Amines aminoalcohols

Aminoalcohols, Nitrated and Nftrited. Similar to the amines, aminoalcohols may be converted into various types of derivatives contg oxynitro groups. Many of these comps are expl, as for instance, di ethanol nitraminedinitr ate (OjNO-CHj-CHjJjiN-NOj diethanol nitrosaminedi nitrate (OaN O-QVCHjVN-NO nitroxyethyleneaminenitrate, O jNO-CH, -CHj -NHj-1 LNO, l,9-dinitroxypentamethylene-2,4,6,8-tetranitramine,... 

Fig. 8. Oligo(ethyleneimine) (20), morpholinodiethanolamine (21), amine/aminoalcohol (22), guanidine (23), and 4-phenolsubstituted (24)-based custom made electrophilic scavenging resins.

Amine/aminoalcohol Resin (22). A suspension of Merifield resin (5 g, 4.3 mmol Cl/g resin, 21.5 mmol) and morpholine (5.2 ml, 60 mmol) in DMF (35 ml) was treated with piperidin-3-yl-methanol (2.3 g, 20 mmol) at 65° for 6 h under a nitrogen atmosphere. Upon cooling to RT, the resin was filtered and washed with DMF, MeOH, Et3N, DMF, MeOH, Et3N, MeOH, DCM, MeOH, DCM, and EtOAc. The resulting amine/aminoalcohol resin was dried at 45° under vacuum overnight. 

As a result of interaction of 843 and pyridine, the adduct 845 is formed [53], The structures of coordination compounds 844 and 845 were proved by x-ray diffraction. As shown above (Sec. 3.4.3.2), the direct ammonia synthesis [55,56] with participation of various ligands (especially aliphatic, aromatic, and heterocyclic amines, aminoalcohols), elemental metals (or their oxides), and NH4SCN in mostly non-aqueous media, opens definite possibilities for obtaining thiocyanate complexes. In this respect, transformation (4.9) should be mentioned [57] ... 

Natural nitrogen containing compounds (amines, aminoalcohols and amino acids) have been the first substrates used to obtain cations (ofetn asymmetric cations), although more recently also other classes of natural compounds have been employed. 

Aliphatic alcohols, monosaccharides, disaccharides, oligopolysaccharides, aliphatic amines, aminoalcohols, amino sugars, amino acids Hypochlorite, arsenite, hydrazine... 

Reactions of enamines with aluminum hydrogen dichloride (540,541) (UAIH4 and AICI3) or aluminum hydrogen dialkyl compounds (542) led to organoaluminum intermediates which could be hydrolyzed to tertiary amines or oxidized to aminoalcohols. The formation of olefins by elimination of the tertiary amine group has also been noted in these reactions. 

A limitation of this approach was the fact that the cyclization could not be accomplished on the resin. This would preclude further functionalization of the core. Therefore an alternate approach was to link the resin to the core via an aminoalcohol spacer as in 93. Furthermore, since linkage was conducted through the P-ketoester component rather than through the nitrogen atom, dihydropyridines 94 could now be formed on the solid support. When the 4-aryl substituent of 94 was nitro, on-resin reduction to the corresponding amine was possible. This allowed for further addition of diversity elements to the core scaffold before cleavage from the resin. 

The carbonyl compound 1 is assumed to react first with amine 2 to give the unstable a-aminoalcohol 5 as intermediate, from which an iminium species 6 is... 

Incorporation of extensive branching in the side chain similarly does not decrease pharmacologic activity. Reductive alkylation of aminoalcohol, 42, with isobutyraldehyde affords the amine, 43. Acylation of the amine with benzoyl chloride probably goes initially to the amide (44). The acid catalysis used in the reaction leads to an N to 0 acyl migration to afford iso-bucaine (45). ... 

In an analogous sequence, reductive alkylation of aminoalcohol, 46, with cyclohexanone affords the secondary amine (47). Acylation with benzoyl chloride affords hexylcaine (48) in a reaction that may again involve acyl migration. 

Reductive amination of dihydropyran (which may be regarded as the dehydration product of the cyclic acetal of 5-hydroxy-pentanal) in the presence of isopropylamine and a trace of acid affords the aminoalcohol, 96. Treatment of this compound with thionyl chloride affords the haloamine, 97. Alkylation of the quinoline, 92, with this halide yields pentaquine (98). ... 

Treatment of the piperidine 74, obtainable from an aminonitrile such as 73, under N-methylation conditions leads to the dimethylamino derivative 75. The carbobenzoxy protecting group is then removed by catalytic hydrogenation. Reaction of the resulting secondary amine 76 with cyclohexene oxide leads to the alkylated trans aminoalcohol. There is thus obtained the anti-arrhythmic agent transcainide (77) [18]. 

Thioacylation of primary and secondary amines, including aminoacids and aminoalcohols, has been readily carried out from phosphonodithioacetate 28 (R = Et) and the resulting phosphorylated thio amides (thio carbamoyl-... 

Not so long ago, the general opinion was that high enantioselectivity can only be achieved with natural, structurally unique, complex modifiers as the cinchona alkaloids. Our results obtained with simple chiral aminoalcohols and amines demonstrate the contrary. With enantiomeric excesses exceeding 80%, commercially available naphthylethylamine is the most effective chiral modifier for low-pressure hydrogenation of ethyl pyruvate reported to... 

Enzymatic resolutions of racemic amines or aminoalcohols via enantioselective acylation... 

Zinc borohydride, which is also a useful reagent,66 is prepared by reaction of ZnCl2 with NaBH4 in THF. Owing to the stronger Lewis acid character of Zn2+, Zn(BH4)2 is more reactive than NaBH4 toward esters and amides and reduces them to alcohols and amines, respectively.67 Zn(BH4)2 reduces carboxylic acids to primary alcohols.68 The reagent also smoothly reduces a-aminoacids to (3-aminoalcohols.69... 

The addition of ammonia to excess methyl acrylate (a linear monomer), followed by amidation with excess ethylenediamine afforded the resultant cascade molecule, and thus Tomalia [37] created the commercially available PAMAM starburst series of dendrimers (2, Fig. 2). Related core molecules such as ethylenediamine and aminoalcohols and other functionalizable groups such as thiol moieties were used to prepare similar dendrimers [38]. This methodology is applicable to most primary amines, resulting in a 1 —> 2 branching pattern. Recently, examples of related Si-, [39] P-, [40] and metallo systems [41], which follow this linear monomer protocol have been reported. 

In determination of the enantiomeric purity of aliphatic primary amines, the use of (S-aminoalcohols and ot-amino acids 1R(—)-myrtenal as a derivatising agent has been tested.1... 

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