Amino alcohols methoxide

Ammonium acetate and sodium methoxide are effective catalysts for the ammonolysis of soybean oil (49). Polyfunctional amines and amino alcohols such as ethylenediamine, ethanolamine, and diethanolamine react to give useful intermediates. Ethylenediamine can form either a monoamide or a diamide depending on the mole ratio of reactants. With an equimolar ratio of reactants and a temperature of >250° C, a cyclization reaction occurs to give imidazolines with ethylenediamine (48) ... 

Removal of the p-methoxybenzyl group is accomplished by treatment with dichloro-dicyanoquinone (DDQ), which forms quantitatively aminal 17 in an 11.5 1 diastereomeric ratio (Yu and Levy, 1984). The solution is treated with sodium methoxide in methanol, which decomposes the aminal into the desired amine 18 and p-methoxybenzaldehyde. Due to the difficulties in separating the p-methoxybenzaldehyde from amino alcohol 18, the aldehyde is reduced in situ with sodium borohydride. The amino alcohol 18 is crystallized from the reaction mixture after neutralization with acetic acid. Additional recrystallization provides the desired amino alcohol 18 in 94% yield. 

The catalytic hydrogenation of nitro alcohol to amino alcohol has been applied to the synthesis of an intermediate leading to sugar alcohols. The condensation of ni-tromethane with pentoses in the presence of sodium methoxide, followed by hydrogenation over platinum oxide and deamination with nitric acid, gave the alditols with one more carbon atom.22 The reaction sequence is as follows pentose — 2-epimeric sodio aci-nitro alcohols —> 2-epimeric hexitylamines —> 2-epimeric hexitols + 2-epi-meric 1,4-anhydrohexitols. The 2-epimeric sodio a -nitro alcohols were hydrogenated to 2-epimeric hexitylamines over platinum oxide in acetic acid. An example is shown in eq. 9.8 with D-ribose. 

The 3a-tropanol 0-riboside (23) has been prepared by trans-glycosylation of the amino-alcohol with l-0-acetyl-2,3,5-tribenzoyl-ribofuranose, catalysed by boron fluoride etherate, followed by Zemplen deacylation in methanol, with sodium methoxide as a catalyst. 

Carbamates by Aminolysis of Carbonate or Dithiocarbonate Esters Diethyl carbonate has been employed for the cydocarbamation of various amino alcohols. The reaction is catalyzed by basic substances, such as sodium methoxide, magnesium methoxide, potassium hydroxide, or sodium or potassium carbonates. Sodium methoxide in xylene [485-487], or potassium or sodium carbonate under reflux [488-493] are the preferred reaction conditions. The reaction has wide scope and synthetic utility. 

Methyl-A-Boc-l-amino-2-cyclohexylethyl phosphinate (1.64 mmol) dissolved in 2.5 ml methyl alcohol at 0°C was treated dropwise with 0.90 ml 2.0 M sodium methoxide (1.8 mmol) over 10 minutes followed by the dropwise addition of 2-trimethylphosphono-acrylate (2.44 mmol) over 2 minutes. The mixture was stirred... 

In most cases, 2-amino-l,3,4-thiadiazoles are alkylated on the ring nitrogen atom in position 3 (68). 2-Acylamino- and 2-tosyl-amino-1,3,4-thiadiazoles (69) are alkylated in the same position by alkyl halides in alkaline medium. One case is known, however, where the base directs the alkylating agent. 2-Acetylamino-5-benzylthio-1,3,4-thiadiazole (70) was methylated in the ring to 71 by methyl bromide and sodium methoxide (a), but in the acetylamino group to 72 by methyl iodide and potassium ier -butoxide in ier -butyl alcohol (6). ... 

The preparation of aziridines and substituted aziridines from a number of sugars that contain substituted amino groups has been described. With such compounds as the sulfonamide (241) and the cyanamide (231), where the functional groups are fmns-diaxial, aziridine formation is the expected course of the reaction under alkaline conditions. Baker and Hullar described the conversion of (241) into the substituted aziridine (188, R = Ts) with methanolic sodium methoxide at room temperature similar transformation of (231) into (242) was accomplished with alcoholic... 

Diacid-based linkers, such as the succinic linker 21, have been described to prepare alcohols. The procedure involves the esterification of the starting alcohol with succinic anhydride and DMAP to yield the hemiester that is anchored to an amino containing-resin by means of an amide bond. The bound alcohol is then elaborated and finally released with a nucleophile. Oligosaccharides have been assembled following this approach and released with aqueous ammonia or sodium methoxide in methanol-dioxane [73, 74]. Peptide alcohols have also been prepared with the succinic linker on BHA resin and released by treatment with NH3 in MeOH for 72-96h or hydrazine in DMF for 24h [75]. Similarly, hydroquinone-0,0 -diacetic acid (linker 22) has been used to link nucleosides to polystyrene or CPG supports. Cleavage of oligonucleotides was carried out with aqueous ammonia [76]. Other diacids with a similar function have also been described [77]. 

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