Reactions Involving Substituents

There are a few examples of reactions involving substituents on the nitrogen atoms of the 1,3,5,7-tetrazocanes. The reaction of tetraacetyltetrazocane 52 with nitric acid was reported as a clean and convenient approach to 1 -acetyl-3, 5,7-trinitro-l,3,5,7-tetrazocane 53 (SOLEX) (Equation 16) <1992USP5120887>. 

Reactions involving substituents at ring carbon atoms have not been well investigated. A straightforward conversion of a nitrile to an aldehyde group in a 1,2-azoniaboratatolidine has been reported (Equation 12) <1996CB1541>. 

Since its discovery in the context of the reactions of the monoterpenoids, examples of the rearrangement have been found in many other systems. Therefore, for the purposes of this chapter, which is concerned with the synthetic utility of the Wagner-Meerwein type of rearrangement, some reactions involving substituents migrating will be included as well as examples of skeletal rearrangement in polycyclic systems. 

Reactions of substituents attached to the ring carbon atoms of aziridines and azirines have been reviewed (B-83MI 101-01, B-83MI 101-02, 84CHEC-I(7)47>. Many of the reactions involving substituents... 

A few reactions involving substituents on the ring sulfur have been reported. On hydrolysis the... 

A number, of reactions involving substituents in the a-position of 5-alkyl-substituted tetrazoles have been reported. Thus new 1-substituted tetrazole-5-carbaldehydes (183) and their 2-substituted isomers have recently been prepared (Scheme 19) and treated with a range of reagents.422 Studies of the relative reactivities of 1-aryl- and 2-... 

Bronsted s original correlation was for proton-transfer reactions but many workers now use the ionisation of an acid as a general measure of polarity for reactions involving substituent groupings similar to the model acid. For example nucleophilic substitution by aryloxide ions into 2,4-dinitrochlorobenze (Eqn. 14) [9] may be... 

Although most chemistry in these ring systems involves reaction at the heteroatom, there are two important reactions involving substituents directly attached to the heteroatom reduction of oxides and formation of ylides (see Section 2.16.11.1). 

There are few examples of reactions involving substituents attached to eight-membered ring heterocycles. 

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