Die Zersetzung von Diazoverbindungen in Gegenwart von Triphenylphosphin

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 23% Ph2C:CH2 and 67% Ph2CO. The CH2N2 replaced by an equimolar amt. of PhCHN2 in 20 ml. tetrahydrofuran and the mixt. refluxed 50 hrs. yielded 23% Ph2C:CHPh, m. 69-71 Deg; 6% trans-stilbene, 34% PhCH:NN:CHPh, 52% Ph2CO, and 33% Ph3PO. With BzH as carbonyl component, PhCHN2 was again added dropwise in 1 hr. to the boiling mixt. and the mixt. refluxed 1 hr. The Et2O-sol. product consisted of 28% cis- and trans-stilbene, 71% PhCH:NN:CHPh and 89% Ph3PO. Ph2P:NN:CH2[10 millimoles, m. 143-5 Deg (decompn.)] and 10 millimoles Ph2CO refluxed 4 hrs. with 1 millimole CuCl in 20 ml. MeOCH2CH2OMe and the filtered soln. dild. with Et2O, treated with MeI, and filtered gave 0.492 g. MePPh3I (corresponding to 12% Ph3P). The filtrate distd. and the bright yellow oil, b14 128-75 Deg, sepd. by column chromatography gave 35% Ph2C:CH2 and 52% Ph2CO. The distn. residue contained 72% Ph3PO. Repetition with 3-fold molar amt. of Ph2P:NN:CH2 and 4 hrs. reflux yielded 32% unchanged material, 51% Ph3PO, 31% unchanged Ph2CO, and 62% Ph2C:CH2. Diazofluorene (20 millimoles) in 15 ml. tetrahydrofuran added dropwise in 15 min. with stirring to 20 millimoles PhCH2NMe2 and 0.5 millimole CuCl with violent evolution of N (exothermic reaction) and the mixt. refluxed briefly, the cooled mixt. dild. with 100 ml. Et2O and washed with dil. HCl, the Et2O ext. dried and evapd. yielded 65% fluorenylenefluorene, m. 189-90 Deg. The acid ext. neutralized, extd. with Et2O and the product distd. gave 60% unchanged PhCH2NMe2. The distn. residue recrystd. from MeOH yielded 12% (9-benzyl-9-fluorenyl))dimethylamine, m. 99-101 Deg. N2CHCO2Et (20 millimoles) similarly decompd. and the basic fraction extd. with Et2O and distd. gave 2.38 g. material, b14 65-150 Deg, contg. mainly PhCH2NMe2 and about 5% PhCH2CH(NMe2)CO2Et, isolated by preparative gas chromatography to yield 0.19 g. pure amine. [on SciFinder (R)]

Published in:
Tetrahedron, 18, 9, 1023-1028
CAN 58:3364
Organometallic and Organometalloidal Compounds
Univ. Heidelberg,Germany.
written in German.
13769-19-2 (Phosphorane, PH5) (alkylidene derivs., olefin formation from); 603-35-0 (Phosphine, triphenyl-) (diazo compd. decompn. in presence of); 103-30-0 (Stilbene, trans-); 588-68-1 (Benzaldehyde, azine) (formation in diazo compd. decompn. in presence of Ph3P); 91-01-0 (Benzhydrol); 530-48-3 (Ethylene, 1,1-diphenyl-); 791-28-6 (Phosphine oxide, triphenyl-) (formation of, in diazo compd. decompn. in presence of Ph3P); 4358-26-3 (TetraphenylBorate) (of phosphonium ions); 6881-57-8 (Phosphonic acid, benzyl-) (prepn. from phenylphosphonoacetic acid); 58-72-0 (Ethylene, triphenyl-); 746-47-4 (D9,9'-Bifluorene); 859-65-4 (Acetophenone, 2-(triphenylphosphoranylidene)-); 1100-88-5 (Phosphonium, benzyltriphenyl-, chloride); 1530-43-4 (Phosphonium, (diphenylmethyl)triphenyl-, chloride); 2065-66-9 (Phosphonium, methyltriphenyl, iodide); 2071-44-5 (Fluoren-9-one, azine); 7143-79-5 (Fluoren-9-amine, 9-benzyl-N,N-dimethyl-); 7253-07-8 (Phosphonium, fluoren-9-yltriphenyl-, bromide); 15990-54-2 (Phosphorane, (methylenehydrazono)triphenyl-); 16721-45-2 (Phosphorane, benzylidenetriphenyl-); 19881-82-4 (Alanine, N,N-dimethyl-3-phenyl-, ethyl ester); 38654-93-2 (Acetic acid, phenylphosphono-); 97469-44-8 (Acetic acid, phenylphosphono-, compd. with p-toluidine) (prepn. of)

 Record created 2006-03-03, last modified 2018-01-27

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