Journal article

Über die Herstellung von Vinyläthern, Vinylthioäthern und Vinylhalogeniden auf der Phosphylen-Basis

cf. CA 55, 13345i. MeOCH2Ph3PCl (I), m. 201-2 Deg (decompn.) (CHCl3-AcOH), was prepd. (86%) from 0.19 mole Ph3P (II) and 0.2 mole ClCH2OMe in 120 ml. C6H6 (60 hrs. at 50 Deg); I borate analog m. 198-9 Deg (Me2CO-EtOH). Ph2CO (0.02 mole) dissolved in 40 ml. Et2O was added to a soln. resulting from the addn. of 0.02 mole PhLi in 20 ml. Et2O to a suspension of 0.02 mole I in 65 ml. Et2O. After 2 hrs., the ppt. was filtered off, washed with Et2O, and treated with dil. HCl and C6H6. MeOCH:CPh2 (III) (82%), m. 38-9 Deg (MeOH), was isolated by evapn. of the Et2O ext. and distn. III was converted to Ph2CHCHO (IV) by heating it 20 hrs. in 200 ml. AcOH-20 ml. H2SO4. BzH (0.7 mole) in 40 ml. tetrahydrofuran (THF) was added to a suspension of 0.1 mole I in 180 ml. THF (to which had been added 0.1 mole PhLi in 92 ml. Et2O). The ppt. was filtered off, the filtrate treated with a satd. soln. of NH4Cl, and the dried org. phase evapd. until 8.9 g. Ph3P(O) (V) crystd. Upon fractionation, the mother liquor yielded 61% PhCH:CHOMe (VI), b15 91-6 Deg. BuLi (0.12 mole) in 94 ml. Et2O was added to a stirred suspension of 0.12 mole I in 50 ml. Et2O at -50 Deg, the mixt. allowed to stand 2 hrs., and then 0.1 mole BzH added. After warming to room temp., the mixt. was kept 2 hrs., hydrolyzed with stirring, the Et2O phase successively washed with 40% NaHSO3, NaHCO3, and H2O, the Et2O removed, and the residue distd. to give a liquid, b14 90-9 Deg, contg. (vapor phase chromatography) 23% cis- and trans-VI, 11% PhCH:CHCH2CH2Me, 0.5% BzH, and PhCH2OH (trace). I (0.033 mole) was treated with 0.03 mole NaOEt in 70 ml. abs. EtOH; 0.03 mole BzH was added to the mixt., which was then warmed 5 hrs. at 65 Deg. EtOH was largely removed and the mother liquor fractionated to yield 0.0187 mole VI, which reacted with 5% H2SO4 to yield PhCH2CHO; 2,4-dinitrophenylhydrazone, m. 120-1 Deg. I (0.105 mole) was treated with 0.067 mole PhCH:CHCHO and 0.1 mole NaOEt in 200 ml. abs. EtOH 24 hrs. at 50 Deg and the mixt. worked up as before to yield 0.061 mole V and 50% MeOCH:CHCH:CHPh (VII), b0.1 74-5 Deg (over LiAlH4), n20D 1.6313. VII was characterized by reaction with maleic anhydride to yield 6-methoxy-3-phenyl-D4-tetrahydrophthalic anhydride, m. 166-7 Deg (C6H6). I was treated with 0.033 mole fluorenone and 0.05 mole NaOMe in 60 ml. abs. MeOH 53 hrs. at 50 Deg to yield 47% 9-(methoxymethylene)fluorene, m. 108-8.5 Deg; 1,3,5-(O2N)3C6H3 addn. product (1:1) m. 198-9 Deg (EtOH). 9-(Ethoxymethylene)fluorene was prepd. by a similar procedure using NaOEt and EtOH; 1,2,3-(O2N)3C6H3 addn. product (1:1) m. 166-7 Deg. I (0.094 mole) was kept 60 hrs. at 50 Deg with 0.033 mole phthalaldehyde and 0.088 mole NaOEt. V (80%) and Ph2P(O)CH2OMe (small amt.), m. 113.5-14 Deg (cyclohexane-AcOEt), were isolated as the Et2O-insol. portion of the residue. After the Et2O ext. was washed with NaHSO3, Na2CO3, and H2O, 55% 1,2-(MeOCH:CH)2C6H4, b0.8 102-3 Deg (over LiAlH4), was obtained by evapn. MeSCH2PPh3Cl (VIII), m. 220-2 Deg (CHCl3-AcOEt), was prepd. (77%) by heating 0.17 mole II and 0.2 mole MeSCH2Cl in 80 ml. C6H6 at 80 Deg with stirring. Treatment of VIII with NaPh4B yielded MeSCH2PPh3(BPh4), m. 210.5-11.0 Deg (MeCO-EtOH). PhLi (0.05 mole) in 46 ml. Et2O was added to 0.05 mole VIII in 100 ml. Et2O (15 min., with stirring) and the mixt. treated with 0.05 mole Ph2CO. The mixt. was agitated 40 hrs., dild. with Et2O, and treated with NH4Cl soln. to give 84% MeSCH:CPh2 (IX), m. 74.0-4.5 Deg (EtOH), from the Et2O layer. IX (0.005 mole) was boiled 20 hrs. in 20 ml. AcOH-20 ml. 10% H2SO4 soln. After