Kinetic studies of Lewis acidity. Part 2. Catalysis by tin(IV) chloride, by some organotin(IV) chlorides, and by tin(II) chloride of the anionotropic rearrangement of 1-phenylprop-2-en-1-ol in tetramethylene sulphone solution
| Autor: | Ja'far Al-Ka'bi, Peter H. Gore, David N. Waters, Robert Hollingworth, Jameel A. Farooqi, Padraig C. Doolan |
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| Rok vydání: | 1986 |
| Předmět: | |
| Zdroj: | Journal of the Chemical Society, Perkin Transactions 2. :501 |
| ISSN: | 1364-5471 0300-9580 |
| DOI: | 10.1039/p29860000501 |
| Popis: | The kinetics have been measured for the rearrangement of 1-phenylprop-2-en-1-ol (1) to 3-phenylprop-2-en-1-ol (2) in tetramethylene sulphone solution, catalysed by various tin(IV) chloride species. The rate coefficients, kn′ at 313.2 K, per unit concentration of the catalyst, were: SnCl4, 305; PhSnCl3, 86.4; p-MeC6H4SnCl3, 18.7; MeSnCl3, 6.60; PrnSnCl3, 5.36; EtSnCl3, 4.69; BunSnCl3, 1.62; (p-CIC6H4)2SnCl2, ca. 3 × 10–2; Ph2SnCl2, 5.1 × 10–3; Et2SnCl2, 1.4 × 10–3, Me2SnCl2, 4.3 × 10–4 dm3 mol–1 s–1. The reaction catalysed by SnCl4 was studied with a range of added compounds, viz. H2O, LiCl, LiCIO4, and 1,8-bis(dimethylamino)naphthalene. Evidence was obtained for the involvement of both anhydrous SnCl4 and its monohydrate as catalysts for the rearrangement. Tin(II) chloride has been found to be an effective catalyst for the rearrangement, with kn(313.2 K)= 3.51 dm3 mol–1 s–1. Addition of phosphoryl chloride to SnCl2 causes a sharp increase in rate, with a maximum corresponding to the species SnCl2·POCl3. The value of kn(303.5 K)≃ 1 200 dm3 mol–1 s–1 makes this catalyst the most powerful yet found for the rearrangement. |
| Databáze: | OpenAIRE |
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