cf. CA 55, 23400c. The Cu salt decompn. of diazo compds. in the presence of Ph3P opens up a new path to the synthesis of phosphorus-ylides. Ph3P (10 millimoles) and 10 millimoles 0.6M CH2N2 in Et2O treated 15 min. with 1 millimole anhyd. CuCl in 70 ml. tetrahydrofuran with vigorous evolution of N and the residue on evapn. hydrolyzed with dil. HCl, the soln. extd. to yield 6.5% Ph3PO, and the aq. phase neutralized with NaBPh4 yielded 13% [MePPh3]BPh4 (I), m. 195-6 Deg. In addn. 0,63 g. H2O- and Et2O-insol. adduct [Ph3P]2.CuCl (II), m. 239-42 Deg (Medoks and Andronova, CA 47, 9290g.) was isolated. Similar decompn. in Et2O gave 79% Ph3P, 13% Ph3PO, and 1.6% I. Decompn. in Et2O with addn. of 5 ml. C5H5N to the CuCl complex yielded 54% Ph3P,15% Ph3PO, and 2.6% I. Ph3P (10 millimoles) treated as above with 10 millimoles PhCHN2 in 20 ml. tetrahydrofuran 1 hr. to complete evolution of N, the red soln. decolorized with HCl, and the products isolated gave 10% PhCH2PPh3Cl, m. 325-8 Deg (PhCH2PPh3BPh4, m. 228-32 Deg), 10% Ph3P, 45% Ph3PO, and 41% PhCH:NN:CHPh. Ph3P (15 millimoles) and 1 millimole CuCl in 15 ml. boiling tetrahydrofuran treated dropwise in 90 min. with 15 millimoles Ph2CN2 in 15 ml. tetrahydrofuran, the mixt. refluxed 4 hrs. to complete evolution of N, and the mixt. hydrolyzed with acid yielded 34% Ph2CHPPh3Cl, m. 280-2 Deg. The Et2O-sol. portion contained 11% Ph3PO and 9% Phe(2HOH. An analogous reaction with 15 millimoles diazofluorene as diazo component yielded 32% 9-fluorenyl triphenylphosphonium bromide, m. 307-10 Deg, 14% fluorenone azine, m. 253-6 Deg, and 71% Ph3PO. Decompn. with 15 millimoles N2CHCO2Et as diazo component yielded 27% [EtO2CCH2PPh3]BPh4 (III), m. 173-5 Deg and 44% Ph3PO. The same reaction with 1 millimole AgNO3 as catalyst gave only 4% III and 67% Ph3PO. Use of 15 millimoles N2CHCOPh and direct treatment of the mixt. with petr. ether, followed by fractional crystn. from C6H6-petr. ether yielded 28% stable Ph3P:CHCOPh, m. 180-2 Deg, together with 5% Ph3P and some Ph3PO. Ph3P:CHPh (25 millimoles prepd. from 9.7 g. PhCH2PPh3Cl and 28 ml. 0.9M PhLi in 50 ml. tetrahydrofuran) decolorized by stirring 2 days (N atm.) with 25 millimoles PhCHN2 in 10 ml. tetrahydrofuran, the decoloration completed by addn. of alc.-Et2O and the mixt. filtered, the unchanged starting material converted into 22% [PhCH2PPh3]BPh4, m. 228-32 Deg, and the filtrate treated with 10 ml. MeI yielded 4.26 g. ppt., purified to give 31% MePPh3I, m. 188-9 Deg. The Et2O-sol. material chromatographed yielded 40% PhCH:NN:CHPh, resin, and small amts. of BzH and Ph3PO. Ph3P (20 millimoles) and 20 millimoles Ph2CO stirred in 70 ml. tetrahydrofuran with 1 millimole CuCl and treated in 1 hr. dropwise with 22 millimoles CH2N2 in Et2O, the tetrahydrofuran evapd. and the residue hydrolyzed, extd. with Et2O and the ext. treated with MeI to remove 18% Ph3P as Ph3PMeI, the Et2O evapd. from 45% Ph3PO and the fraction, b14 142-72 Deg, chromatographed over neutral Al2O3 yielded
