Cycloalkyl tertiary

R may be methyl or primary secondary or tertiary alkyl it may also be a cycloalkyl alkenyl or aryl group)... 

Dialkyl peroxides have the stmctural formula R—OO—R/ where R and R are the same or different primary, secondary, or tertiary alkyl, cycloalkyl, and aralkyl hydrocarbon or hetero-substituted hydrocarbon radicals. Organomineral peroxides have the formulas R Q(OOR) and R QOOQR, where at least one of the peroxygens is bonded directly to the organo-substituted metal or metalloid, Q. Dialkyl peroxides include cyclic and bicycflc peroxides where the R and R groups are linked, eg, endoperoxides and derivatives of 1,2-dioxane. Also included are polymeric peroxides, which usually are called poly(alkylene peroxides) or alkylene—oxygen copolymers, and poly(organomineral peroxides) (44), where Q = As or Sb. 

Amines are derivatives of ammonia in which one or more of the hydrogens is replaced with an alkyl, aryl, cycloalkyl, or heterocycHc group. When more than one hydrogen has been replaced, the substituents can either be the same or different. Amines are classified as primary, secondary, or tertiary depending on the number of hydrogens which have been replaced. It is important to note that the designations primary, secondary, and tertiary refer only to the number of substituents and not to the nature of the substituents as in some classes of compounds. 

R and Rf are = or f primary, secondary, tertiary alkyl, cycloalkyl, aralkyl and heterocyclic radicals... 

The tertiary amine can be aliphatic, cycloalkyl, or heterocyclic (including pyridine). 

In going from a secondary to a tertiary cycloalkyl fluoride, one observes the usual deshielding effect as is exemplified by the isomeric 1 -lluoro-1 -mcthyl-4-t-butylcyclohcxancs. Of course, these two isomers exist essentially in the single conformation given, because of the presence of the 4-t-butyl substituent. 

Tertiary cycloalkyl cations, such as the 1-methylcyclopent-l-yl cation 28, show high stability in strong acid solutions. This ion can be obtained from a variety of precursors (Figure 3.7).143,144 It is noteworthy to mention that not only cyclopentyl- but also cyclohexyl-type precursors give 1 -methylcyclopent-1 -yl cation 28. This indicates that the cyclopentyl cation has higher stability, which causes isomerization of the secondary cyclohexyl cation to the tertiary methylcyclopentyl ion. 

Sorensen and co-workers150 have prepared tertiary cycloalkyl cations of different ring sizes, n = 4 (small ring), n = 5-7 (common rings), n = 8-11 (medium rings),... 

Oxidation with trimethylamine N-oxide is not complicated by side reactions and proceeds in a stepwise fashion such that one primary alkyl group is oxidized at 25 C, the second at 65 C and the third at 120 C. ° The trimethylamine evolved can be estimated and thus the method can be used for the quantitative estimation of organoboranes. The rates of oxidation are not markedly solvent dependent and there is a clear cut ease of oxidation in the order tertiary alkyl > secondary cycloalkyl > secondary alkyl > primary alkyl > branched primary alkyl > vinyl. Some examples of useful differentiation are shown in equations (23) and (24). ... 

Dialkyl peroxides (1), R-O-O-R (R and R are = or primary, secondary, tertiary alkyl, cycloalkyl, aralkyl and heterocyclic radicals Homolytic decompn when heated or irradiated with prodn of free radicals for org synthesis difficult to hydrolyze and reduce rearrangement crosslinking and polymerization polymeric peroxides are thick liqs or amorph wh powds used as polymerization catalysts Primary radicals are unstable, lowest members such as dimet peroxide are shock sens and dangerous expls sensitivity lessens with increasing mw polymeric peroxides (copolymers of olefins and Oj) explode on heating... 

The tertiary amine can be aliphatic, cycloalkyl, or heterocyclic (including pyridine). The reaction of NaOH with an amine containing two distal alkene units, followed by addition of a neodymium catalyst leads to a bicyclic amine. " ... 

The stereochemistry of dehydrohalogenation with DBU has been studied by several authors. Wolkoff (82JOC1944) studied in detail the stereochemical consequences of dehydrohalogenation of secondary and tertiary alkyl and cycloalkyl halides with DBU. A comparison of the product distributions obtained in the elimination reactions of alkyl halides with DBU, with weak bases, and with anionic bases indicated that the elimination reactions with DBU very probably follow an E2C-like mechanism. 

Amines. Primary amines, RNHj, where R is alkyl, arylalkyl, or cycloalkyl, when boiled with Raney nickel (no Hj) are converted into the secondary amine (80% yield) and some tertiary amine (10%). n-Hexylamine —> di-n-hexylamine (70%) and tri-n-hexylamine (9%). The reaction is considered to involve dehydrogenation to the aldimine followed by addition of the starting amine, elimination of ammonia, and hydrogenation. 

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