Article

 

Reactions of Vinylcyclopropane and Bicyclopropyl Compounds With Maleic Anhydride

 

C. K. Jankowski,^1* A. Pelletier,¹ Eduardo Díaz,² Jacqueline M. R. Belanger,³ J.R. J. Paré,³ C. Lamouroux,¹ and J. Boivin⁴

 

¹ Département de Chimie et Biochimie, Université de Moncton, Moncton , NB, E1A 3E9, Canada. ^*Responsible author: jankowc@moncton.ca.

² Instituto de Química, Universidad Nacional Autónoma de México. Circuito Exterior, Ciudad Universitaria. Coyoacán 04510, México, D.F.

³ CTE, Division of green chemistry, Environment Canada, Ottawa, 325 River Road, K1A 0H3 Canada.

⁴ Institut des substances naturelles, CNRS, 91198 Gif– sur– Yvette, France. Tel 1 506 858 4331, fax 4541.

 

Received June 22, 2009
Accepted November 20, 2009

 

Abstract

Vinylcyclopropane and bicyclopropyl C₆ compounds are studied as diene precursors in the Diels–Alder reaction. Their rearrangement under different thermal and microwave conditions leads to specific isomeric hexa–, penta– or butadienes, condensed with maleic anhydride as a dienophile. Adduct stereochemistries were compared to those of previously–synthesized model compounds, and are fully characterized with 2D NMR and GC–MS spectroscopies. Some unsaturated terpenes bearing vinylcyclopropane moieties were also condensed, and their adduct structures assigned.

Key words: Microwave, Thermal Diels–Alder Reactions, Diene Precursors, Vinylcyclopropane as a Diene.

 

Resumen

Vinilciclopropano y compuestos biciclopropilos C₆ se estudiaron como precursores de dienos en reacciones de Diels–Alder. La transposición de estos compuestos bajo condiciones térmicas o de irradiación de microondas conduce específicamente a hexa–, penta– o butadienos isoméricos, los cuales cicloadicionan con anhídrido maleico como dienófilo. La estereoquímica de los aductos se estableció por comparación con aductos modelo previamente preparados y se caracterizaron por espectroscopia de RMN de dos dimensiones y CG–EM. Algunos terpenos insaturados llevando consigo el sistema vinil–ciclopropano también se condensaron, y fue asignada la estructura de sus aductos.

Palabras clave: Microondas, reacciones térmicas de Diels–Alder, precursores de dienos, vinilciclopropanos como dienos.

 

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32. The above mentioned difficulties are related to the six carbon or lower chains of dienes involved and to the cyclopropylcarbinols. The other isomeric model C₆ dienes were not commercially accessible . Some of them cannot be obtained from the cyclopropane compounds of this study and then are not potential diene precursors.

33. The small volume stainless steel vessel conditions are relatively close to those applied in using the MW methods.