- Novel and highly selective conversion of alcohols and thiols to alkyl nitrites with triphenylphosphine/2,3-dichloro-5,6-dicyanobenzoquinone/Bu 4NNO2 system
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Alkyl nitrites were prepared in good to excellent yields by treatment of alcohols and thiols with triphenylphosphine/2,3-dichloro-5,6- dicyanobenzoquinone/Bu4NNO2 in acetonitrile. This method is highly selective for the conversion of primary alcohols to alkyl nitrites in the presence of secondary and tertiary alcohols and thiols.
- Akhlaghinia, Batool,Pourali, Ali Reza
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p. 1747 - 1749
(2007/10/03)
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- Preparation of alkyl nitrates, nitrites, and thiocyanates from alcohols utilizing trichloroisocyanuric acid with triphenylphosphine
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Alcohols in acetonitrile are converted into alkyl nitrates, nitrites, or thiocyanates by the action of triphenylphosphine and trichloroisocyanuric acid along with silver nitrate, silver nitrite, or sodium thiocyanate, respectively.
- Hiegel, Gene A.,Nguyen, Jeremiah,Zhou, Yan
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p. 2507 - 2511
(2007/10/03)
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- Oxidative Dealkylation of Hydroquinone Ethers with Nitrogen Dioxide in the Convenient Preparation of Quinones
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Various Hydroquinone dialkyl ethers (R2Q) are effectively converted by nitrogen dioxide into the corresponding quinone (Q) and alkyl nitrite (RONO) in dichloromethane at room temperature or below.The preparative procedure for the isolation of crystalline quinones in quantitative yield merely involves the convenient removal of the low boiling solvent in vacuo.Isotopic labelling studies demonstrate that the oxidative dealkylation proceeds via alkoxy scission of the labile cation radical (R2Q-cation radical) formed via the oxidation of the hydroquinone ether by nitrogen dioxide ( as the disproportionated ion pair NO+NO3-).The electron-transfer mechanism is confirmed by the spectral observation of R2Q-cation radical (identified by the isolation of the crystalline salt R2Q-cation radical-SbCl6-) and its rapid conversion into quinone and alkyl nitrite by combination with nitrate (NO3-) and nitric oxide (NO).
- Rathore, Rajendra,Bosch, Eric,Kochi, Jay K.
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p. 1157 - 1166
(2007/10/02)
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- Micellar Effects in the Nitrous Acid Deamination Reaction of (R)-2H>-1-Octanamine
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The nitrous acid deamination of 1-octanamine (1) afforded mixtures of isomeric octenes, octanols, and octyl nitrites.The aggregation of 1*HClO4 in micelles induced the formation of dioctyl ethers and of 1-nitrooctane as additional products.In homogeneous solution (submicellar aqueous conditions or HOAc), 2H>-1-octanol was obtained from 2H>-1 with ca. 95 percent inversion of configuration.Above the critical micelle concentration, the enantiomeric purity of 2H>-1-octanol decreased while 2H>-1-nitrooctane was formed with ca. 90 percent retention of configuration. 1-Octyl..NO2 radical pairs, rather than ion pairs, are likely to intervene on the retentive route to 1-nitrooctane and 1-octyl nitrite.Equilibration, via NO exchange, of (R)-2H>-1-octyl nitrite with the more abundant (S)-2H>-1-octanol is thought to account for the diminished ee of both products.
- Brosch, Daniel,Kirmse, Wolfgang
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p. 1118 - 1121
(2007/10/02)
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- Proton Acidity and Chemical Reactivity in Molten Salt Hydrates
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Molten Ca(NO3)2*4H2O has been used as a model system for studies of proton acidity and chemical reactions (including ester hydrolyses and aromatic nitrations) in molten salt hydrates.Increases in proton acidity caused by addition of acidic hydrates such as AlCl3*6H2O and Cd(NO3)2*4H2O or of aqueous HNO3 can be quantified in terms of changes in Hammett acidity H0, but usually not by the downfield shifts observed in the NMR spectrum.The rates of hydrolysis of selected primary esters (e.g., n-octyl acetate) were found to be linearly dependent on nitric acid concentration, indicating that the acidity of these melts can be changed with little change in water activity.The measurement of kinetic parameters is complicated, however, by side reactions between the organic substrates and HNO2, NO2 (or NO2+) and other species originating from the nitrate ions in the melt.
- Franzyshen, S. K.,Schiavelli, M. D.,Stocker, K. D.,Ingram, M. D.
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p. 2684 - 2688
(2007/10/02)
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- Acetyl Nitrite: a Useful Nitrosating Reagent
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Acetyl nitrite has been prepared, and shown to be a useful reagent for the study of the mechanism of deamination of primary amines.
- Kyte, Andrew B.,Jones-Parry, Richard,Whittaker, David
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