H atoms in the a-position to a quadricovalent P atom could be exchanged by D with D2O under mild alk. conditions. The phosphonium salts, which can be readily deuterated under these conditions, served as the key intermediates for the synthesis of selectively labeled substances. A mixt. of 10 millimoles appropriate phosphonium salt stirred 0.5 hr. with 5 cc. 99.7% D2O, filtered, stirred 2 hrs. at 22 Deg with 0.53 g. Na2CO3 or with 0.08 g. NaHCO3 or without basic catalyst, filtered, and acidified with 2N DCl, DBr, or D3PO4 gave the corresponding labeled compd. [Ph3PCH2Cl]Cl (I) (2.50 g.), m. 260-1 Deg, gave in this manner 2.32 g. [Ph3PCD2Cl]Cl (II), m. 261-3 Deg. Similarly were prepd. the [Ph3PCD2R]X listed in the table. [Ph3PCH2Ph]Cl (13.8 g.), m. 329-33 Deg, in 25 cc. 2:3 D2O-(CH2OMe)2 refluxed to soln., treated with a concd. soln. of 0.13 Na2CO3 in D2O, kept 3 hrs. at 60 Deg, and acidified with DCl-D2O yielded 13.4 g. [Ph3PCD2Ph]Cl (IV), m. 333-5 Deg. m.p.; R, X, catalyst, m.p., [Ph3PCH2R]X; D, Br, Na2CO3, 230-1 Deg, 232-3 Deg; Pr, Br, Na2CO3, 240-1 Deg, 240-1 Deg; MeO, Cl (III), Na2CO3, 194-7 Deg, 196-200 Deg; MeS, Cl, NahCO3, 225-6 Deg, 224-6 Deg; Br, Br, NaHCO3, 237-9 Deg, 237-40 Deg; CO2Me, Br, none, 156 Deg, 157 Deg; Ac, Cl, none, 237-40 Deg, 237-40 Deg; Bz, Cl, none, 267-71 Deg, 270-2 Deg; [Ph3PCH2Ph]Br (4.33 g.) in 30 cc. D2O and 30 cc. (CH2OMe)2 treated at 33 +- 1 Deg with 0.05 g. NaHCO3 showed a 15-min. half-time for the exchange. [Ph3PCHMe2]Br (3.85 g.), m. 239-40 Deg, in 25 cc. (CH2OMe)2 stirred 5 hrs. with 11 millimoles PhLi-Et2O and treated with 1 cc. 2N DBr in D2O gave 3.38 g. [Ph3PCDMe2]Br, m. 239-41 Deg (CH2Cl2-AcOEt). [Ph3PCH2I]I (V) (15.0 g.), m. 231-3 Deg, refluxed 5 min. with 30 cc. D2O and 350 cc. C5H5N gave 8.8 g. [Ph3PCD2I]I (VI), m. 231-3 Deg (MeOH-Et2O); similar results were obtained by refluxing 1.0 g. V in 500 cc. CH2Cl2 with 5 cc. 0.1N NaHCO3 in D2O. [Ph3PCH2CH:CH2]Br (4.0 millimoles), m. 214-19 Deg, in 40 cc. H2O and 60 cc. (CH2OMe)2 kept 2 days at room temp. and acidified with concd. HBr gave 0.80 g. [Ph3PCH2CH(OH)Me]Br (VII), m. 221-3 Deg (iso-PrOH). Ph3P and MeCH(OH)CH2Cl (10 millimoles each) heated 10 hrs. at 160 Deg gave 1.38 g. VII, m. 221-3 Deg. III (44 millimoles) heated during 15 min. to 235 Deg and kept 10 min. at 95 Deg yielded 2.57 g. ClCD2OMe (VIII), b. 54-7.5 Deg, and 9.4 g. Ph3P, m. 79-81 Deg (EtOH). The hydrolysis of VIII developed the odor of CH2O. VIII in dry Et2O treated with Ph3CNa in abs. Et2O until the red color persisted and then hydrolyzed gave Ph3CCD2OMe, m. 