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Abwandlung der Phosphylen-Methodik : über Phosphin-alkylene als olefinbildende Reagenzien

cf. CA 50, 10030g. The stationary ligands on the P were varied in order to obtain an insight into the mechanism of the carbonyl-olefination with triphenylphosphylenes. The results demonstrated that the substitution of the Ph by p-MeC6H4, p-MeOC6H4, piperidino, and morpholino groups favored the betaine formation with carbonyl derivs., but rendered the decompn. reaction via the 4-ring markedly more difficult. (o-MeOC6H4)3P (I)(20 g.), m. 204-6 Deg, in 200 cc. Et2O and 20 g. MeBr kept 24 hrs. and the deposit boiled with C6H6 left 24 g. I.MeBr, m. 234-6 Deg (H2O). I.MeBr (10 millimoles) shaken 5 hrs. with 10 millimoles PhLi in 60 cc. Et2O, the mixt. treated with 10 millimoles BzPh in a small amt. of dry Et2O, shaken 15 hrs., heated 16 hrs. at 65 Deg, filtered, the residue extd. with C6H6, and treated with N HCl gave 81% I.MeBr; the C6H6 ext. concd. and dild. with petr. ether pptd. 10% (o-MeOC6H4)3PO (II), m. 215-17 Deg (subliming from 175 Deg). I (0.5 g.) in 20 cc. AcOH treated dropwise with excess 30% H2O2 and refluxed briefly gave II, m. 217-18 Deg (H2O). The original Et2O filtrate treated with dil. HCl, the mixt. evapd., and the residual oil chromatographed on Al2O3 yielded 11% Ph2C:CH2 (III), b16 150-60 Deg, and 58% unchanged BzPh. I.MeBr (5 millimoles) treated in the usual manner with 5 millimoles PhLi in Et2O, the ppt. suspended in dry Et2O, kept 14 days with 50 millimoles MeI, and the mixt. hydrolyzed with acid gave 69.5% I.EtI, m. 225-7 Deg (decompn.)(EtOH-Et2O). I (0.1 g.) and 1.5 g. EtI in 30 cc. Et2O kept 20 hrs. at 85 Deg yielded 86% I.EtI, m. 227-9 Deg (H2O). PCl3 (0.02 mole) in 50 cc. dry Et2O added dropwise with stirring during 0.5 hr. to 0.08 mole p-MeC6H4Li in 100 cc. Et2O and the mixt. decompd. after 24 hrs. with aq. NH4Cl gave 82% (p-MeC6H4)3P (IV), m. 145-6 Deg (EtOH). IV (18 g.) and 40 g. MeBr in 200 cc. C6H6 gave during 24 hrs. 96.5% IV.MeBr, m. 220.5-22 Deg (BuOH-Et2O). Powd. IV.MeBr (10 millimoles) and 10 millimoles PhLi in 60 cc. Et2O shaken 3 hrs., treated with 10 millimoles BzPh, the mixt. shaken 10 hrs., decompd. with 10 cc. N HCl, and filtered gave 81% (p-MeC6H4)3PO (V), m. 144-5 Deg (C6H6-petr. ether); the Et2O phase gave 69% III. (p-MeC5H43P:CH2 (VI) (5 millimoles) and 10 millimoles BzH heated 7 hrs. at 65 Deg gave 12% V, m. 143-4 Deg, and an oil which with Ph4BNa gave 61% [PhCH(OH)CH2(p-MeC6H4)3P]BPh4, m. 170-1 Deg; the original Et2O filtrate yielded 6% styrene. (p-MeOC6H4)2P (17 g.), m. 131-2 Deg, and 20 g. MeBr in 200 cc. Et2O gave during 24 hrs. 91% [(p-MeOC6H4)3PMe]Br (VII), m. 214-16 Deg (EtOH-Et2O). VII (10 millimoles) and 10 millimoles PhLi in 60 cc. Et2O shaken 20 hrs., treated with 10 millimoles BzPh in dry Et2O, the mixt. shaken 40 hrs., filtered, and the residue decompd. with HCl gave (p-MeOC6H4)3PO (VIII), m. 146-6.5 Deg (C6H6-petr. ether); the filtrate treated with N HCl and the Et2O phase worked up yielded addnl. VIII and 45% III; the aq. HCl phase neutralized and treated with KI yielded 15% iodide analog of VII, m. 