- A Robust Methodology for the Synthesis of Phosphorothioates, Phosphinothioates and Phosphonothioates
-
A robust methodology for the synthesis of phosphorothioates, phosphinothioates and phosphonothioates, including those bearing low molecular weight S-alkyl side-chains, is presented. Application of the “caesium effect” in conjunction with the disulfide 3,3’-dithiobis(propionitrile), which acts as a shelf-stable sulfur source, avoids recourse to malodorous alkanethiols and toxic P?Cl precursors. A diverse range of sulfur-containing organophosphorus targets, including phosphorus-based heterocycles, may be prepared in consistently high yields. This chemistry also provides ready access to the corresponding DBU salts which are potential substrates for Pd-catalysed coupling reactions. (Figure presented.).
- Jones, David J.,O'Leary, Eileen M.,O'Sullivan, Timothy P.
-
supporting information
(2020/03/27)
-
- Solvent-free preparation method of alkylthiophosphonate
-
The invention discloses a solvent-free preparation method of an alkylthiophosphonate. The method comprises the following steps: 1) mixing an alcohol compound, a sulfur powder and a pH reagent, and reacting under the action of Bronsted acid at a temperatur
- -
-
Paragraph 00222-0028
(2019/03/06)
-
- Acid/Phosphide-Induced Radical Route to Alkyl and Alkenyl Sulfides and Phosphonothioates from Sodium Arylsulfinates in Water
-
A newly developed aqueous system with acid and phosphide was introduced in which odorless and stable sodium arylsulfinates can in situ generate arylsulfenyl radicals. These radicals have high reactivity to react with alkynes, alkenes, and H-phosphine oxides for the synthesis of alkyl and alkenyl sulfides and phosphonothioates. The control experiments and quantum calculations are also performed to gain insights into the generation mechanism of arylsulfenyl radicals. Notably, the chemistry is free of thiol odors, organic solvents, and metals.
- Lin, Ya-Mei,Lu, Guo-Ping,Wang, Gui-Xiang,Yi, Wen-Bin
-
p. 382 - 389
(2017/04/26)
-
- Metal- and base-free reductive coupling reaction of P(O)-H with aryl/alkyl sulfonyl chlorides: a novel protocol for the construction of P-S-C bonds
-
Novel and efficient synthesis of S-aryl/alkyl phosphinothioates from P(O)-H and aryl/alkyl sulfonyl chlorides under metal- and base-free conditions is described. This reaction provides an alternative strategy for the construction of P-S-C bonds in moderate to excellent yields. Moreover, this method can be readily applied to gram-scale preparation.
- Wang, Dungai,Zhao, Jinlong,Xu, Weigang,Shao, Changwei,Shi, Zheng,Li, Liang,Zhang, Xinghua
-
supporting information
p. 545 - 549
(2017/01/25)
-
- Catalyst- and oxidant-free coupling of disulfides with H-phosphine oxide: construction of P–S bond leading to thiophosphinates
-
An efficient protocol for the synthesis of thiophosphinates is presented, involving direct coupling of P–S bond between disulfides and H-phosphine oxide in moderate to good yields with good functional group compatibility. This procedure shows some advanta
- Xia, Minfang,Cheng, Jiang
-
supporting information
p. 4702 - 4704
(2016/10/03)
-
- N-(diphenylphosphinothioyl)hydroxylamine: Preparation, characterisation and base-induced transposition of sulfur and oxygen atoms in its O-benzoyl derivative
-
N-(Diphenylphosphinothioyl)hydroxylamine 5 has been prepared from Ph2P(S)Cl using H2NOSiMe3 and has been converted into its O-benzoyl derivative Ph2P(S)NHOCOPh 6. The principal reaction of the derivative 6 with base (NaOMe or ButNH2) is rearrangement, transposition of sulfur and oxygen giving Ph2P(O)NHSCOPh 7; this then reacts further, forming the phosphinic amide Ph2P(O)NH2 together with PhCO2Me or PhCONHBut. The rearrangement probably involves intramolecular nucleophilic displacement of benzoate by the P=S group of 6, forming an intermediate with P, N and S atoms in a three-membered ring.
