Metal-amides

Ester eliminations are normally one of two types, base catalyzed or pyrolytic. The usual choice for base catalyzed j5-elimination is a sulfonate ester, generally the tosylate or mesylate. The traditional conditions for elimination are treatment with refluxing collidine or other pyridine base, and rearrangement may occur. Alternative conditions include treatment with variously prepared aluminas, amide-metal halide-carbonate combinations, and recently, the use of DMSO either alone or in the presence of potassium -butoxide. 

Strong bases such as alkali metals, metal hydrides, metal amides, metal alkoxides, and organometallic compounds initiate the polymerization of a lactam by forming the lactam anion XXXIV [Hashimoto, 2000 Sebenda, 1989 Sekiguchi, 1984], for example, for e-caprolactam with a metal... 

Amides. Metal ions catalyze the hydrolysis of a variety of amides, including acylamino acids, dipeptides and tripeptides, and amino acid amides. In all these compounds it is possible for a metal ion to complex with one or more ligand groups, either amine or carboxylate ion functions, in addition to the amide group. Thus the structural prerequisites for the metal ion catalysis of amide hydrolysis are the same as those for ester hydrolysis. 

Sesbanine (608), a unique alkaloid isolated from Sesbania Drumondii seeds, which seems to exhibit potent antitumor activity, has been synthesized by prior carefull exploration for pyridine tertiary amide metalation (Scheme 179) (83TL2649). In the optimum case, LiTMP metalation of the diisolpropyl amide 447b for 15 min. followed by condensation with 3-... 

Boyd, S. A., Sommers, L. E., and Nelson, D. W. (1979). Infrared spectra of sewage sludge fractions Evidence for an amide metal binding site. Soil Sci. Soc. Am. J. 43, 893-899. 

Non-enolizable amides, for example N,N-dialkyl pivalamides [212], benzamides, thiobenzamides [213], or phosphinamides (Ph2P(0)NR2[214]), can be lithiated a to the amino group by treatment with sBuLi[54, 213, 215] or tBuLi[216], without further additives, in THF at -78 °C. N,N-Dimethylbenzamides can be attacked at the carbonyl group by these organolithium reagents to yield ketones [217] or alcohols, but with sterically more demanding amides metalation is usually faster than addition. 

Alkali metals Alkali metal hydrides Alkali metal amides Metal alkyls Grignard reagents... 

Lubricants Reduce polymer adhesion to metal surfaces acids Derivatives of fatty acids (esters, amides, metal... 

Alternative methods include deprotonation of the amine, to enhance its nucleophilicity, by one equivalent of sodium methoxide, sodium amide, metallic sodium,n-butyllithium, sodium hydride in dimethyl sulfoxide or Grignard reagent. Under less drastic basic conditions 2-hydroxypyridine catalyzes the reaction at elevated temperatures (130-170 °C). ... 

They are often blended into compounds that are developed for injection molding applications. Where such an additive is absent, molded components tend to stick to mold surfaces. To prevent this, mold surfaces must be treated between every cycle, or they can be coated with a range of semipermanent mold release treatments. Inclusion of an internal release agent prevents mold surface build-up, surface charring, and simplifies production. Internal mold release agents may include hydrocarbons, alcohols, carboxylic acids, halogenated compounds, ketones, carboxylic acid esters, amides, metal salts, and silicone compounds. 

This reaction can be initiated by strong bases (metal hydrides, alkali metals, metal amides, metal alkoxides, and organometallic compounds), protonic acids, or by water. Water is often used as the initiator (cf. Problem 10.7) for industrial polymerization of lactams and the process is referred to as hydrolytic polymerization. Anionic initiation with bases is preferred when polymerization is to be carried out in the mold itself for converting monomer directly into a molded object. Cationic initiation with acids, however, is not so useful because both the extents of conversion and polymer molecular weights are significantly lower (Odian, 1991). 

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