride salts, this activated phosphinyl reagent exhibits good stability and can be stored indefinitely at 0 ℃. This compound in a single step from hydroxylamine hydrochloride and diphenylphosphinic chloride[1].

General Description

O-(Diphenylphosphinyl)hydroxylamine is a general reagent for electrophilic C-amination, which aminates a variety of stable carbanions and Grignard reagents.

Synthesis

The general procedure for the synthesis of diphenylphosphinic acid hydroxylamine from diphenylphosphinic acid chloride is as follows: to a 5 L four-necked round-bottomed flask (RBF) equipped with an overhead stirrer and a thermocouple are added sequentially (1) a solution of 60.85 grams (1.52 moles, 2.4 eq.) of NaOH dissolved in 180 mL of water, (2) 110.12 grams (1.58 moles, 2.5 eq.) of hydroxylamine- HCl dissolved in a solution of 180 mL of water, and (3) 180 mL of dioxane. The mixture was cooled to 0°C in an ice/acetone bath. Subsequently, 150 g of ice was added and a solution of diphenylphosphinic chloride (150.0 g, 0.634 mol, 1 eq.) dissolved in 180 mL of dioxane pre-cooled to about 10°C was added all at once. During the reaction the mixture becomes very viscous with the formation of a white precipitate and vigorous stirring is required. The internal temperature of the reaction rises to 22°C. After continued stirring for 5 to 10 minutes, the reaction mixture was diluted with 2.5 L of ice water and filtered through a large 15 cm diameter sintered funnel. The filter cake was drained on a glass stock for 1 hour, after which it was transferred back into 5 L of RBF. The solid was suspended in 500 mL of ice-cold 0.25 N NaOH solution with vigorous stirring for 5 to 10 min, filtered again, and washed twice with ice water, followed by drying on a porous filter overnight. The partially dried product was dried in a vacuum oven (50 °C, 0.1 Torr) for 12 h, after which it was well pulverized using a mortar and pestle grinder. Finally, the product was dried in a vacuum oven for another 16 hours to give 122 g (82% yield) of the target product diphenylphosphinoylhydroxylamine as a white powder.

References

[1] J. P. Anselm, J. L. Ferrari. “A New Journal for Organic Synthesis: Organic Preparations and Procedures International.” Journal of Chemical Education 48 5 (1971): 349.

O-Diphenylphosphinylhydroxylamine(72804-96-7)Related Product Information

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• O-(2-(vinyloxy)ethyl)hydroxylamine
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