Preparation of some ketoorganostannanes and ketoorganochlorostannanes. Intramolecular coordination in ketoorganochlorostannanes
| Autor: | Kuang-Hsin Tsai, Henry G. Kuivila, Perry L. Maxfield, Nicholas M. Scarpa, Karl R. Wursthorn, James E. Dixon, Terry M. Topka |
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| Rok vydání: | 1975 |
| Předmět: |
Organic Chemistry
chemistry.chemical_element Photochemistry Biochemistry Medicinal chemistry Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Nucleophile Reagent Intramolecular force Pyridine Electrophile Materials Chemistry Physical and Theoretical Chemistry Trimethyltin chloride Tin |
| Zdroj: | Journal of Organometallic Chemistry. 86:89-107 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/s0022-328x(00)88515-0 |
| Popis: | Ketoorganostannanes of the structure Me3Sn(CH2)n COR with n = 2,3 and R = Me, Ph have been prepared by the oxidation of the corresponding alcohols, and by the reaction of the appropriate cyanoalkyltrimethylstannanes with methyl or phenyl Grignard reagents. The ketoorganostannanes have been converted to the chloro analogs Me2Sn(Cl)(CH2)nCOR by methyl-chlorine exchange with trimethyltin chloride. The reactions with these ketones are considerably faster than that with n-butyltrimethylstannane, suggesting that intramolecular nucleophilic catalysis of an electrophilic displacement reaction occurs. Evidence that the ketoorganochlorostannanes have a structure involving intramolecular coordination between the carbonyl oxygen and the tin is provided by studies of the infrared, ultraviolet, proton and carbon-13 magnetic resonance, and Mossbauer spectra. Pyridine is shown to compete with intramolecular carbonyl in coordination to the chlorotin function, the effect being more pronounced when n = 3 than when n = 2, reflecting the greater stability of the five-membered ring complex. |
| Databáze: | OpenAIRE |
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