Amination alkyl groups

Let us start with octahedral ML. For the moment L will be a simple o donor ligand. In other words, L has one valence orbital which is pointed toward the metal and there are two electrons in it. Examples arc the lone pair of a phosphine, amine, alkyl group, 15.5, or even the s orbital of a hydride, 15.6. Some ML examples are Cr(PMe3)6, 15.7, or the tris(cthylcncdiamine)Fe complex, 15.8 (here the ethyl-enediaminc group is H2NCH2CH2NH2). What we arc initially concerned with arc... 

Thus, the values calculated for effective polarizability at the nitrogen atom for a series of 49 amines carrying only alkyl groups was correlated directly with their proton affinities, a reaction that introduces a positive charge on the nitrogen atom by protonation (Figure 7-7) [40. ... 

If, however, a tertiary amine has two alkyl groups and also an aryl group having the para position unsubstituted, then the action of nitrous acid is to insert the nitroso group directly into this para position. Dimethylaniline, for example, when treated with nitrous acid readily gives p-nitrosodimethyl-... 

Alkyl groups attached to aromatic rings are oxidized more readily than the ring in alkaline media. Complete oxidation to benzoic acids usually occurs with nonspecific oxidants such as KMnO, but activated tertiary carbon atoms can be oxidized to the corresponding alcohols (R. Stewart, 1965 D. Arndt, 1975). With mercury(ll) acetate, allyiic and benzylic oxidations are aJso possible. It is most widely used in the mild dehydrogenation of tertiary amines to give, enamines or heteroarenes (M. Shamma, 1970 H. Arzoumanian. 1971 A. Friedrich, 1975). 

Amines are named m two mam ways m the lUPAC system either as alkylamines or as alkanamines When primary amines are named as alkylamines the ending amine IS added to the name of the alkyl group that bears the nitrogen When named as alkan amines the alkyl group is named as an alkane and the e ending replaced by amine... 

Alkylamines are named m two ways One method adds the ending amine to the name of the alkyl group The other applies the principles of sub stitutive nomenclature by replacing the e ending of an alkane name by amine and uses appropriate locants to identify the position of the ammo group Arylammes are named as derivatives of aniline... 

The alkylation desctibed in this article is the substitution of a hydrogen atom bonded to the carbon atom of a paraffin or aromatic ring by an alkyl group. The alkylations of nitrogen, oxygen, and sulfur are described in separate articles (see Amines Ethers). 

Wetting times of /V,/V-dimethy1-/ -alkyl amine oxides as a function of the alkyl chain length show a minimum with dimethyl dodecyl amine oxide (Table 3). Foam generation of dimethyl-/ -alkylamine oxides solutions show a maximum when the alkyl group contains 14 carbons. 

Ritter Reaction (Method 4). A small but important class of amines are manufactured by the Ritter reaction. These are the amines in which the nitrogen atom is adjacent to a tertiary alkyl group. In the Ritter reaction a substituted olefin such as isobutylene reacts with hydrogen cyanide under acidic conditions (12). The resulting formamide is then hydroly2ed to the parent primary amine. Typically sulfuric acid is used in this transformation of an olefin to an amine. Stoichiometric quantities of sulfate salts are produced along with the desired amine. 

MonoaLkylation using small alkyl groups of the 1-, 2 - and 3 -amines tends to reduce potency somewhat, whereas alkylation of the 3-amino group reduces activity considerably (147). 1-/V-Alkylation, as in the case of 1-A[-acylation, can lead to resistance to some bacterial resistance reactions, eg,... 

Cl Acid Gieen 25 [4403-90-1] (3) (Cl 61570) was also invented in 1894. This dye shows improved wetfastness, and is prepared from leucoquinizarin by reaction with 2 moles of i)-toluidine in a similat manner to the preparation of Cl Acid Violet 43 (134). Wetfastness and leveling properties may be altered by choosing the substituents of arylamines. The introduction of alkyl groups into aromatic amines improves the wetfastness and affinity in neutral or weekly acid baths. Examples ate Cl Acid Blue 80 [4474-24-27] (131) (Cl 61585) and Cl Acid Gieen 27 [6408-57-7] (132) (Cl 61580). 

Enby 6 is an example of a stereospecific elimination reaction of an alkyl halide in which the transition state requires die proton and bromide ion that are lost to be in an anti orientation with respect to each odier. The diastereomeric threo- and e/ytAra-l-bromo-1,2-diphenyl-propanes undergo )3-elimination to produce stereoisomeric products. Enby 7 is an example of a pyrolytic elimination requiring a syn orientation of die proton that is removed and the nitrogen atom of the amine oxide group. The elimination proceeds through a cyclic transition state in which the proton is transferred to die oxygen of die amine oxide group. 

Alkylamine (Section 22.1) Amine in which the organic groups attached to nitrogen are alkyl groups. 

The acid-catalyzed reaction of acetophenone with acyclic secondary amines results in the formation of the expected enamine and a rearrangement product. The latter product arises from the transfer of one of the amino N-alkyl groups to the cnamine s carbon to produce a ketimine (53a). 

Amination of the deactivated carbanion of 4-benzylpyridine formed with excess sodamide presumably proceeds because the strong indirect deactivation is overcome by electrophilic attack by Na+ at the partially anionic azine-nitrogen and by concerted nucleophilic attack by H2N at the 2-position via a 6-membered cyclic transition state (75). However, in simple nucleophilic displacement a carbanion will be more deactivating than the corresponding alkyl group, as is true in general for anionic substituents and their non-ionic counterparts. 

Tertiary amines from quaternary ammonium salts by migration of an alkyl group... 

Extension of the alkyl group on the carbon bearing the amine changes the pharmacologic profile. Reductive amination of 1-phenylbutanone-2 (60) with pyrrolidine in formic acid gives pro-litane (61), a central nervous system stimulant agent with antidepressant properties. 

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