- Harger, Martin J. P.
-
p. 3205 - 3209
(2007/10/03)
-
- A NEW, UNEXPECTED REACTION OF PHOSPHONOCHLORIDOTHIONATES WITH ALKYL ARYL ETHERS AND ALKYL CHLORIDES UNDER THE FRIEDEL-CRAFTS REACTION CONDITIONS
-
Phosphonochloridothionates have been found to react in the presence of Lewis acids with alkyl aryl ethers to give S-alkyl O-aryl phosphonothiolates and with alkyl halides to form products of the S-alkylation. Key words: Alkyl arel ethers; phosphonochloridothionates; alkylation; S-alkyl O-aryl phosphonothiolates; S-alkyl alkyl(aryl) dichlorophosphonium salts; conductivity.
- Omelanczuk, Jan
-
-
- PHASE-TRANSFER CATALYTIC ALKYLATION OF HYDROTHIOPHOSPHORYL COMPOUNDS. IV. REACTIONS WITH PRIMARY ALKYL HALIDES
-
A convenient general method for the synthesis of compounds containing a thiophosphoryl group was elaborated on the basis of the Michaelis-Becker reaction with the use of the method of phase-transfer catalysis. The influence of the nature of the hydrothiophosphoryl compounds, of the alkylating agents, and of the reaction conditions on the yields of alkylated products was investigated in detail.
- Aladzheva, I. M.,Odinets, I. L.,Petrovskii, P. V.,Mastryukova, T. A.,Kabachnik, M. I.
-
p. 431 - 437
(2007/10/02)
-
- THE REACTIONS OF α-ALKOXYALLYLPHOSPHINE OXIDE YLIDES WITH SILICON, SULPHUR AND PHOSPHORUS ELECTROPHILES
-
Anions (2), derived from α-methoxyallylphosphine oxides (1), react with silicon, sulphur and phosphorus electrophiles in a highly regioselective fashion to give the products of γ-attack.
- Devchand, Dipak K.,Murray, Alistair W.,Smeaton, Elizabeth
-
p. 4635 - 4638
(2007/10/02)
-
- PHOSPHORORGANISCHE VERBINDUNGEN 90 Methodische Ausgestaltung der P-C und P-S-Cyanolyse am Beispiel einiger Heterophosphoniumsalze
-
Treatment of allylamido-phosphonium salts with dry tetrabutylammonium cyanide in methylenechloride delivers after removal of the allyl group phosphinous acid amides with retention of configuration (P-C-cyanolysis).Allyl-O-alkylphosphonium salts undergo the Arbosov reaction under the above conditions, while allyl-S-alkyl phosphonium salts undergo fission of the P-S bond (P-S cyanolysis).Equally good results were obtained using KCN in methylene chloride accompained by catalytic amounts of 18-crown-6 ether; thus optically active benzyl-methyl-phenyl-phosphine-sulfid gave the corresponding phosphine with retention of configuration.Dithiophosphinic acid esters and thiophosphinic acid amides, after conversion to the corresponding quasiphosphonium salts via S-alkylation and subsequent treatment with tetrabutylammonium cyanide in methylenechloride, also give the corresponding thiophosphinous acid ester and phosphinous acid amide respectively.Thiophosphinic acid O-alkyl esters (R2P(S)OR') give however the thiophosphinic S-alkyl ester (R2P(O)SR') via an Arbusov reaction.The P-C cyanolysis of allyl-triphenylphosphoniumbromide using KCN/18-crown-6 or tetrabutylammonium cyanide in aprotic medium stops at the stage of the intermediary red-coloured ylide; addition of a proton-donor then results in the subsequent rearrangement to the corresponding propenyl-phosphonium salt.
- Horner, Leopold,Jordan, Manfred
-
p. 215 - 220
(2007/10/02)
-