218-20 Deg (H2O). VII treated in the usual manner with PhLi and then with BzPh gave 72% [(p-MeOC6H4)3PCH2CH(OH)Ph]BPh4, (IX), m. 211-13 Deg (decompn.) (BuOH). VII (10 millimoles) and 10 millimoles BzH heated 16 hrs. at 65 Deg and processed in the usual manner yielded 68% IX, m. 210-12 Deg (BuOH). (PhO)3P (X), b0.2 168-9 Deg, (10 millimoles) and 12 millimoles MeI in 5 cc. dry MeNO2 heated 3 hrs. in a sealed tube at 110-20 Deg, cooled, and dild. with dry Et2O pptd. X.MeI, m. 114-19 Deg (sealed capillary). X.MeI (6 millimoles) in 10 cc. dry Et2O treated dropwise with stirring with 6 millimoles Ph3Na in 58 cc. Et2O, the mixt. stirred 0.5 hr., treated with 6 millimoles BzPh, kept 2 days, heated 8 hrs. at 110 Deg, and worked up yielded 0.94 g. III. [Me3O]BF4 (28 millimoles) and 28 millimoles X stirred 5 hrs. at 65 Deg under N gave [MeP(OPh)3]BF4 (XI), m. 69 Deg (sealed capillary). XI, powd. PhOK, and BzPh (28 millimoles each) in 60 cc. dry tetrahydrofuran shaken 0.5 hr. under N, heated 18 hrs. at 140 Deg, filtered, and distd. gave 1.95 g. hOH, 1.0 g. III, and 2.5 g. unchanged BzPh; during the distn. 3.5 g. KBF4 sepd. from the mixt. Methyltripiperidinophosphonium iodide (XII), m. 254-5 Deg (decompn.), and PhLi (10 millimoles each) shaken 2 days in 32 cc. Et2O, decompd. with 150 cc. 0.1N HI, the aq. phase neutralized, and evapd. gave 3.1 g. unchanged XII; the Et2O phase treated with 10 millimoles BzPh in a little dry Et2O and the Et2O decanted gave a residue of the betaine, which treated with 0.3N HI yielded (2-hydroxy-2,2-diphenylethyl)tripiperidinophosphonium iodide (XIII). XIII heated at 70-80 Deg/0.05 mm. gave BzPh and XII. XIII (15 millimoles) in 50 abs. tetrahydrofuran shaken 12 hrs. with 15 millimoles PhLi in 16 cc. Et2O, treated with 15 millimoles BzPh, heated 36 hrs. at 110 Deg, and worked up gave 53% III and 3% BzPh. Trimorpholinophosphine (0.29 mole), m. 152-6 Deg, in 700 cc. 1:1 CH2Cl2-C6H6 treated dropwise at 0 Deg with 0.38 mole MeI, the mixt. kept 10 hrs. at room temp., and filtered gave 45% methyltrimorpholinophosphonium iodide (XIV), m. 328-30 Deg (decompn.) (aq. EtOH), which with NaBPh4 in hot MeOH gave the tetraphenylboronate, m. 239-40 Deg (Me2CO-EtOH). XIV and PhLi (12 millimoles each) in 50 cc. Et2O shaken 4 days and the ppt. treated with aq. HI gave 75% XIV. The trimorpholinophosphine-methylene from a similar run heated 41 hrs. at 70 Deg with an equiv. amt. of BzPh gave 88% unchanged BzPh, but no III. XIV and PhLi (36 millimoles each) in 90 cc. tetrahydrofuran stirred 10 min., treated with 36 millimoles BzPh, the mixt. heated 18 hrs. at 75 Deg, filtered, and the filtrate worked up gave 72% III, b14 132-6 Deg, and 12% BzPh. A similar run in dry (CH2OMe)2 heated 38 hrs. gave 80% III, 8% BzPh, and 33% trimorpholinophosphine oxide, m. 186-8 Deg (cyclohexane). A run with XIV and BzH in (CH2OMe)2 heated 20 hrs. at 65 Deg, filtered, and the residue treated with H2O yielded 49% 2-hydroxy-2-phenylethyl)trimorpholinophosphonium iodide, m. 268-70 Deg (MeOH-EtOH), stable on brief boiling with dil. HI; a soln. in hot MeOH gave with Ph4BNa the tetraphenylboronate, m. 272-4 Deg. [on SciFinder (R)]

