- A study on the acidic hydrolysis of cyclic phosphinates: 1-Alkoxy-3-phospholene 1-oxides, 1-ethoxy-3-methylphospholane 1-oxide, and 1-ethoxy-3-methyl-1,2,3,4,5,6-hexahydrophosphinine 1-oxide
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The hydrochloric acid-catalyzed hydrolysis of phosphinates was studied on 1-alkoxy-3-phospholene 1-oxides, 1-ethoxy-3-methylphospholane 1-oxide, and 1-ethoxy-3-methyl-1,2,3,4,5,6-hexahydrophosphinine 1-oxide as the model compounds. Under the conditions applied, the isomerization of the 3-phospholene moiety to the 2-phospholene ring also occurred leading to mixtures of the corresponding 1-hydroxy-3-phospholene oxide and 1-hydroxy-2-phospholene oxide. According to our optimized method, using 3 equivalents (0.5?mL) of concentrated hydrochloric acid in 1?mL of water per ca. 2 mmol of the substrate at reflux, the completion required 3-10?hour. The hydrolyses were characterized by pseudo-first-order rate constants and the isomerizations by rate constants. The application of p-toluenesulfonic acid under microwave irradiation at 140°C in the hydrolysis of 1-alkoxy-3-methyl-3-phospholene oxides associated with reaction times of 1-3?hour. The reactivity order of the 5- and 6-ring phosphinates in hydrolysis was set up.
- Keglevich, Gy?rgy,Rádai, Zita,Harsági, Nikoletta,Szigetvári, áron,Kiss, Nóra Zsuzsa
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- Synthesis of Some 1-aryl-2,3-dibromophospholanes as novel anti-cancer agents
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Novel phosphorus heterocyclic compounds, 3-methyl-1-(3-bromophenyl as well as some 3-substituted phenyl)-2- phospholene 1-oxides (1d as well as 1b, 1c, and 1f), were synthesized from 1-phenyl-2-phospholene 1-oxide 1a via 3-methyl-1-(3-nitrophenyl)-2-phospholene 1-oxide (1b). 1-(4-Bromophenyl)-2- phospholene 1e was prepared by Grignard coupling reaction of 1-chloro-3-methyl-2-phospholene 1-oxide with 4-bromophenylmagnesium bromide. 2,3-Dibromo-3-methyl-1-arylphospholane 1-oxides (2a-2e) were prepared by the addition reaction of bromine to the C=C double bond of 2-phospholenes 1a-1e. The substituent effect of the phenyl group of the 1-aryl-phospho lanes 2 on the observed anti-proliferative effect against U937 leukemia cell lines evaluated by MTT in vitro methods showed that 2,3-dibromo-3-methyl-1-(4-bromophenyl) phospholane (2e) was the most active among 2. These novel dibromophosphorus heterocyclic derivatives exhibit much higher anti-cancer activity than Gleevec (molecular targeting chemotherapeutic agent) against U937 cells.
- Yamada, Manabu,Asai, Kazuhide,Yamashita, Junko,Suyama, Takuya,Niimi, Taishi,Maddali, Kasthuraiah,Fujie, Michio,Nakamura, Satoki,Kimura, Motohiko,Tanaka, Yasutaka,Toda, Mitsuo,Yamashita, Mitsuji
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scheme or table
p. 173 - 180
(2011/06/24)
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- Improved Synthesis of 1-Methoxy-3-methyl-2-phospholene Oxide Utilising Multivariate Optimization Analysis
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The synthesis of 1-methoxy-3-methyl-2-phospholene oxide from 1,1,1-trichloro-3-methyl-3-phospholene initially gave low yields of around 25percent.Attempts to optimise the yield by classic traditional methods, that is, changing only one variable at a time (OVAT) resulted in no significant improvement in the yield.Using multivariate optimization techniques, the yield was rapidly and significantly improved to around 90percent.Data was also gathered on the significant variables and the important variable interactions.
- Coleman, Gregory V.,Price, Dennis,Horrocks, A. Richard,Stephenson, James E.
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p. 629 - 632
(2007/10/02)
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- Novel Synthesis of 2-Pphosphinoylphospholane 1-Oxide Derivatives
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Reactions of 2-phospholene 1-oxides with N-bromoacetamide in aqueous organic solvent produced 2-bromo-3-hydroxyphospholane 1-oxides, which reacted with sodium salts of dialkyl phosphonates to afford novel 2-phosphinoylphospholane 1-oxide derivatives.A 4-phosphinoyl-2-phospholene derivative was also prepared.
- Miyamoto, Yasushi,Yamashita, Mitsuji,Oshikawa, Tatsuo
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p. 2004 - 2006
(2007/10/02)
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