- One-Pot Anodic Conversion of Symmetrical Bisamides of Ethylene Diamine to Unsymmetrical gem-Bisamides of Methylene Diamine
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Symmetrical bisamides of ethylene diamine of type ArCONHCH2CH2NHCOAr undergo anodic C-C bond cleavage in acetonitrile-LiClO4 under controlled-potential electrolysis. The electrogenerated carbocation intermediates react with the solvent acetonitrile to afford unsymmetrical gem-bisamides of type ArCONHCH2NHCOMe in a one-pot reaction. The yields of the latter products are moderate (up to 60%). Other minor products involve two symmetrical gem-bisamides of type ArCONHCH2NHCOAr and MeCONHCH2NHCOMe and fragmentation products (e.g., ArCONHCHO, ArCONH2, and ArCN).
- Golub, Tatiana,Dou, Gui-Yuan,Zeng, Cheng-Chu,Becker, James Y.
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supporting information
p. 7961 - 7964
(2019/10/11)
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- The cyclopropylcarbinyl route to γ-silyl carbocations
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The mesylate derivative of cis-1-hydroxymethyl-2-trimethylsilylcyclopropane has been prepared, along with a number of related mesylates and triflates with substituents on the 1-position. These substrates all solvolyze in CD3CO2D to give products derived from cyclopropylcarbinyl cations that undergo further rearrangement to give 3-trimethylsilylcyclobutyl cations. These 3-trimethylsilylcyclobutyl cations are stabilized by a long-range rear lobe interaction with the γ-trimethylsilyl group. When the substituent is electron-withdrawing (CF3, CN, or CO2CH3), significant amounts of bicyclobutane products are formed. The bicyclobutanes are a result of γ-trimethylsilyl elimination from the cationic intermediate that has an unusually long calculated Si-C bond. The solvolysis chemistry of mesylate and triflate derivatives of trans-1-hydroxymethyl-2-trimethylsilylcyclopropane and 1-substituted analogs can be quite different since these substrates do not generally lead to 3-trimethylsilylcyclobutyl cations.
- Creary, Xavier
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supporting information
p. 1769 - 1780
(2019/08/07)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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- A new simple method for the synthesis of cyclobutyl cyanide
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A clean and efficient intramolecular cyclization of δ- halovaleronitrile to cyclobutyl cyanide was achieved using NaOH and phase- transfer catalysts in a solid-liquid system at 70°C.
- Cohen, Shlomo,Rothenberg, Gadi,Sasson, Yoel
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p. 3093 - 3094
(2007/10/03)
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- Substituted sulfonamides, process of preparation and medicines containing same
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The present invention concerns new substituted sulfonamides, and the physiologically acceptable salts possibly in the form of complexes, esters and amides thereof, represented by the formula: STR1
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- Two-Carbon Elongation/Annulation of Alcohols to Nitriles
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Alcohols were replaced by a two-carbon nitrile unit in good to excellent yields via dehydrative alkylation with (phenylsulfonyl)acetonitrile under modified Mitsunobu conditions followed by desulfonylation using magnesium.Diols and haloalcohols furnished cycloalkylnitriles.
- Lai, Jing-Yu,Yu, Jurong,Hawkins, R. David,Falck, J. R.
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p. 5691 - 5694
(2007/10/02)
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- A New Synthetic Route to Aliphatic and Alicyclic Nitriles via Homolytic Desulfurization of α-(Dithiocarbamoylthio) Nitriles
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Chloroacetonitrile was transformed into aliphatic and alicyclic nitriles through (dimethyldithiocarmoylthio)acetonitrile.The key steps in the synthetic route consisted of mono- and dialkylation via sulfur-stabilized carbanion and homolytic desulfurization using tributyltin hydride.
- Yanagawa, Makato,Moriya, Osamu,Watanabe, Yoshihiko,Ueno, Yoshio,Endo, Takeshi
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p. 2203 - 2204
(2007/10/02)
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- ANALYSE STRUCTURALE EN SERIE CYCLOBUTANIQUE. Partie 1. Derives monosubstitues et gem disubstitues du cyclobutane
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Methylene bending mode analysis of some cyclobutane-d2 molecules reveals that in the dissolved state (solvent CCl4), bromocyclobutane occurs exclusively in a pseudo-equatorial form, whereas, under the same conditions, cyclobutanol and 1-bromocyclobutane carbonitrile exist both in pseudo-axial and pseudo-equatorial conformations.NMR spectroscopy confirms the results obtained for bromocyclobutane and leads to the conclusion that the pseudo-equatorial conformer is predominant in the case of cyclobutanol as well as in that of cyclobutane carbonitrile.A theoretical study of cyclobutanol in the gaseous state by the P.C.I.L.O. method gives results which are consistent with a pseudo-equatorial conformer.
- Karimine, Mohamed,Galsomias, Jacqueline,Lere-Porte, Jean-Pierre,Petrissans, Jean
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p. 321 - 332
(2007/10/02)
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- ISOLATION AND CHARACTERIZATION OF 2--1-CYANOBICYCLOPENTANE DERIVED FROM 1-CYANOBICYCLO-BUTANE AND Pt(II) COMPLEXES
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2--1-cyanobicyclopentane, obtained by the reaction of 1-cyanobicyclobutane with di-μ-chlorodichlorobis(ethylene)diplatinum(II) followed by the treatment with pyridine, has been isolated and characterized.
- Miyashita, A.,Watanabe, Y.,Takaya, H.
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p. 2595 - 2598
(2007/10/02)
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