Chloro aluminum amides

Grignard and alkyl lithium reagents were found to add to the carbonyl group of a tricyclic vinylogous amide. However, the same compound underwent the usual vinylogous reduction with lithium aluminum hydride (712). Grignard additions to di- and trichloroenamines gave a-chloro- and dichloroketones (713). 

A -( 1-Chloro- or bromoalkyl)amides are generally moisture-sensitive, unstable compounds, which are often directly used without further purification. Standard Lewis acids such as boron trifluoride-diethyl ether, aluminum(lll) chloride, zinc(II) chloride, tin(IV) chloride and titani-um(IV) chloride are used to generate the /V-acyliminium ion, although sometimes a catalyst is not necessary. 

Amide reduction with lithium aluminum hydride, 39, 19 Amine oxide formation, 39, 40 Amine oxide pyrolysis, 39, 41, 42 -Aminoacetanilide, 39, 1 Amino adds, synthesis of, 30, 7 2-Amino-4-anilino-6-(chloro-METHYl) -S-TRIAZINE, 38, 1 -Aminobenzaldehyde, 31, 6 hydrazone, 31, 7 oxime, 31, 7 phenylhydrazone, 31, 7 > -Aminobenzoic add, 36, 95 2-Aminobenzophenone, 32, 8 c-Aminocaproic acid, 32, 13 6-Aminocaproic acid hydrochloride,... 

The aminocarbonyl group attached to the C = C bond in 2-chloro-3.3,4,4,5.5-hexafluorocyc-lopent-l-enecarboxamide (8) activates the C-Cl bond to complete hydrogenolysis with lithium aluminum hydride the number of C-F bonds reduced is dependent on the amount the hydride used, while the amide group remains unaffected under milder conditions.131... 

An early approach to the synthesis of cephalotaxine (Scheme 32) was reported by Dolby et al. (64) in 1972, shortly before Auerbach s and Wein-reb s report (22). The Vilsmeier-Haack condensation of piperonylamide 187 with pyrrole yielded ketone 188, which was successively reduced with sodium borohydride, hydrogenated, and acylated to give the precursory chloro amide 189. The photocyclization of 189 produced lactam 190, which, after reduction of the carbonyl with lithium aluminum hydride and subsequent oxidation with mercuric acetate, yielded the enamine 43. This mate-... 

CHLORO-l-HYDROXYBENZENE (106-48-9) Combustible. solid (flash point 249°F/ 121°C). Reacts with oxidizers, with a risk of fire or explosions. Incompatible with sulfuric acid, nitric acid, caustics, aliphatic amines, amides. Attacks active metals, aluminum, copper, etc. 

OXALIC ALDEHYDE (107-22-2) Flammable solid, but normally sold as an inhibited 40% solution. A highly reactive reducing agent. Violent reaction with water causes polymerization. Temperatures above boiling point of 122°F/50°C can cause polymerization. Reacts, possibly violently, with strong acids, caustics, ammonia, amines, amides, aldehydes, chloro-sulfonic acid, ethylene amine, hydroxyl-containing materials. Corrosive to metals aluminum, copper, tin, steel, zinc. 

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