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Straightforward formation of carbocations from tertiary carboxylic acids via CO release at room temperature.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 2/7/2019, Vol. 48 Issue 5, p1574-1577, 4p
- Publication Year :
- 2019
-
Abstract
- We report an unprecedented mode of reactivity of carboxylic acids. A series of tertiary carboxylic acids, containing at least one phenyl α-substituent, undergo loss of carbon monoxide at room temperature (295 K), by a one pot reaction with 0.5–1 molar equivalents of WCl<subscript>6</subscript> in dichloromethane. A plausible mechanism for the Ph<subscript>3</subscript>CCO<subscript>2</subscript>H/WCl<subscript>6</subscript> reaction, leading to [CPh<subscript>3</subscript>][WOCl<subscript>5</subscript>] and Ph<subscript>3</subscript>CCl, is proposed on the basis of DFT calculations. The analogous reactions involving CEt(Ph)<subscript>2</subscript>CO<subscript>2</subscript>H, CMe(Ph)<subscript>2</subscript>CO<subscript>2</subscript>H and CMe<subscript>2</subscript>(Ph)CO<subscript>2</subscript>H selectively afforded stable hydrocarbons (alkene or indene, depending on the case), apparently resulting from the rearrangement of elusive tertiary carbocations. [ABSTRACT FROM AUTHOR]
- Subjects :
- X-ray diffraction
DENSITY functional theory
CHEMICAL reactions
Subjects
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 48
- Issue :
- 5
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 134382454
- Full Text :
- https://doi.org/10.1039/c8dt04416c