neutralization, the soln. was extd. with Et2O, the Et2O evapd., and the residue crystd. from EtOH to yield 63% unchanged IX and 5% IV, isolated as its 2,4-dinitrophenylhydrazone, m. 148.5-9.5 Deg (EtOH). PhLi (0.074 mole) in 70 ml. Et2O was added with stirring to 0.075 mole VIII in 150 ml. THF and the mixt. stirred 15 min. after addn. BzH (0.067 mole) was then added (exothermic reaction) and heating continued 60 hrs. at 55 Deg. After filtration and in vacuo remov l of solvent, the residue was taken up in Et2O, the Et2O layer washed (H2O), the Et2O evapd., and petr. ether added to ppt. V. From the filtrate, 70% MeSCH:CHPh (X), b12 126-7 Deg, n20D 1.6334, was obtained by fractional distn. X was oxidized to a cis-trans mixt. of MeSO2CH:CHPh (XI), m. 50 Deg (petr. ether), with H2O2 in AcOH. cis-XI, m. 64 Deg (CHCl3), was isolated by fractional crystn. A mixt. of 0.021 mole X and 0.021 mole Me2SO4 was kept 60 hrs., dissolved in EtOH, and treated with a warm EtOH soln. of 0.025 mole NaPh4B to give Me3S(Ph4B), m. 328-30 Deg (Me2CO-EtOH). Me3O(BF4) (0.078 mole) in 60 ml. CH2Cl2 reacted with 0.08 mole X in 10 ml. CH2Cl2 to yield 73% Me2SCH:CHPh(BF4) (XII), m. 103-4 Deg (EtOH). Crude XII (0.025 mole) dissolved in 50 ml. Et2O was stirred with 0.05 mole PhLi in 47 ml. Et2O (exothermic reaction), the mixt. allowed to stand overnight, the soln. decanted and washed with H2O, the solvent removed, and the oil distd.; the fraction b760 34-90 Deg contained Me2S; the fraction b760 90-115 Deg contained PhC.tplbond.CH and X. trans-Stilbene was isolated from the residue. II (1 mole) and 1 mole paraformaldehyde (XIII) in 1 l. Et2O was stirred 10 hrs. with 500 ml. 33% HBF4; the ppt. was filtered off, washed with H2O, THF, and Et2O to yield 64% HOCH2PPh3(BF4) (XIV), m. 128-30 Deg (CH2Cl2AcOEt). II (2 moles) and 2 moles XIII in 1 l. Et2O was treated 3 hrs. with HCl to give HOCH2PPh3Cl (XV), m. 194-8 Deg (pptd. from CH2Cl2 with Et2O). XV was dissolved in 1.2 l. CH2Cl2 and heated 30 min. with 3 moles SOCl2, the volatile materials removed, the residue dissolved in warm CH2Cl2, and 440 g. ClCH2PPh3Cl (XVI), m. 260-1 Deg (CH2Cl2-AcOEt), pptd. with hot AcOEt. Equiv. amts. of XVI and NaBPh4 in EtOH yielded ClCH2PPh3(Ph4B), m. 222.0-3.8 Deg (Me2CO). XVI (0.115 mole) was refluxed with 0.110 mole NaOMe in 200 ml. MeOH under N; after 15 min., 0.1 mole BzH in 50 ml. MeOH was added. After being refluxed 15 min., the mixt. was treated with 5 g. NH4Cl and the solvent removed. The residue was extd. with boiling petr. ether, the exts. combined, concd., chromatographed on Al2O3LiBr, and eluted with 1 l. petr. Et2O to give 5.7 g. ClCH:CHPh (XVII), b13 81.5-2.5 Deg, n20D 1.5734. BuLi (0.12 mole) in THF was added dropwise to 0.115 mole XVI in 50 ml. THF; 0.1 mole BzH was added at -70 Deg and the mixt. warmed to 20 Deg and maintained 15 hrs. with stirring to give 35% XVII. When (MeOCH2)2 was used as the solvent, 67% XVII was obtained; when Et2O was used, 39% XVII was obtained. At 20 Deg, trans-1-phenyl-1-pentene, b12 109-9.5 Deg, n20D 1.5294, and a small amt. of the cis isomer were formed. BuLl (0.115 mole) in 90 ml. Et2O was added to 0.115 mole XVI in 50 ml. Et2O at -30 Deg; 0.1 mole Ph2CO was added at -30 Deg and the mixt. worked up as before (chromatography) to yield 67% Ph2C:CHCl (XVIII), b14 165-95 Deg, m. 42-3 Deg (MeOH). BuLi (0.04 mole) in 22 ml. Et2O was added dropwise to a soln. of 0.035 mole II in 45 ml. CH2Cl2 with stirring, 0.028 mole Ph2CO was added at -50 Deg, and after 3 days Et2O and H2O were added. II was pptd. as Ph3PMeI (by addn. of MeI) and the soln. concd. to give x-Ph2C(OH)C6H4P(O)Ph2. The mother liquor was chromatographed on Al2O3 to yield 1.88 g. XVIII. [on SciFinder (R)]

