17417-07-1

Upstream product

• 1111-96-2 tributyldifluorophosphorane 
• 10025-85-1 nitrogen trichloride 
• 998-40-3 tributylphosphine 
• 814-29-9 Tributylphosphine oxide 
• 75-69-4 trichlorofluoromethane 

Relevant academic research and scientific papers

Long sought synthesis of quaternary phosphonium salts from phosphine oxides: Inverse reactivity approach

Quaternary phosphonium salts (QPS), a key class of organophosphorus compounds, have previously only been available by routes involving nucleophilic phosphorus. We report the realisation of the opposite approach to QPS utilising phosphine oxides as the electrophilic partner and Grignard reagents as nucleophiles. The process is enabled through the crucial intermediacy of the derived halophosphonium salts. The route does not suffer from the slow kinetics and limited availability of many parent phosphines and a broad range of QPS were prepared in excellent yields.

Structure of R3PCl2 compounds in the solid state and in solution: Dependency of structure on R. Crystal structures of trigonal bipyramidal (C6F5)3PCl2, Ph2(C6F5)PCl2 and of ionic Prn3PCl2

A number of triorganophosphorus dichloride compounds R3PCl2, (R3 = substituted aryl, mixed aryl-alkyl or triaryl) have been synthesized from diethyl ether solution and characterised by analytical and 31P-{1H} NMR data in CDCl3 solution. The majority of the compounds are ionic, [R3PCl]Cl, in CDCl3 solution, in keeping with analogous species containing the heavier halogens [R3PX]X (X = Br or I), according to 31P-{1H} NMR studies. In contrast, the compounds R3PCl2 [R3 = (C6F5)3 or (C6F5)Ph2] have a molecular five-co-ordinate trigonalbipyramidal structure both in CDCl3 solution and in the solid state. The crystal structures of these two compounds have been determined and represent the only crystallographic studies of trigonal-bipyramidal compounds of stoichiometry R3PCl2. The compound (C6F5)3PCl2 exhibits almost perfect trigonal-bipyramidal geometry, whereas (C6F5)Ph2PCl2 shows significant distortion. This may be due to the asymmetry of the equatorial groups around the phosphorus atom. Why R3PCl2 [R3 = (C6F5)3 or (C6F5)Ph2] adopt a trigonal-bipyramidal structure is reasoned to be due to the acidity of the parent tertiary phosphines, which favours this geometry for the dihalogen adducts, a phenomenon previously observed for dihalogen adducts of tertiary arsines. The crystal structure of Prn3PCl2, the first crystallographically characterised example of an ionic R3PCl2 compound which does not contain a solvent molecule, has been found to contain two Prn3PCl2 entities. The first consists of an ionic [Prn3PCl]+ unit weakly linked by a long Cl ... Cl contact to a Cl-, d(Cl ... Cl) 3.207(3) A. The second shows a discrete [Prn3PCl]+ cation, the Cl- anion being associated with δ+ H atoms on a [Prn3PCl]+ moiety. This compound was prepared and crystallised from diethyl ether and its relation to the solvated complex [Ph3PCl ... Cl ... ClPPh3]Cl·CH2Cl2 is discussed.

CHLOR-FLUOR -AUSTAUSCHREAKTIONEN MIT TRIALKYLFLUOR-PHOSPHORANEN

Trialkyldifluorophosphoranes R3PF2 (R = iPr, nBu) were found to react with chlorides or organoelement chlorides, EClm or ERm-zClz (EIV, m = 4, z = 1,2; EV, m = 3, z = 1,2) of elements belonging to main groups IV and V with chlorine/fluorine exchange to form the halophosphonium salts +Cl- (X = F, Cl) and the fluoro derivatives, EFm or ERm-zFz.With AlCl3 ionic products of composition are obtained.The transition metal chlorides, NiCl2, PdCl2 NiCl2(PMe3)2, and CoCl2 were found to be less reactive.Chlorine/fluorine exchange has been observed only the case of CoCl2.

REGIOSPECIFIC PREPARATION OF α,α-DIHALOFLUOROMETHYL PERFLUOROALKYL KETONES.

Acylation of F-phosphoranium salts with F-acyl chlorides gives the corresponding Z-perfluoro betaine in high yield.Subsequent chlorination or bromination regiospecifically yields the α,α-dihalofluoromethyl perfluoroalkyl ketones.