Naming amines

Aromatic diazonium compounds became industrially very important after Griess (1866a) discovered in 1861/62 the azo coupling reaction, by which the first azo dye was made by C. A. Martius in 1865 (see review by Smith, 1907). This is still the most important industrial reaction of diazo compounds. Hantzsch and Traumann (1888) discovered that a heteroaromatic amine, namely 2-aminothiazole, can also be diazotized. Heteroaromatic diazonium compounds were, however, only used for azo dyes much later, to a small extent in the 1930 s, but intensively since the 1950 s (see Zollinger, 1991, Ch. 7). 

The tetracyano derivative of 2.49, 5-diazo-l,2,3,4-tetracyanocyclopentadiene (2.52), and its heterocyclic analogue, 2-diazo-4,5-dicyano-imidazole (2.53) can be obtained by diazotization of the corresponding amines, namely the (anionic) 1-amino-... 

The thioxotetrazinoquinazoline 7 was reacted with paraformaldehyde and secondary amines, namely diethylamine and piperidine (Mannich reaction), to afford the corresponding derivatives (Equation 2) <1999IJB850>. 

Of these reactions, the reaction of the peroxyl radical with phosphite is the slowest. The rate constant of this reaction ranges from 102 to 103 L mol 1 s 1 which is two to three orders of magnitude lower than the rate constant of similar reactions with phenols and aromatic amines. Namely, this reaction limits chain propagation in the oxidation of phosphites. Therefore, the chain oxidation of trialkyl phosphites involves chain propagation reactions with the participation of both peroxyl and phosphoranylperoxyl radicals ... 

Separate correlation lines are observed for mono-, di-, and ttialky 1-amines namely, after proper rescaling [139], we obtain... 

Until recently, only two reports existed for 1 1 adducts of silver halides with amines, namely AgT piperidine57 and Agl-morpholine.381 The first had a tetrameric cubane structure whilst the second was described as a stair polymer adduct. The range has now been extended to include 2-and 3-methylpyridine, quinoline and triethylamine.382 In each case the adduct was obtained by recrystallization of silver(I) iodide from neat base. The colourless crystals were found to lose base readily on exposure to the atmosphere and structural data were collected from crystals mounted in argon-filled capillaries, containing mother liquor. 

Galceran et al. (199) developed an SPE-HPLC method for the determination in beef extract of five mutagenic amines, namely Trp-P-1 (3-amino-1,4-dimethyl-5//-pyrido[4,3-fc]indole),... 

The triazene linker can be used for the immobilization of aromatic diazonium salts, and therefore for aromatic amines, but not for aliphatic amines due to the instability of their diazonium salts. Cleavage of the linker can be achieved under mild acidic conditions to yield the benzylamine resin and the corresponding diazonium salt [136,145,146]. The main difference between the preparation of triazenes in solution and triazenes on solid support is the respective amine, namely bisben-zylamine and polymer-supported benzylamine 114. In solution, it was used in excess to quench unstable diazonium salts and force the reaction to completion. In the solid-phase approach it was immobilized and cannot be used in excess with respect to low loadings. A simple three-step procedure (Scheme 36) starting from benzylamine resin 114 via carboxylate 115 led to the successful preparation of ester resins 116 in essentially higher loadings. Treatment of resin 114 with 4-carboxy-benzene diazonium tetrafluoroborate yielded benzoic acid resin 115. 

Given the structure of an amine, name it. Also, given the name of an amine, write its structural formula. 

Utilization of a,(3-unsaturated amides derived from the chiral amine, namely, camphor sultam, has been made by several groups to test the feasibility of [l,3]dipolar cycloaddition reactions with these chiral systems. This methodology has been applied to the synthesis of (35,4/ )ethyl-l-azabicyclo[2.2.1]heptane-3-carboxylate (see above for non-specific syntheses).433... 

The team also used A iV-carbonyldiimidazole (CDI) as the coupling reagent to generate sorafinib (1) directly from amines—namely, 4-chloro-3-trifluoromethylaniline... 

Some substances manifest both electronic and electrolytic conductance at the same time. Among such conductors are some metal compounds such as solid silver sulphide, cuprous oxide, zinc oxide, cuprous chloride and similar substances. A special group includes solutions of alkali- and alkaline-earth metals in amines, namely in liquid ammonia, where appart from cations of metals and electrons bonded to the ammonia also free electrons are present at higher concentrations of solutions, whereby the conductance is considerably increased. 

