Nitrogen compounds tertiary amines

Alkylation can also be carried out, in certain compounds, at positions a to other heteroatoms, for example, at a position a to the nitrogen of tertiary amines. Alkylation a to the nitrogen of primary or secondary amines is not generally feasible because an NH hydrogen is usually more acidic than a CH hydrogen. a-Lithiation of... 

Excellent procedures are available for the preparation of primary, secondary, and tertiary amines by the reduction of a variety of nitrogen compounds. Primary amines can be obtained by hydrogenation or by lithium aluminum hydride reduction of nitro compounds, azides, oximes, imines, nitriles, or unsubstituted amides [all possible with H2 over a metal catalyst (Pt or Ni) or with LiAlH4] ... 

Phenyl-l,2,4-triazoline-3,5-dione (589) reacts with primary alcohols ROH to yield the ester-amides (590) and nitrogen, while tertiary amines or pyridine afford the bicyclic compound (591). " With heptalene, a mixture of stereoisomeric cyclo-adducts (592) is obtained.Thermolysis of the amino-azimine (593) yields mainly phenyl isocyanate and dimethylcarbamoyl azide, Me2NCON3." ... 

Nuclear magnetic resonance (nmr) spectroscopy is useful for determining quaternary stmcture. The N-nmr can distinguish between quaternary ammonium compounds and amines, whether primary, secondary, or tertiary, as well as provide information about the molecular stmcture around the nitrogen atom. The C-nmr can distinguish among oleic, tallow, and hydrogenated tallow sources (194). 

Tertiary amines can be oxidized to form amine oxides in which the amino nitrogen atom is linked to a single oxygen atom. The resulting compounds are basic dissolving in water thus ... 

The similarity between the cryptands and the first of these molecules is obvious. Compound 7 7 is a urethane equivalent of [2.2.2]-cryptand. The synthesis of 7 7 was accomplished using a diacyl halide and l,10-diaza-18-crown-6 (shown in Eq. 8.13). Since amidic nitrogen inverts less rapidly than a tertiary amine nitrogen, Vogtle and his coworkers who prepared 7 7, analyzed the proton and carbon magnetic resonance spectra to discern differences in conformational preferences. Compound 7 7 was found to form a lithium perchlorate complex. 

The fluoraza reagents consist of two types of compounds one in which a fluorine atom is bound to the nitrogen atom of an amide or, more often, a sulfonamide and one in which a fluorine atom is bound to the nitrogen atom of a tertiary amine such as pyridine, quinuclidine, or triethylenediamine 1,4-diaza-bicyclo[2 2.2]octane. The positive charge on the nitrogen is counterbalanced by a non-nucleophilic anion such as triflate or tetrafluoroborate. 

The oxidation of amines by mercuric acetate is an old reaction (54) which up until recent years was employed primarily to modify alkaloid structures (55). A systemic study of the oxidizing action of mercuric acetate by Leonard and co-workers led to the development of a general method for the synthesis of enamines from cyclic tertiary amines. An observation made after a large number of compounds were oxidized, but which is worth noting at the onset, is that a tertiary hydrogen alpha to the nitrogen atom is removed preferentially to a secondary a-hydrogen. 

The activation energy of substitution of an unactivated aromatic halide (e.g., fiuorobenzene and 2-chloronaphthalene ) is over 30 kcal while that of activated compounds is 5-20 kcal. For the tabulated reactions (Tables II-VIII) with alkoxide and with primary, secondary, or tertiary amines, resonance activation (cf. 278 and 279) by ortho or para nitrogens is found to be greater than inductive activation (cf. 251). This relation is qualitatively demonstrated in... 

Summary If the molecular weight is odd, then the compound contains an odd number of nitrogens. Fragment ions observed at even-mass numbers suggests the presence of nitrogen. The loss of ammonia is fairly common in nitrogen compounds and may not indicate exclusively that an amine is present. Chemical derivatization will easily determine if the unknown is a tertiary amine. 

Other nitrogen compounds, among them hydroxylamine, hydrazines, and amides (15-9), also add to alkenes. Even with amines, basic catalysts are sometimes used, so that RNH or R2N is the actual nucleophile. Tertiary amines (except those that are too bulky) add to Michael-type substrates in a reaction that is catalyzed by acids like HCl or HNO3 to give the corresponding quaternary ammonium salts. " ... 

The nitrogen atom in quinolizidine derivatives behaves as a tertiary amine and hence it can undergo quaternization by reaction with alkyl halides. For instance, berberine derivative 101 was transformed into 102 by treatment with 3-iodopropanol followed by anion exchange. Compound 102 was then transformed into intermediate 103, which was employed as a precursor for the the preparation of bis-ammonium salt 104 (Scheme 10). This compound showed ultrashort curare-like activity in rhesus monkeys <2001JOC3495>. 

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