Organophosphorus compounds. XII. Proton and phosphorus-31 NMR spectroscopic studies of the protonation and cleavage of trialkyl(aryl)phosphates and phosphites, dialkyl phosphonates, and phosphorus oxy acids in fluorosulfuric acid, and fluorosulfuric acid-antimony pentafluoride

Infrared data were obtained for chloromethylphosphorous dichloride, chloromethylphosphonic dichloride (also Raman data), and chloromethylthiophosphonic dichloride over the region 45–3800 cm−1. Infrared data were also obtained for bromomethylphosphonic dibromide in the region 300–3800 cm−1. Infrared spectra for these compounds were recorded at different temperatures, and show that the pentavalent compounds exist as rotational isomers at room temperature. A previous study of chloromethylphosphonic dichloride and chloromethylthiophosphonic dichloride has established that these two compounds exist as rotational isomers, but the present study gives additional significant information. The infrared spectrum for methylphosphonic dichloride in the region 45–600 cm−1 has been recorded for purpose of comparison with the ClCH2–P series. No spectral evidence was observed for the P—CH3 torsion vibration in methylphosphonic dichloride.

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Organophosphorus compounds. V. Dialkyl alkylphosphonates from alkyl halides and sodium dialkyl phosphonates in liquid ammonia

Australian Journal of Chemistry ◽

10.1071/ch9650163 ◽

1965 ◽

Vol 18 (2) ◽

pp. 163 ◽

Cited By ~ 5

Author(s):

A Meisters ◽

JM Swan

Keyword(s):

Carbon Tetrachloride ◽

Good Yield ◽

Benzyl Chloride ◽

Liquid Ammonia ◽

Organophosphorus Compounds ◽

Alkyl Halides ◽

Ethyl Bromide ◽

Equivalent Quantity ◽

Dialkyl Phosphonates

Liquid ammonia is a useful solvent for the reaction of various alkyl halides with sodium dialkyl phosphonates. In this medium ethyl bromide, amyl bromide, octyl bromide, ally1 chloride, and benzyl chloride give the corresponding dialkyl alkylphosphonates in good yield. In other cases, alternative products are formed. Thus sodium diethyl phosphonate reacts with carbon tetrachloride or chloroform in liquid ammonia to give diethyl phosphoramidate; dibromomethane gives diethyl methylphosphonate and an equivalent quantity of diethyl phosphoramidate. p-Nitrobenzyl bromide gives mainly 1,2-di(p-nitrophenyl)ethane, 1-bromooct-1-yne is reduced to oct-1-yne, and 3-bromoprop-1-yne gives mainly propyne together with some diethyl prop-l- ynylphosphonate.

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Spectroscopic studies of organophosphorus compounds—III

Tetrahedron ◽

10.1016/s0040-4020(01)82141-4 ◽

1966 ◽

Vol 22 (7) ◽

pp. 2203-2211 ◽

Cited By ~ 5

Author(s):

M. Arshad ◽

A. Beg ◽

M.S. Siddiqui

Keyword(s):

Organophosphorus Compounds ◽

Spectroscopic Studies

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Spectroscopic studies of organophosphorus compounds—II

Tetrahedron ◽

10.1016/0040-4020(68)89021-0 ◽

1968 ◽

Vol 24 (1) ◽

pp. 191-198 ◽

Cited By ~ 3

Author(s):

M. Arshad A. Beg ◽

Samiuzzaman

Keyword(s):

Organophosphorus Compounds ◽

Spectroscopic Studies

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Catalytic Deoxygenative Coupling of Aromatic Esters with Organophosphorus Compounds

10.26434/chemrxiv.11973585 ◽

2020 ◽

Cited By ~ 1

Author(s):

Miki B. Kurosawa ◽

Ryota Isshiki ◽

Kei Muto ◽

Junichiro Yamaguchi

Keyword(s):

Organophosphorus Compounds ◽

Palladium Catalysis ◽

Sodium Formate ◽

Bifunctional Catalyst ◽

Phosphorus Compounds ◽

Aromatic Esters ◽

Dialkyl Phosphonates

We have developed a deoxygenative coupling of aromatic esters with diarylphosphine oxides/dialkyl phosphonates under palladium catalysis. In this reaction, aromatic esters can work as novel benzylation reagents to give the corresponding benzylic phosphorus compounds. The key of this reaction is the use of phenyl esters, an electron-rich diphosphine as a ligand, and sodium formate as a hydrogen source. Arylcarboxylic acids were also applicable in this reaction using (Boc)<sub>2</sub>O as an additive. Palladium/dcype worked as a bifunctional catalyst to activate the acyl C–O bond of the ester and to support the reduction with sodium formate.

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Catalytic Deoxygenative Coupling of Aromatic Esters with Organophosphorus Compounds

10.26434/chemrxiv.11973585.v1 ◽

2020 ◽

Author(s):

Miki B. Kurosawa ◽

Ryota Isshiki ◽

Kei Muto ◽

Junichiro Yamaguchi

Keyword(s):

Organophosphorus Compounds ◽

Palladium Catalysis ◽

Sodium Formate ◽

Bifunctional Catalyst ◽

Phosphorus Compounds ◽

Aromatic Esters ◽

Dialkyl Phosphonates

We have developed a deoxygenative coupling of aromatic esters with diarylphosphine oxides/dialkyl phosphonates under palladium catalysis. In this reaction, aromatic esters can work as novel benzylation reagents to give the corresponding benzylic phosphorus compounds. The key of this reaction is the use of phenyl esters, an electron-rich diphosphine as a ligand, and sodium formate as a hydrogen source. Arylcarboxylic acids were also applicable in this reaction using (Boc)<sub>2</sub>O as an additive. Palladium/dcype worked as a bifunctional catalyst to activate the acyl C–O bond of the ester and to support the reduction with sodium formate.

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SPECTROSCOPIC STUDIES OF ORGANOPHOSPHORUS COMPOUNDS: PART I. THE CONSTITUTION OF ALKYLPHOSPHINE – CARBON DISULFIDE ADDUCTS

Canadian Journal of Chemistry ◽

10.1139/v65-078 ◽

1965 ◽

Vol 43 (3) ◽

pp. 608-613 ◽

Cited By ~ 15

Author(s):

M. Arshad A. Beg ◽

M. S. Siddiqui

Keyword(s):

Carbon Disulfide ◽

Infrared Spectra ◽

Organophosphorus Compounds ◽

Spectroscopic Studies ◽

Phosphorus Compound ◽

Acceptor Molecule ◽

Phosphine Oxides

The constitution of the alkylphosphine – carbon disulfide adducts has been investigated by the study of their infrared spectra. Certain definite features of the spectra of the adducts are the shift of the P—C asymmetric vibrations to higher frequencies and the large shifts in the fundamentals of the acceptor molecule. These features are attributed to the formation of a quadruply connected phosphorus compound. From a comparison of the spectra of the carbon disulfide adducts with those of the corresponding phosphonium compounds, phosphine oxides and phosphines, evidence is provided for the structure of these compounds which has been suggested to be of the phosphonium type.

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