40547-38-4Relevant academic research and scientific papers
Fluorinated phosphorus compounds part 8. The reactions of bis(fluoroalkyl) phosphorochloridates with sulfur nucleophiles
Timperley, Christopher M.,Saunders, Sally A.,Szpalek, Josef,Waters, Matthew J.
, p. 161 - 171 (2003)
The reactivity of bis (fluoroalkyl)phosphorochloridates to nucleophiles is summarised. Previous data and the results described here indicate that reactivities decrease in the order: amines > alcohols > thiols. The synthesis of CF3CH2OP(O)(SEt)2 in 30% yield was accomplished by treating CF3CHOP(O)Cl2 with two molar equivalents of EtSH and Et3N in ether. The chloridates (CF3CH2O)2P(O)Cl and (C2F5CH2O)2-P(O)Cl did not react with MeSH in ether at -78 °C or when heated with Pb(SMe)2 in benzene. Ethanethiol and propanethiol reacted with fluorinated chloridates in the presence of triethylamine to give thiolates (RFO)2P(O)SR in 13-41% yield where RF was CF3CH2, C2F5CH2, C3F7CH2 or (CF3)2CH and R was Et or n-Pr. Similarly, reaction of phosphorobromidates (RFCH2O)2P(O)Br, made by brominating the corresponding bis(fluoroalkyl) H-phosphonates, with benzenethiol gave derivatives (RFCH2O)2P(O)SPh in 43 and 46% yield where RF was CF3 and C2F5, respectively. Treatment of the chloridothiolate Cl(EtO)P(O)SMe, prepared in two steps from triethyl phosphite, with flouroalcohols and triethylamine in ether gave species RFO(EtO)P(O)SMe in 62-74% yield where RF was CF3CH2, C2F5CH2, C3F7CH2 or (CF3)2CH. The reactions of bis(trifluoroethyl) phosphorochloridate with 2-mercaptoethanol, 3-mercaptopropanol and ethane-1,2-dithiol gave several unexpected products whose structures were tentatively assigned.
Phosphoranimines containing cationic N-imidazolinium moieties
Klaehn, John R.,Rollins, Harry W.,McNally, Joshua S.,Arulsamy, Navamoney,Dufek, Eric J.
, p. 254 - 265 (2017/06/23)
Three new monomeric phosphoranimines (PAs; R′[sbnd]N[dbnd]PR3) were synthesized by the Staudinger route using 2-azido-1,3-dimethylimidazolinium hexafluorophosphate [ADMImPF] and various phosphines to form their respective PA salts of triphenylphosphine (1), tri(n-octyl)phosphine (2), and tris(2,2,2-trifluoroethoxy)phosphite (3). These PA salts have a cationic imidazolinium moiety attached to nitrogen. Interestingly, 2 is a room temperature ionic liquid (RTIL) with a melting point around ?5?°C and a viscosity of 740cP at 25.5?°C. 1 and 2 show stability to moisture exposure and atmosphere for weeks whereas 3 is not stable toward atmospheric moisture undergoing decomposition to form 2-amino-1,3-dimethylimidazolinium phosphate (4). Thermal analyses reveal that 1 and 2 are stable to 90?°C under nitrogen, but 3 undergoes degradation by exposure to moisture and/or elevated temperature. All compounds exhibit similar multinuclear NMR chemical shifts as compared to their corresponding phosphine oxide counterparts. However, their respective X-ray structure determinations indicate that 2 has an open structure with the octyl groups that avoid the ionic charges, whereas 1 and 3 have tighter structural packing of the hexafluorophosphate to their pendant groups.
