Amidation treatments

Benzocyclobutenone was first prepared from 1 -bromobenzocyclobutene by hydrolysis followed by chromium trioxide oxidation.3 More recent procedures involve hydrolysis of 1,1-dichloro- or 1,1-dimethoxybenzocyclobutene which in turn have been obtained through cycloaddition of the appropriate 1,1-disubstituted ethylenes to benzyne generated either from anthranilic acid through diazotization5 6 or from bromobenzene through sodium amide treatment.7.3 Benzocyclobutenone has... 

Unsubstituted oxazolidinediones are prepared directly from the unsubstituted C-3 amides. Treatment of 4-deacetylvinblastine amide (59) with sodium hydride in tetrahydrofuran followed by the addition of dimethyl carbonate gives 4-deacetyl-3-oxazolidinedione (101) in 40% yield. 

A number of other secondary nitramide explosives have been prepared from the action of mixed acid on the parent amide. Treatment of sulfuryl chloride with two equivalents of ethanolamine, followed by nitration of the resulting sulfamide (64) with mixed acid, yields the nitramide explosive A, A -dinitro-A, A -bis(2-hydroxyethyl)sulfamide dinitrate (65). " ... 

Figure 10.10 The synthesis of 2R-methylbutanoic acid, illustrating the use of a chiral auxiliary. The chiral auxiliary is 2S-hydroxymethyltetrahydropyrrole, which is readily prepared from the naturally occurring amino acid proline. The chiral auxiliary is reacted with propanoic acid anhydride to form the corresponding amide. Treatment of the amide with lithium diisopropyla-mide (LDA) forms the corresponding enolate (I). The reaction almost exclusively forms the Z-isomer of the enolate, in which the OLi units are well separated and possibly have the configuration shown. The approach of the ethyl iodide is sterically hindered from the top (by the OLi units or Hs) and so alkylation from the lower side of the molecule is preferred. Electrophilic addition to the appropriate enolate is a widely used method for producing the enantiomers of a-alkyl substituted carboxylic acids...

In general, on chemical modification carbon nanotubes exhibit much less toxicity or nontoxicity to living cell lines that have been investigated so far.117,118 For instance, Dumortier et al. conducted an in vitro cell uptake study of the functionalized SWNTs with B and T lymphocytes and macrophages.117 Two types of functionalized SWNTs were used, one prepared via 1,3-dipolar cycloaddition reaction and the other obtained through oxidation/amidation treatment. Both types of the functionalized nanotubes were rapidly taken up by lymphocytes and macrophages without affecting the overall... 

Other pyridine derivatives have been aminated with alkali metal amides. Treatment of 2,3 -bipyridine (116) with sodium amide afforded the isomers shown in Scheme 46 (77MI1). In a similar fashion, 2,2 -bipyridine gave 6,6 -diamino-2,2 -bipyridine, 3,3 -bipyridine yielded 6-amino-3,3 -bipyridine, and 4,4 -bipyridine afforded 2,2 -diamino-4,4 -bipyridine upon treatment with sodium amide (78RCR1042). The amination of 2-chloro-5-nitropyridine gave the Chichibabin products 2-amino-6-chloro-3-nitropyridine and 4-amino-2-chloro-5-nitropyridine in low yields (<3% of each) on treatment with potassium amide in liquid ammonia. The main product was 2-amino-5-nitropyridine, obtained primarily by the S fANRORC) mechanism (85JOC484). 

A -Trimethylsilylimines (108) can be conveniently generated in situ by treatment of nonenolizable aldehydes with lithium bis(trimethylsilyl)amide. Treatment of a solution of (108) with allylmagnesium bromide affords after aqueous work-up homoallyiamine (109) in good/excelient yield (equation 24).- Although the methodology works best with nonenolizable aldimines, it nonetheless provides a convenient method for preparing many primary homoallylamines. 

Amino-l,2-dihydroacronycine (40 ) could be easily converted into variously substituted amines and amides. Treatment of 40 with formaldehyde and sodium borohydride afforded 2-dimethylamino-l,2-dihydroacronycine (42). Both aliphatic and aromatic amides were obtained from 4 upon treatment with acid anhydrides in pyridine. This latter reaction is exemplified by the preparation of 2-acetylamino-l,2-dihydroacronycine (43J and 2-benzoylamino-l,2-dihydroacronycine (44) using acetic anhydride and benzoic anhydride, respectively (53). 

Methylation of amides. Treatment of an amide, for example, benzamide, with chloromethyl methyl sulfide in TFA or methanesulfonic acid gives the substituted amide in good yield. This product is converted into the N-methyl-amide when refluxed in 90% ethanol in the presence of a large excess of Raney nickel. 

Hydrolysis of amides. Treatment of an aqueous suspension of an amide with 1 eq. of sodium peroxide at 50° (or on a steam bath) added gradually results in hydrolysis within 1 hr. Yields are usually greater than 85%. Extremely water-insoluble amides fail to react. The reaction is particularly valuable for heterocyclic carboxamides when the derived acid is prone to decarboxylation. 

Opening of a, -Epoxy Esters and Amides. Treatment of aromatic a,/3-epoxyamides with samarium iodide leads to the highly stereoselective synthesis of a./S-unsaturated amides with high diastereocontrol (eq 52). If the reaction is run on a substrate that contains y-protons, then a base-promoted reaction produces the (E)-a-hydroxy-, y-unsaturated amide (eq 53). ... 

Israel R, Gross R, Bomba P (1980) Adult respiratory distress syndrome associated with acute nitrofurantoin toxicity. Respiration 39 318 Iwarson S, Lundin P (1979) Multiple attacks of jaundice associated with repeated sulfon-amid treatment. Acta Med Scand 206 219... 

Griggs RC, Engel WK, Resnick JS. (1970) Acetazol-amide treatment of hypokalemic periodic paralysis. Ann Intern Med 73, 39—18. 

Reactions with Secondary Amides. Treatment of AT-alkyl or A -aryl secondary amides with thionyl chloride in an inert solvent such as methylene chloride results in the formation of imidoyl chlorides (eq Q)." Upon heating, the imidoyl chlorides from N-alkylamides undergo scission to generate nitriles and alkyl chlorides via the von Braun degradation (eq 10). ... 

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