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By Gerald Holton, Stephen G. Brush

ISBN-10: 0201029707

ISBN-13: 9780201029703

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Log k vs log Ρ curves are given in Fig. 7 χ 10~ sec . 6°C. Log k vs log Ρ curves are given in Fig. 2. In all cases, the experimental data extended into the high pressure region. 6°C. The classical empirical Kassel fit parameter s and the Slater parameter η for methyl and ethyl isocyanide were determined analytically from the shape 17 9 19 22 23 14,30 -5 -1 œ 5 1 4 -1 4 1 4 1 4 1 44 Κ. Μ. Moloney and B. S. Rabinovitch οι 0 1 log | 0 ρ 2 3 4 (mm) Fig. 8°C. For clarity the 260° curve is arbitrarily displaced by one log k unit to the left in the figure, whereas the 199°C curve is displaced the same distance to the right; actually, both of these curves would almost coincide with the 230°C curve.

That the rearrangement proceeds with very little charge separa­ tion. -methoxyphenyl isocyanide) and the retention of configuration in the rearrangement of optically active sec-butyl isocyanide. 2 2 3. Isonitrile-Nitrile Rearrangement 43 Extended Huckel calculations of Van Dine and Hoffmann (VH) are not in good agreement with the experimental findings of Casanova et al? VH find in every isonitrile studied that there is an increase in positive charge at the migrating carbon atom (R group) in the transition state.

Chem. 27, 3651 (1962). 114. , / . Org. Chem. 26, 2202 (1961). 115. , Bull. Chem. Soc. Jap. 38, 858 (1962). 116. Nef, I. , Ann. Chem. 270, 267 (1892). 117. Nef, I. , Ann. Chem. 280, 291 (1894). 118. Nef, I. , Ann. Chem. 287, 265 (1895). 119. Nef, I. , Ann. Chem. 298, 202 (1897). 120. Nef, I. , Ann. Chem. 298, 368 (1897). 121. Nef, I. , Ann. Chem. 309, 126 (1899). 122. , Angew. Chem. 76, 440 (1964); Angew. , Int. Ed. Engl. 3, 382 (1964). 123. , Angew. Chem. 76, 500 (1964); Angew. , Int. Ed. Engl.

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Introduction to Concepts and Theories in Physical Science by Gerald Holton, Stephen G. Brush


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