Primary-tertiary amines

The lower members of other homologous series of oxygen compounds— the acids, aldehydes, ketones, anhydrides, ethers and esters—have approximately the same limits of solubility as the alcohols and substitution and branching of the carbon chain has a similar influence. For the amines (primary, secondary and tertiary), the limit of solubility is about C whilst for the amides and nitriles it is about C4. 

Ammonia can act as a nucleophile toward primary and some secondary alkyl halides to give primary alkylamines Yields tend to be modest because the primary amine IS itself a nucleophile and undergoes alkylation Alkylation of ammonia can lead to a mixture containing a primary amine a secondary amine a tertiary amine and a quaternary ammonium salt... 

In practice, ammonia is most frequendy used. With hexa, the initial reaction steps differ, but the final resole resins are identical, provided they contain the same number of nitrogen and CH2 groups. Most nitrogen from ammonia or hexa is incorporated as diben2ylamine with primary, tertiary, and cycHc amine stmctures as minor products. 

Alkylation (Section 22.12) Amines act as nucleophiles toward alkyl halides. Primary amines yield secondary amines, secondary amines yield tertiary amines, and tertiary amines yield quaternary ammonium salts. 

Th - three classes of aliphatic amines (primary, secondary, ind tertiary) maybe distinguished by their behaviour with nitrous... 

Charge-transfer complexes with pyrimidine and purine bases as well as with solvents like hexa-methylphosphoramide and dimethyl sulfoxide are reported in Ref 66. The action of aromatic amines (primary, secondary, or tertiary) resulted in fume-offs or unidentifiable tars, in all cases purple or red colors developed prior to more violent reactions (Ref 66)... 

Similarly, primary amines give tertiary as well as secondary amines. In order to minimize this, the aldehyde or ketone is treated with an excess of ammonia or primary amine (unless of course the higher amine is desired). 

One of the exciting results to come out of heterogeneous catalysis research since the early 1980s is the discovery and development of catalysts that employ hydrogen peroxide to selectively oxidize organic compounds at low temperatures in the liquid phase. These catalysts are based on titanium, and the important discovery was a way to isolate titanium in framework locations of the inner cavities of zeolites (molecular sieves). Thus, mild oxidations may be run in water or water-soluble solvents. Practicing organic chemists now have a way to catalytically oxidize benzene to phenols alkanes to alcohols and ketones primary alcohols to aldehydes, acids, esters, and acetals secondary alcohols to ketones primary amines to oximes secondary amines to hydroxyl-amines and tertiary amines to amine oxides. 

Primary amine-containing polymeric particles are available from a number of manufacturers and have either aliphatic or aryl amine groups on their surface. Occasionally, a particle type may have secondary or tertiary amines present, but these should be avoided for covalent coupling, as primary amines typically give better reaction yields than secondary amines and tertiary amines are unreactive. 

Since the order of increasing CL intensity for alkyl amines reacted with Ru(bpy)32+ is tertiary amines > secondary amines > primary amines, pharmaceutical compounds bearing a tertiary amine function (e.g., antihistamine drugs [99], anticholinergic drugs [100], erythromycin [101], and its derivatives [102]) have been sensitively determined after HPLC separation (Table 3). The method was applied to the detection of d- and L-tryptophan (Trp) after separation by a ligand-exchange HPLC [103], The detection limits for d- and L-Trp were both 0.2 pmol per injection. Oxalate in urine and blood plasma samples has also been determined by a reversed-phase ion-pair HPLC (Fig. 18) [104], Direct addition of... 

Amino acids labeled with DNS-C1 were determined using the Ru(bpy)32+ CL reaction after HPLC separation with a reversed-phase column [104, 105], DNS derivatives are expected to produce intense CL owing to their secondary and tertiary amino groups. The detection limit for DNS-Glu was 0.1 pM (2 pmol/ injection). Although underivatized amino acids could be detected by Ru(bpy)32+ CL, the DNS derivatives showed improved detection limits by three orders of magnitude [105], An approach to convert primary amines to tertiary amines was also reported [106], In this method, divinyl sulfone (DVS) was used for a cycloaddition reaction of primary amines (Fig. 19). The DVS derivatives after HPLC separation were sensitively detected (e.g., detection limits for propylamine and 3-aminopentane were 30 and 1 pmol, respectively). 

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. 

Carboxylic acid, aldehyde, ketone, ether, alcohol, ester, ester-R (the chain attached to the oxygen atom being a generic substituent), anhydride, acetal, amide, epoxide, acid halyde, primary amine, primary imine, cyano, secondary amine, secondary imine, tertiary amine, nitro derivative, metal-1, metal-2, carbene, halo derivative. 

Hofmann amine separation org chem A technique to separate a mixture of primary, secondary, and tertiary amines they are heated with ethyl oxalate there is no reaction with tertiary amines, primary amines form a diamide, and the secondary amines form a monoamide when the reaction mixture is distilled, the mixture is separated into components. haf-mon am,en, sep-3,ra-sh3n ... 

Amines are organic derivatives of ammonia in which one or more hydrogen atoms in ammonia has been replaced by alkyl groups. There are three structural types of amine primary, secondary and tertiary. They are classified according to the number of alkyl groups attached to the nitrogen atom. 

The second important feature of the reaction mechanism of the epoxy compound curing under the action of amines (primary, secondary and tertiary) and their mixtures consists in formation of various hetero-, auto-, inter- and intramolecular donor-acceptor complexes between the components of the reaction system — the starting substances and reaction products. Consideration of this complex formation can adequately explain the reaction kinetics. 

Tertiary amines. Primary- amines bearing an a-hydrogen atom arc converted in high yield to symmetrical secondary amines when heated at 185° in the presence of about 0.2 mole % of this ruthenium complex (equation l).1 Use of larger amounts of... 

SAM-PT and SAM-S strong amines isolated on cation-exchange resin (primary, tertiary, and secondary amines, primarily aliphatic). 

Ethane (crit. temp., upper layer, 39.8) LCST, 38.1 n-Heptane Cyclohexane Decalin Tetralin Paraffin waxes Paraffinic oils Naphthenic oils Higher alcohols (Cf. Figure Fourteen Amides Five primary Amines Six secondary Amines Three tertiary Amines m-Aminobenzoic acid (m.p. 174)... 

Among isomeric amines, primary amines have the highest boiling points, and tertiary amines the lowest. 

---