This possible mechanism is applicable only to compounds having a hydrogen atom attached to the nitrogen atom, yet Kuhn and Birkofer found that mutarotation occurs in pyridine solutions of derivatives of secondary amines, namely, n-glucosylpiperidine and iVjiV -dibenzyl-D-glucosylamine, where no such hydrogen atom is available. To explain mutarotation in such cases they postulated the formation of an acyclic imonium ion by expulsion of a proton from a substituted ammonium ion. 

Metabolites derived by loss of an alkyl or arylalkyl group from ethers [Eq. (4)], thioethers [Eq. (5)], amines [Eq. (6)], and amides [Eq. (7)] represent common biotransformation pathways (R, R" = H, alkyl or aryl). These processes involve oxidation on carbon adjacent to the heteroatom. The intermediates are generally unstable and readily decompose to the corresponding alcohol, thiol, amine, or amide and an aldehyde. Intermediates formed from amides [Eq. (7)] are more stable and may be detected as excreted metabolites. If a secondary carbon atom is adjacent to the heteroatom, then this portion of the molecule is released as a ketone. The heteroatom may also be located in a cyclic structure (e.g., morpholine, piperazine). Two processes have been adopted for amines, namely, N-dealkylation or deamination, that are essentially the same event. In general, which of the two terms applies depends on the... 

Sulfinamide 46, developed by the same group, represents the most recent addition to this family. Here, the original formyl group of the proline derived catalyst 16 was replaced by the t BuSO moiety, which resulted in high enantio selectivities (<97% ee at 0 °C with 10mol% catalyst loading Table 4.10) [Ilf]. The striking feature of this catalyst is its efficiency with imines derived from nonaro matic amines, namely, benzyl, allyl, propyl, isobutyl, and p methoxybenzyl amine (Table 4.10), which renders 46 superior to 43 and dwarfs other catalysts (e.g., 16,19, and 45). Needless to say, this new feature broadens the synthetic arsenal beyond the N aryl substrates and opens new synthetic avenues. In comparison, the valine derived catalyst 47 proved to be less efficient with imines derived from aromatic... 

Mustafa et al. (64T531) (Scheme 21) found that pyrazol-3-one 67 condensed readily with formaldehyde in the presence of piperidine or morpholine to give the corresponding Mannich bases 68a,b. However, when primary amines, namely ethylamine, aniline, 2- or 4-toluidine were used instead, 4-( [(3-oxopyrazol-4-yl)-methyl]amino methyl)-pyrazol-3-ones 69a-d were obtained. 

The reversibility of the zwitter ion adduct formation in Eq. 8.6 also affected the rate law of the formation of amino-substituted alkylmetal complexes. Thus, kinetic studies indicated [33] that the rate of the formation of /i-aminoalkyl complex 4 in Scheme 8.20 was second-order with respect to the concentration of the amine, namely rate = [amine] [complex]. This is consistent with a reaction sequence shown in Scheme 8.20 involving a reversible formation of the zwitter ionic intermediate, followed by the rate-determining deprotonation by the second amine molecule. The observed rate constant appeared to contain contributions from both the equilibrium constant of the first step and the rate constant of the second deprotonation, so that the direct comparison of the rate of the initial nucleophilic attack at the coordinated alkene between Pd and Pt complexes was not possible. However, the higher overall reactivity (ca. 70 times) of Pd complex than Pt complex was consistent with the higher ionization potential of Pd than Pt. This difference in the ionization potential then would lead to the weaker jt basicity of Pd(II) than Pt(II) for jt back-donation to alkene jt orbital, and therefore facilitated the nucleophilic attack at the Pd-alkene complex more than that at the Pt complex. 

Number Amine Name Molecular Weight Abbreviation... 

Liebermann discovered the reaction between nitrous acid and phenols and secondary amines named after him. He prepared amino-naphthols from nitro-naphthols, synthesised the dihydroxyanthraquinones anthrarufin and chrysazin, and studied the reduction of anthraquinone. Another dihydroxy-anthraquinone, quinizarin, was discovered by F. Grimm by heating hydro-quinone with phthalic anhydride. 

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