Triphenylphosphine Dichloride

Abstract

image [ 2526‐64‐9 ] C 18 H 15 Cl 2 P (MW 333.20) InChI = 1S/C18H15Cl2P/c19‐21(20,16‐10‐4‐1‐5‐11‐16,17‐12‐6‐2‐7‐13‐17)18‐14‐8‐3‐9‐15‐18/h1‐15H InChIKey = ASWXNYNXAOQCCD‐UHFFFAOYSA‐N (conversion of alcohols, 6–10 phenols, 13 and enols 15 into alkyl chlorides; synthesis of vic ‐dichlorides 16 or chlorohydrins 17 from epoxides; conversion of carboxylic acids 11 and derivatives 20 into acyl chlorides; chlorination 23,24 or dehydration 11 of the CONH group; production of iminophosphoranes from amines and related compounds 27–29 ) Alternate Name: dichlorotriphenylphosphorane; triphenyldichlorophosphorane; chlorotriphenylphosphonium chloride. Physical Data: adduct: 2 white crystalline solid; mp 85–100 °C; 4 fp 20 °C. Ph 3 P: mp 80.5 °C; bp 377 °C (in inert gas); d 25 4 1.194 g mL −3 ; n 80 D 1.6358. Cl 2 : mp −101 °C; bp −34.6 °C; d 0 3.214 g L −1 . Solubility: adduct: slightly sol ether, THF, PhMe; sol CCl 4 , CH 2 Cl 2 , DMF, MeCN, pyridine; insol petroleum ether. Ph 3 P: sol ether, PhH, CHCl 3 , AcOH; less sol alcohol; pract insol H 2 O. Cl 2 : sol CCl 4 , alcohol. Form Supplied in: very hygroscopic solid; commercially available; purity ≈80%; the remainder is 1,2‐dichloroethane. The precursors Ph 3 P and Cl 2 are both widely available. Ph 3 P: odorless platelets or prisms; purity ≈99%; typical impurity is Ph 3 PO ≈1%. Cl 2 : greenish‐yellow gas, with suffocating odor; purity >99.3%; typical impurities are Br 2 , C 2 Cl 6 , C 6 Cl 6 , and H 2 O. Analysis of Reagent Purity: adduct: 2,3 31 P NMR (various solvents and solid state) +47 to +66 (ionic form), −6.5 to +8 (covalent form); Raman (solid state) ν(PCl) 593 cm −1 (ionic form), 274 cm −1 (covalent form). Typical impurities, Ph 3 P and Ph 3 PO: 31 P NMR (various solvents) −5 to −9 and +25 to +42, respectively. Preparative Methods: various preparations have been described; 5 the adduct is usually prepared just before use by addition of a stoichiometric amount of Chlorine to Triphenylphosphine in a dry solvent. 2 Handling, Storage, and Precautions: adduct: exceedingly sensitive to moisture; incompatible with strong oxidizing agents and strong bases; may decompose on exposure to moist air or water; do not get in eyes, on skin, or on clothing; keep containers closed and store in a cool dry place; these reagents should be handled in a fume hood.