135-7 Deg, and small amts. of Ph3CH, m. 88-9 Deg, and p-Ph2CHC6H4CPh3, m. 225-8 Deg. The VIII treated overnight with 30 millimoles Ph3P in 50 cc. dry C6H6, and then cryst. ppt. treated in H2O with NaHCO3 to weakly alk. reaction yielded 7.8 g. III, m. 200-1 Deg. VI (8.0 g.) with 3 cc. 33% NaOD-D2O distd. immediately yielded 1.2 g. CD3I, which treated in dry Et2O with Ph3P yielded [Ph3PCD3]I (IX), m. 189-90 Deg. CD3I treated with Ph3CLi in Et2O until the red color persisted yielded Ph3CCD3, m. 93.5-94 Deg (MeOH). IV (8.0 g.) stirred 24 hrs. with 40 cc. N NaOD in D2O gave 2.1 cc. PhCD3, m. 108-9 Deg. IX (20.0 g.) stirred 1 hr. with 50 cc. 10% NaOD-D2O and 50 cc. dry (CH2OMe)2 and refluxed 1 hr. yielded 5.6 g. Ph2P(O)CD3 (X), m. 112.5-13.5 Deg (C6H6-Et2O). X (5.00 g.) in 50 cc. dry C6H6 and 3.8 g. LiAlH4 in 50 cc. Bu2O heated 4 hrs. at 100 Deg gave 2.63 g. Ph2PCD3, b. 145-6 Deg (pressure unstated). [Ph3PCD2Ph)Br (8.7 g.) in 30 cc. dry (CH2OMe)2 treated dropwise with stirring with 23 cc. 0.93N PhLi-Et2O, the mixt. refluxed 2 hrs., neutralized with D3PO4, and stirred with LiI, and the product filtered off gave 1.42 g. (PhCD:)2, which was sepd. chromatographically into the cis isomer, m. 0-1 Deg, and the trans isomer, m. 121.5-23 Deg. Ph3P:CDPh (XI) (20 millimoles) with 2.20 g. BzH stirred 15 hrs. at room temp. yielded 3.26 g. PhCH:CDPh, which contained mainly the trans isomer, m. 123-5 Deg. XI (20 millimoles) treated at -30 to -20 Deg with 2.2 g. PhNO in 20 cc. dry (CH2OMe)2 and th mixt. kept overnight yielded 2.3 g. PhCD:NPh (XII), m. 52.5-3.5 Deg (MeOH). II (12.2 g.) in 50 cc. dry (CH2OMe)2 treated dropwise during 0.5 hr. with 46 cc. 0.77M PhLi-Et2O at -25 Deg, and the mixt. stirred 1 hr., warmed to room temp., and treated 1 hr. with 5.5 g. BzH in 10 cc. (CH2OMe)2 yielded 3.95 g. PhCH:CDCl, b8 72-6 Deg. I (52 g.) and the equiv. amt. PhLi-Et2O in 200 cc. (CH2OMe)2 treated overnight at -20 Deg with 10 g. PhCDO and hydrolyzed with 25 cc. 2N D3PO4 yielded 9.4 g. PhCD:CHCl (1:1 cis-trans), b10 75-80 Deg. XII (20 millimoles) from XI with PhNO refluxed 1 hr. with 2N H2SO4 gave 1.39 g. PhCDO, b8 55-8 Deg. CF2:CClF (94 g.) and 85 g. PhC.tplbond.CH heated 20 hrs. at 120 Deg in an autoclave yielded 106 g. 3,4,4-trifluoro-3-chloro-1-phenyl-1-cyclobutene, which hydrolyzed with hot concd. HCl gave 71% 1-phenyl-1-cyclobutene-3,4-dione, m. 152-3 Deg, a 13.30-g. portion and 2.33 g. Na in 66 cc. D2O heated with a free flame yielded 2.94 g. PhCDO, b8 55-7 Deg. The ir spectra of [Ph3PMe]Br and [Ph3PCD3]Br were recorded. [on SciFinder (R)]