    Keywords: Olefins (formation of ; from alkylidene phosphoranes); Vinyl compounds (halogenated ; prepn. of); Aldehydes; Carbonyl compounds (reactions of ; with methylene phosphorane derivs.); Ethers; Sulfides (vinyl) ; 1-Pentene 1-Pentene Boron compounds Boron compounds Ether Ether Sulfone


    CAN 55:124531 10E Organic Chemistry: Benzene Derivatives Univ. Heidelberg,Germany. Journal 0009-2940 language unavailable. 13769-19-2 (Phosphorane) (alkylidene derivs., in formation of olefins); 99-35-4 (Benzene, 1,3,5-trinitro-) (compds. with 9-(alkoxymethylene)fluorenes); 622-25-3 (Styrene, b-chloro-); 4541-89-3 (Ethylene, 2-chloro-1,1-diphenyl-) (formation from (chloromethyl)triphenylphosphonium chloride); 103-30-0 (Stilbene, trans-) (formation from dimethylstyrylsulfonium fluoborate reaction with PhLi); 536-74-3 (Benzene, ethynyl-) (formation of, from dimethylstyrylsulfonium fluoborate reaction with PhLi); 1549-80-0 (Sulfonium, dimethylstyryl-, fluoborate); 3300-07-0 (Fluorene, 9-(methoxymethylene)-); 4455-77-0 (Phosphine oxide, (methoxymethyl)diphenyl-); 7715-02-8 (Sulfide, methyl styryl); 15096-10-3 (Sulfide, 2,2-diphenylvinyl methyl-); 19684-54-9 (Fluorene, 9-(ethoxymethylene)-); 35678-16-1 (Sulfonium, trimethyl-, tetraphenylborate); 40237-72-7 (Ether, 2,2-diphenylvinyl methyl); 66164-41-8 (Ether, methyl 4-phenyl-1,3-butadienyl); 100121-57-1 (Benzene, o-bis(2-methoxyvinyl)-); 101093-94-1 (4-Cyclohexene-1,2-dicarboxylic anhydride, 3-methoxy-6-phenyl-); 102452-57-3 (Fluorene, 9-(ethoxymethylene)-, compd. with 1,3,5-trinitrobenzene); 102467-20-9 (Fluorene, 9-(methoxymethylene)-, compd. with 1,3,5-trinitrobenzene); 119659-91-5 (Methanol, [(diphenylphosphinyl)phenyl]diphenyl-) (prepn. of); 20677-71-8 (Phosphonium, [(methylthio)methyl]triphenyl-); 47107-68-6 (Phosphonium, (hydroxymethyl)triphenyl-); 50443-22-6 (Phosphonium, (chloromethyl)triphenyl-) (salts); 50443-21-5 (Phosphonium, (methoxymethyl)triphenyl-) (salts, prepn. and olefin formation from)


    • LSCO-ARTICLE-1961-001

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


  • There is no available fulltext. Please contact the lab or the authors.

Related material