2D ultrafast HMBC 1H,31P: obtaining mechanistic details on the MichaelisArbuzov reaction.
J Org Chem
; 80(2): 799-805, 2015 Jan 16.
Article
en En
| MEDLINE
| ID: mdl-25479557
ABSTRACT
Ultrafast NMR spectroscopy (UF-NMR) can be used to monitor chemical reactions in real time and to provide insights into their mechanisms and the nature of the intermediates formed. Here, we have developed a 2D 1H,31P UF-HMBC method and the corresponding NMR experimental setup to enable the study of a MichaelisArbuzov reaction at two different temperatures, 25 and 70 °C. The specific reaction studied was between triethyl phosphite and benzyl bromide to produce diethylbenzyl phosphonate. Our results show that at 70 °C the reaction takes place directly, without the detection of an intermediate by 1H,31P UF-HMBC. In contrast, at 25 °C, using zinc bromide as a catalyst, our results show the formation of benzyltriethoxy phosphonium bromide as an intermediate. The experiments again show the power of UF-NMR in mechanistic studies of reactions involving various phosphorus chemical species.
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Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Compuestos de Bencilo
/
Espectroscopía de Resonancia Magnética
/
Organofosfonatos
Idioma:
En
Revista:
J Org Chem
Año:
2015
Tipo del documento:
Article