    Keywords: Olefins (formation of ; from alkylidene phosphoranes) ; Boron compounds Phosphonium Phosphonium Phosphonium Phosphonium Phosphonium Phosphonium Phosphonium Phosphonium

    Note:

    CAN 55:70467 10E Organic Chemistry: Benzene Derivatives Univ. Heidelberg,Germany. Journal 0009-2940 language unavailable. 13769-19-2 (Phosphorane) (alkylidene derivs., in formation of olefins); 530-48-3 (Ethylene, 1,1-diphenyl-) (formation of, in benzophenone reaction with methylenephosphorane derivs.); 47468-19-9 (Phosphonium, tris(p-methoxyphenyl)methyl-) (halides); 797-70-6 (Phosphine oxide, tri-p-tolyl-); 803-17-8 (Phosphine oxide, tris[p-methoxyphenyl]-); 1038-95-5 (Phosphine, tri-p-tolyl-); 1590-85-8 (Tetrasilane, 1,4-dimethyl-1,1,2,2,3,3,4,4-octaphenyl-); 4167-91-3 (Phosphorane, iodomethyltriphenoxy-); 4441-12-7 (Phosphine oxide, trimorpholino-); 38958-00-8 (Phosphorane, methylenetri-p-tolyl-); 47467-89-0 (Phosphine oxide, tris[o-methoxyphenyl]-); 61249-20-5 (Phosphonium, methyltri-p-tolyl-, bromide); 61249-25-0 (Phosphonium, tris(o-methoxyphenyl)methyl-, bromide); 100529-20-2 (Phosphorane, iodomethyltrimorpholino-); 103209-37-6 (Benzhydrol, a-[(iodotripiperidinophosphoranyl)methyl]-); 103209-37-6 (Phosphorane, (2-hydroxy-2,2-diphenylethyl)iodotripiperidino-); 108904-02-5 (Phosphorane, methylenetrimorpholino-); 109654-28-6 (Phosphorane, methylenetripiperidino-); 110436-76-5 (Phosphorane, (b-hydroxyphenethyl)iodotrimorpholino-); 110436-76-5 (Benzyl alcohol, a-[(iodotrimorpholinophosphoranyl)methyl]-); 111066-73-0 (Phosphorane, methylenetriphenoxy-); 114278-59-0 (Phosphorane, tris[p-methoxyphenyl]methylene-); 114278-95-4 (Phosphorane, tris[o-methoxyphenyl]methylene-); 116957-16-5 (Phosphonium, ethyltris(o-methoxyphenyl)-, iodide); 860440-90-0 (Phosphonium, (2-hydroxy-2,2-diphenylethyl)tripiperidino-, iodide) (prepn. of); 119-61-9 (Benzophenone) (reaction of, with methylenephosphorane derivs.); 100-52-7 (Benzaldehyde) (reaction with methylenephosphorane derivs.)

    Reference

    • LSCO-ARTICLE-1961-002

    Record created on 2006-03-03, modified on 2016-08-08

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