Carboxylic acid dimethyl amides

The treatment of 3-benzoyl-2-phenylisoxazolidine with strong base generated an aldehyde and a ketimine <74X1121). Under these conditions dimethyl 2-a-methoxyisoxazolidine-3,3-dicarboxylic acid (186) produced isoxazoline-2-carboxylic acid. Reaction of the monomethyl amide (187) gave the corresponding isoxazoline-2-carboxamide (Scheme 60). CD was used in the conformational studies <79X213). 

The other three methods have not been studied extensively. The dimethyl-cadmium route has been used on a 17a-methyl-17 -carboxylic acid. ° The reaction of the acid amide with a Grignard reagent is described only in a Spanish patent,with a high yield claimed, and the methyllithium reaction has apparently been tried only on D-norsteroids. ... 

Compositions and functions of typical commercial products in the 2-alkyl-l-(2-hydroxyethyl)-2-imidazolines series are given in Table 29. 2-Alkyl-l-(2-hydroxyethyl)-2-imidazolines are used in hydrocarbon and aqueous systems as antistatic agents, corrosion inhibitors, detergents, emulsifiers, softeners, and viscosity builders. They are prepared by heating the salt of a carboxylic acid with (2-hydroxyethyl)ethylenediamine at 150—160°C to form a substituted amide 1 mol water is eliminated to form the substituted imidazoline with further heating at 180—200°C. Substituted imidazolines yield three series of cationic surfactants by ethoxylation to form more hydrophilic products quatemization with benzyl chloride, dimethyl sulfate, and other alkyl halides and oxidation with hydrogen peroxide to amine oxides. 

Butyl-piperidine-2-carboxylic acid (2,6-dimethyl-phenyl)-amide, C18H28N20, MW 288.44, [2180-92-9]... 

Pinacolone, o-(diphenylphosphino)benzoyl-coordination chemistry, 401 Piperidine, IV-hydroxy-metal complexes, 797 pA a values azole ligands, 77 Plant roots amino acids, 962 carboxylic acids, 962 Plastocyanin copper binding site, 557 copper(II) complexes, 772 copper(II) site in, 770 Platinum, dichlorobis(benzonitrile)-IR spectrum, 264 Platinum, cis-dichlorodianunine-antitumor activity, 34, 979 Platinum, ethylenebis(triphenylphosphine)-reactions with 5,6-dimethyl-2,l,3-benzothiadiazole, 194 Platinum blue formation, 265 Platinum complexes acetylacetone reactions, 380 amides, 491 amidines... 

Other amide compounds were also identified from radiolysis of DEHDMBA (A(iV-di(2-ethylhexyl)-3,3-dimethyl butanamide) and mixtures of DEHBA [N.N-di(2-ethylhexyl)- -butanamide]-DEHiBA V,V-di(2-cthylhcxyl)-i,vo-butanamide] in TPH by CPG-FTIR light primary and secondary amides and functionalized tertiary amides with high molecular masses (196). Carboxylic acids represented a large... 

Decarboxylation of 5,7-dimethyl-8-oxo-6-aza-8//-indeno[2,1 - ]thiophene-4-carboxylic acid could be effected by heating an admixture of it and copper powder <87H(26)1535). Direct sublimation in vacuo afforded the desired product (58%). 9-Chloro-2- and 3-methyltriazolo[4,5-/]quinoline-7-carboxylic acids are decarboxylated under similar conditions <93H(36)259>. The cyano group of 8-cyano-7-oxo-4,5,6,7-tetrahydrothiazolo[4,5-/]quinolines can be converted into an amino group by cone. HC1 mediated hydrolysis to the amide, followed by Hofmann rearrangement <89H(29)I517>. 

Radical nucleophile oxidation based on one-electron oxidation, known as the Minisci reaction, is employed for the functionalization of /V-heterocycles with acidic hydrogen peroxide in the presence of iron(II) salts (Figure 3.112).472 A range of A-heterocycles (pyridines, pyrazines, quinolines, etc.) which are activated towards attack by nucleophilic radicals when protonated are suited to this chemistry. The Minisci reaction is suitable for the preparation of carboxylic amides (from formamide), carboxylic esters (from pyruvic esters via a hydroxyhydroperoxide), aldehydes (from 1,3,5-trioxane) and alkylated pyridines (either from carboxylic acids or from alkyl iodides in dimethyl sulfoxide).473 The latter reaction uses dimethyl sulfoxide as the source of methyl radical (Figure 3.112). 

Cyanomethylindole 12d also proved to be a versatile intermediate toward the synthesis of sumatriptan (Scheme 4).7,8 Hydrogenation of the cyano group of 12d m the presence of dimethylamine provided sumitriptan (1) directly, which was isolated as the hemisuccinate salt. Alternatively, the cyano group of 12d was hydrolyzed to the carboxylic acid (18) and then transformed into the dimethyl amide 19. Finally, the amide was reduced with LiAlHt to afford sumatriptan (1). Although this is a longer synthesis of 1, the intermediate 18 allows for the preparation of various tryptamine analogs. 

The sulfmylation of esters, - lactones, carboxylic acids, > amides and lactams may be effected by reacticm of the corresptHiding lithium enolates in THF at -78 to 0 C with dimethyl or difdie-nyl disulfides, or, less conunmily, with methyl or fdienyl sulfmyl halides. The enolates of ketones, however, are insufficioitly nucleq diilic to react with dialkyl sulfides unless HMPA is added to the re-acticm mixture, although they do react smoothly with diaryl sulfides. This difference allows the selective sulfenylation of esters in the presence of ketones (entry 5, Table 3). ... 

The direct fluorination with elemental fluorine at — 78 "C of trimethylsilyl enol ethers derived from diketones results in the formation of the corresponding monofluoro diketones 11 in moderate yield. The trimethylsilyl ethers from cyclic diketones undergo smooth fluorination to give the enol forms, c.g. 12, and not the keto forms.Higher yields are generally observed for the analogous reactions of silyl derivatives of esters, carboxylic acids, malonates, dimethyl amides and lactones (Table 4). ... 

Hydroboration. Thexylborane stabilized as the triethylamine complex is not useful for hydroboration, because 2,3-dimethyl-2-butene is displaced with formation of RBH2-N( 2145)3. However, TBDA is a useful reagent for hydroboration and for various reductions. Thus it reacts with 1-octene to form di- -octylthexylborane in quantitative yield. It is comparable to thexylborane-THF for reduction of aldehydes and ketones. Carboxylic acids are reduced to the corresponding alcohol. 10-Undecenoic acid is reduced selectively to undecanoic acid (90% yield). Tertiary amides are reduced very rapidly to f-amines. Acid chlorides and nitriles are reduced very slowly. 

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