Amines, tertiary

Pnmary amine Secondary amine Tertiary amine... 

Nitrosation (Section 22 15) The reaction of a substance usu ally an amine with nitrous acid Pnmary amines yield dia zonium 10ns secondary amines yield N nitroso amines Tertiary aromatic amines undergo nitrosation of their aro matic ring... 

This reaction can also be utili2ed to prepare functionali2ed initiators by reaction of butyUithium with a substituted 1,1-diphenylethylene derivative. For example, polymers end functionali2ed with primary amine, tertiary amine, phenol, and bis(phenol) groups have been prepared in essentiaUy quantitative yield by using the reaction of butyUithium with the corresponding substituted (or protected) 1,1-diphenylethylene (87). 

Methyl bromide slowly hydrolyzes in water, forming methanol and hydrobromic acid. The bromine atom of methyl bromide is an excellent leaving group in nucleophilic substitution reactions and is displaced by a variety of nucleophiles. Thus methyl bromide is useful in a variety of methylation reactions, such as the syntheses of ethers, sulfides, esters, and amines. Tertiary amines are methylated by methyl bromide to form quaternary ammonium bromides, some of which are active as microbicides. 

Gold nanoparticles stabilized by primary amine, tertiary amine, sulfide, and thiols... 

Scheme 2. Production of size-regulated gold nanoparticles stabilized by primary amines, tertiary amines, sulfides, and thiols formed by the controlled thermolysis of gold(I) thiolate complex in the presence of amine (reprinted from Ref. [11], 2005, with permission from Elsevier).

It is well known that alkyl substitution changes the basicity of amines. However, solvation effects lead to an anomalous order of basicities in solution (NH3 tertiary amine < primary amine < secondary amine). From gas-phase proton affinity data the intrinsic effects of alkyl substituents can be evaluated and a quite regular order (NH3 < primary amine < secondary amine < tertiary amine) is obtained91. 

Compared with primary and secondary amines, tertiary amines are virtually unreac-tive towards carbenes and it has been demonstrated that they behave as phase-transfer catalysts for the generation of dichlorocarbene from chloroform. For example, tri-n-butylamine and its hydrochloride salt have the same catalytic effect as tetra-n-butylammonium chloride in the generation of dichlorocarbene and its subsequent insertion into the C=C bond of cyclohexene [20]. However, tertiary amines are generally insufficiently basic to deprotonate chloroform and the presence of sodium hydroxide is normally required. The initial reaction of the tertiary amine with chloroform, therefore, appears to be the formation of the A -ylid. This species does not partition between the two phases and cannot be responsible for the insertion reaction of the carbene in the C=C bond. Instead, it has been proposed that it acts as a lipophilic base for the deprotonation of chloroform (Scheme 7.26) to form a dichloromethylammonium ion-pair, which transfers into the organic phase where it decomposes to produce the carbene [21]. 

Tertiary amines. Tertiary amine type compounds, react with nitrous acid to yield secondary-amine type N-nitroso compounds. The myth that tertiary amines do not nitrosate to yield N-nitroso compounds, is a remarkable feat of misinformation that has persisted for over 100 years (23, 24, 25). 

Reductive alkylation of ammonia should give primary amines, reductive alkylation of primary amines secondary amines, and reductive alkylation of secondary amines tertiary amines. In reality, secondary and even tertiary amines are almost always present to varying extents since the primary amines formed in the reaction of the carbonyl compounds with ammonia react with the carbonyl compounds to give secondary amines, and the secondary amines similarly afford tertiary amines according to Scheme 128. In addition, secondary amines may be formed, especially at higher temperatures, by additional reactions shown in Scheme 129. Depending on the ratios of the carbonyl compounds to ammonia or amines, different classes of amines predominate. 

Seven TCA drugs are available in the United States for treatment of major depression. They are generally categorized as tertiary or secondary amines. Tertiary amines include imipramine (Tofranil), amitriptyline (Elavil), trimipramine (Surmontil), and doxepin (5m-equan). Desipramine (Norpramin), nortriptyline (Pam-elor), and protriptyline (Vivactil) are secondary amines. 

Ans. (a) alcohol (hydroxyl) (b) amine (tertiary amine) (c) ester (d) chloride (e) ketone (f) carboxylic acid (g) ester (triglyceride) (h) amide (i) ether (/ ) aldehyde (k) bromide (dibromide) (Z) alkyne (triple bond)... 

Aluminum powder Aluminum alkyls Grinding Heating Carboxylic acid chlorides Ethers Tertiary amines Tertiary phosphines Metal chlorides... 

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