- Correlation of the rates of solvolysis of acetic p-toluenesulfonic anhydride (acetyl p-toluenesulfonate) and a comparison with acetyl halides
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The specific rates of solvolysis of acetyl p-toluenesulfonate have been measured by a rapid-response conductivity technique at temperatures in the temperature range of -10 to -55 °C. For 13 solvents at -39.6 °C, an extended Grunwald-Winstein equation correlation led to sensitivities to changes in solvent nucleophilicity of 0.56 and to changes in solvent ionizing power of 0.61. In 89.1% acetone at -20 °C, the comparison with acetyl bromide solvolysis led to a kOTs/kBr ratio of 1.4. In methanol and methanol-d at -39.6 °C, the solvent deuterium isotope effect k MeOH/kMeOD is 0.99. These results are consistent with an SNl reaction with appreciable nucleophilic solvation or an S N2 reaction with a loose transition state. These two approaches lead to similar structures for the transition state. A solution of the acetyl p-toluenesulfonate was conveniently prepared by the rapid reaction of acetyl chloride with silver p-toluenesulfonate in acetonitrile. Copyright 2013 John Wiley & Sons, Ltd. Correlation of the rates of solvolysis of acetic p-toluenesulfonic anhydride (acetyl p-toluenesulfonate) and a comparison with acetyl halides. Copyright
- Kevill, Dennis N.,Ryu, Zoon Ha
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p. 983 - 988
(2014/01/06)
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- SYNTHESIS OF STERICALLY HINDERED SECONDARY AMINOETHER ALCOHOLS
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Severely sterically hindered secondary aminoether alcohols are prepared by reacting organic carboxylic, organic carboxylic acid halides, acid anhydrides or a ketene with an alkyl, alkaryl or alkylhalo sulfonate to yield a sulfonic. Carboxylic anhydride compound which is then reacted with a dioxane to cleave the ring of the dioxane, yielding a cleavage product which cleavage product is then aminated with an alkylamine and hydrolyzed with base to yield the severely sterically hindered secondary aminoether alcohol.
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Page/Page column 17
(2008/06/13)
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- Syntheses of 1-substituted furan-fused 3-sulfolenes and their Diels-Alder reactions
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The preparation of 1-substituted 4H,6H-dihydrothienofuran 5,5-dioxides and their intermolecular Diels-Alder reactions with typical dienophiles are described. 1-Acetyl-1d and 1-nitro-furansulfolene 1e were prepared by simple new methods.Acetyl and nitro substituents in the furan moiety did little to diminish its Diels-Alder reactivity relative to the corresponding furans.Furthermore, on reaction with dimethyl fumarate, 1-acetylfuransulfolene 1d acted like the corresponding 3,4-dimethylenefuran.
- Suzuki, Takayoshi,Fuchii, Hideyuki,Takayama, Hiroaki
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p. 2699 - 2704
(2007/10/03)
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- SYNTHESES OF 2-SUBSTITUTED FURAN-ANNULATED 3-SULFOLENES AND THEIR DIELS-ALDER REACTIONS
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The preparation of 2-substituted 4,6-dihydrothienofuran-5,5-dioxides (1b-e) and their intramolecular Diels-Alder reactions with typical dienophiles are described.
- Suzuki, Takayoshi,Fuchii, Hideyuki,Takayama, Hiroaki
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- A novel and versatile route to mixed p-toluenesulphonic carboxylic anhydrides
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A versatile route to the mixed p-toluenesulphonic carboxylic anhydrides (1) via the reaction of tetra-n-butylammonium carboxylate (2) with p-toluenesulphonyl chloride in a neutral medium is described.Some of the synthetic applications of the proposed method are described.
- Kumar, Arvind,Srivastava, Nivedita,Mital, Alka
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p. 606 - 607
(2007/10/02)
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