Azidocyclohexane

PREPARATION OF AZEPIN-2-ONES VIA THE PHOTO-INDUCED RING EXPANSION OF AZIDOCYCLOHEXANES... 

PHOTO-INDUCED RING EXPANSION OF 1-TRIISOPROPYLSILYLOXY-1-AZIDOCYCLOHEXANE PREPARATION OF e-CAPROCACTAM... 

PHOTO-INDUCED RING EXPANSION OF l-TRIISOPROPYLSILYLOXY-1-AZIDOCYCLOHEXANE PREPARATION OF e-CAPROLACTAM [2 Azepin-2-one, hexahydro- from Silane, [(1-azidocyclohexyl)oxy]tris(1-... 

A. 1-Triisopropylsilyloxy-1-azidocyclohexane A 2-L, two-necked, round-bottomed flask is equipped with a magnetic stirrer, argon inlet, and a rubber septum (Note 1). The flask is charged with freshly-distilled 1-triisopropylsilyloxycyclohexene (25.47 g, 100 mmol. Note 2) and anhydrous dichloromethane (1.0 L, Note 3). Azidotrimethylsilane (68.5 mL, 500 mmol. Note 4) is added via syringe, immediately followed by anhydrous Dowex 50 X 8-100 (24.98 g. Note 5) in a single portion from a dry flask. The suspension is stirred vigorously at ambient temperature for ca. 48 hr (Note 6). The reaction mixture is filtered to recover the Dowex resin and solvent is removed under reduced pressure to... 

Triisopropylsilyloxy-1 -azidocyclohexane Silane, [ 1 -azidocyclohexyl)oxy]tris 1 -methylethyl)- (13) (172090-42-5)... 

Azidocyclohexane. See Cyclohexyl Azide under Cyclohexane and J.H.Boyer et al,... 

Intermolecular reactions of this type can be slow if either of the reaction partners has a bulky substituent. Reactions with chloroboranes R2BCI or RBCI2 go under much milder conditions. The stereochemistry of the carbon-boron bond is retained in the product for example, the borane (11) gave the amine (12 90%) on reaction with azidocyclohexane. 

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