Alkylamides

Some of these compounds have been known for over 30 years, but interest in the former in particular has been stimulated recently by their potential use as precursors for deposition of metal oxides using the sol-gel or MOCVD process. These compounds are particularly interesting insofar as many of them involve very bulky ligands and therefore have low coordination numbers (see Section 4.5). 

The volatile air-sensitive silylamides Ln[N(SrMc3)2]3 are the best-characterized alkylamides. They are made by salt-elimination reactions in a solvent like THF  

Use of a highly fluorinated amide has permitted the synthesis of [Sm[N(SiMe3)(C6F5)]3] 

The neodymium compound [( -C6H5Me)Nd N(C6F5)2 3] has a -bonded toluene molecule with a distorted piano-stool geometry. 

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Physical Properties. Acetoacetic esters are high boiling Hquids with pleasant odors. Lower A/-aLkylamides are water-soluble Hquids acetoacetamide and acetoacetaryHdes are soHds. 4-Chloroacetoacetates are high boiling lachrymatory Hquids. Some physical properties are Hsted in Tables 3 and 4. 

Hydroxy-2-Naphthalenecarboxylic Acid. l-Hydroxy-2-naphthoic acid is made similarly to the isomer (2-hydroxy-1-naphthoic acid) by reaction of dry sodium 1-naphthalenolate with CO2 in an autoclave at ca 125°C. It has been used in making triphenylmethane dyes and metalli able a2o dyes. Alkylamides and arylamides of l-hydroxy-2-naphthalenecarboxyhc acid are cyan couplers, ie, components used in indoaniline dye formation in color films (see Color PHOTOGRAPHY). 

Zirconium dichiorohis(dimethylamide) [87227-57-4] ZrCl2[N(CH2)2]2 h made direcdy from methylamine and zirconium tetrachloride but all of the halogens can be substituted by treating zirconium tetrachloride with the appropriate lithium alkylamide (229). Zirconium arylamines are made from zirconium alkoxides which first are converted to aryloxides (230). 

Special reactions of hydrazides and azides are illustrated by the conversion of the hydrazide (205) into the azide (206) by nitrous acid (60JOC1950) and thence into the urethane (207) by ethanol (64FES(19)105Q) the conversion of the same azide (206) into the N-alkylamide (208) by ethylamine the formation of the hydrazone (209) from acetaldehyde and the hydrazide (205) and the IV-acylation of the hydrazide (205) to give, for example, the formylhydrazide (210) (65FES(20)259). It is evident that there is an isocyanate intermediate between (206) and (207) such compounds have been isolated sometimes, e.g. (211). Several of the above reactions are involved in some Curtius degradations. 

Caibamates ate formed from an amine with a wide variety of reagents, of which the chloroformate is the most common amides are formed from the acid chloride. -Alkyl caibamates are cleaved by acid-catalyzed hydrolysis A/-alkylamides are cleaved by acidic or basic hydrolysis at teflux. conditions that cleave peptide bonds. 

Other methods for the synthesis of a-oxygenated A-alkylamides (or carbamates) include addition of oxygen nucleophiles to A-acyl (or A-alkoxycarbonyl) iminium ions, generated via either... 

Lithium alkylamides (in situ generated from the amine and either n-BuLi or sec-BuLi) generally give higher yields under milder conditions. Thus, n-BuLi (5%) catalyzes the addition of primary and secondary amines to styrene to afford (-phenethy-lamines in moderate to good yields (e.g., Bq. 4.32) [155]. NH, and PhNHj, however, do not add to styrene under these conditions. a-Methylstyrene and 1,1-diphenyleth-ylene can also be hydroaminated. 

Further studies showed that the alkylamide catalysts can also be generated in situ from the amine and n-BuLi or sec-BuLi [155]. The resulting product mixture (> 99% 1,4-adduct) depends on the nature of the amine and the nature of the solvent (Scheme 4-6). 

Sodium alkylamides can also be generated in situ by reacting the amine with sodium naphthalene in THF [207, 208]. This procedure has been used for the condensation of secondary amines with different 1,3-dienes to give high yields of monoalky-lated products without formation of 1 2 telomers. In the case of primary amines, mixtures of mono- and dialkylated products are obtained together with unidentified... 

Chemically bonded stahonary phases, e.g. alkylamide silica reversed phases, were also developed. Despite a generally good stability and good quality of resolution and less interachons with free silanol groups, correlahons between log Pod and log kw are relahvely poor compared to a number of other stahonary phases [26]. Finally, monolithic silica stahonary phases have also been applied for Upo-philicity determinahon of a series of P-blockers [27]. 

Czajowska, T. and Jaroniec, M., Selectivity of alkylamide bonded-phase with respect to organic acids under reversed-phase conditions, J. Chromatogr. A, 762(1 2), 147, 1997. 

Figure 10.8 Nanotube formation upon introducing a c/s-double bond in a diaminopyridine alkylamide and their corresponding alkyl chain packing in DAP-2. Reprinted with permission from [75] (2004) American Chemical Society.

Recently, such a procedure has been used by Wu and Shanks [22] upon a preparation of partially hydrophobized polyacrylamide (PAAm). In this work, the transamidation reaction has been employed to convert amide groups of the parent polymer to the alkylamide groups of the modified PAAm. Scheme 2 shows the reaction chart for the case of the N-isopropylamide derivative. 

Amino-3-azidocarbonylfuroxan 143 can be transformed to the /V-alkylamide derivatives 144 of 4-amino-3-furoxancarboxylic acids and their oxidation products 145 (Scheme 36) <2003FES677>. 

Fig. 32 Predicted versus observed mutagenic activities (log TA100) for mutagens in Table 17 (entries 1-43, 48-58 squares), di-tert-butylated analogues 31c-e, 32a (122, 123, entries 44—47, closed circles) and alkylamides 30b, 29a-e (124, entries 36, 59-63, triangles) based upon QSAR (4).

Lithium alkylamides react with dimethyltin dichloride to give the cyclotristannazane, which is methylated by trimethyl-aluminum, -gallium, or -indium, giving the metal stannylamides, which are coordinatively dimerized (Equation (167)).503... 

With these guidelines we synthesized a series of meta-substituted analogues of the lead compound 1 with alkylamide and alkylsulfonamide substituents. A full analysis of the SAR that was developed during this optimization process can be found in [14]. In what follows we report on the progress of the optimization process in chronological order, referring to the various compounds by their serial number, which reflects the order of their synthesis (data summarized in Table 19.2). 

On the basis of IR evidence it has been proposed84 that alkylamidates are the strongest known hydrogen-bonding carbonyl bases and that the order of hydrogen-bond basicity may be alkylamidates w FLMPA > vinylogous amides benzamidates > amides (Table 8). 

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