Trialkyl Phosphates. I. Halogenation of Trialkyl Phosphites in the Presence of Alcohols

1966 ◽  
Vol 31 (3) ◽  
pp. 872-875 ◽  
Author(s):  
Arlen W. Frank ◽  
Charles F. Baranauckas
Keyword(s):  
Trialkyl Phosphates ◽  
Trialkyl Phosphites

Friedel-Crafts Alkylation of Aromatic Compounds with Phosphorus Esters

1972 ◽  
Vol 27 (11) ◽  
pp. 1339-1348 ◽  
Author(s):  
G. Sosnovsky ◽  
M. W. Shende
Keyword(s):  
Aluminum Chloride ◽  
Aromatic Compounds ◽  
Heterogeneous Reaction ◽  
Isomer Distribution ◽  
Aromatic Substrates ◽  
Trialkyl Phosphates ◽  
Strong Lewis Acid ◽  
Trialkyl Phosphites ◽  
Dialkyl Phosphites ◽  
Heterogeneous Reaction Conditions

The alkylations of aromatic compounds with trialkyl phosphites (1), dialkyl phosphites (2), and trialkyl phosphates (3) in the presence of aluminum chloride were studied involving several raction variables, such as time, ratio of reactants, nature of catalyst and solvent, and combinations thereof. Extensive disproportionation and isomerization were observed in the reaction with monosubstituted alkylbenzenes under heterogeneous reaction conditions obtained by the use of an excess of aromatic substrates. A combination of aluminum chloride—nitromethane complex and dichloromethane as solvent was used to eliminate these undesirable effects and to give homogeneous and practically non-isomerizing conditions. The scope of the reaction was studied with a number of aromatic substrates, and their relative reactivities were compared to that of benzene in competitive isopropylations with triisopropyl phosphite. The relative rates and isomer distributions showed low substrate and low positional selectivities and poor agreement with Brown’s selectivity relationship. The substrate selectivity was somewhat higher and the positional selectivities were somewhat lower than those obtained in competitive isopropylation reactions with other isopropylating agents. The selectivity factor, Sf, and partial rate factors were calculated. An electrophilic alkylation mechanism is proposed on the basis of (1) the relative rates of isopropylation, (2) the isomer distribution of dialkylated aromatics, and (3) the necessity of a strong Lewis acid in these reactions.

DIAMAGNETIC SUSCEPTIBILITIES OF SOME COMPOUNDS CONTAINING OXYGEN LINKED TO NITROGEN OR PHOSPHORUS

1964 ◽  
Vol 42 (8) ◽  
pp. 1817-1821 ◽  
Author(s):  
M. W. Lister ◽  
R. Marson
Keyword(s):  
Amine Oxide ◽  
Phosphine Oxides ◽  
Trialkyl Phosphates ◽  
Trialkyl Phosphites ◽  
Dialkyl Phosphites ◽  
Carboxylic Esters ◽  
Usual Formula ◽  
Extra Oxygen ◽  
Oxygen Atoms

The diamagnetic susceptibilities of a number of compounds containing oxygen linked to nitrogen or phosphorus have been measured. The results are interpreted in terms of the apparent contribution of the oxygen atoms to the susceptibility in these and other series of compounds, and are compared with other evidence on the nature of the bonds to oxygen. The results support the usual formula of an amine oxide as R3N → O, but phosphine oxides behave as would be expected for R3P = O. Phosphorus oxyhalides have molar susceptibilities about 4.6 (in units of −10−6 e.m.u.) larger than the corresponding trihalides, a difference close to that for singly bound oxygen in ethers or alcohols. Each oxygen contributes 4.4 in trialkyl phosphites, as might be expected for P(OR)3; but the value in dialkyl phosphites is 4.9 per oxygen, thereby showing behavior similar to that of carboxylic esters. The extra oxygen in trialkyl phosphates as compared with trialkyl phosphites contributes 9.4, a surprisingly large amount.

scholarly journals 1,1′-Dibenzyl-bis-(triazolyl)diphenylphosphine dioxide: a new efficient organocatalyst for silicon tetrachloride-mediated enantioselective Abramov-type phosphonylation of aldehydes with trialkyl phosphites

RSC Advances ◽  
2017 ◽  
Vol 7 (82) ◽  
pp. 52101-52104 ◽  
Author(s):  
Nicolas Sevrain ◽  
Jean-Noël Volle ◽  
Jean-Luc Pirat ◽  
Tahar Ayad ◽  
David Virieux
Keyword(s):  
Silicon Tetrachloride ◽  
Trialkyl Phosphites

Asymmetric phosphonylation of aldehydes with trialkyl phosphites mediated by SiCl4 and 1,1′-dibenzyl-bis-(triazolyl)diphenylphosphine dioxide organocatalyst.

The Formation of Dialkyl Isobenzofuran-1-ylphosphonates by Lewis Acid Promoted Reaction of o-Phthalaldehyde with Trialkyl Phosphites

Synthesis ◽  
2006 ◽  
Vol 2006 (24) ◽  
pp. 4124-4130
Author(s):  
Hirofumi Nakano ◽  
Kenji Yamana ◽  
Toshikazu Ibata
Keyword(s):  
Lewis Acid ◽  
Trialkyl Phosphites
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