Copper benzoyl chloride

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

The dienone 858 is synthesized by coupling of the alkenyl copper reagent 856 with crotyl chloride (857) in the presence or absence of ZnCl2[731], Tetrabutyllead (859) reacts with benzoyl chloride to afford butyl phenyl ketone[732]. 

Upon acylation of the copper complex with benzoyl chloride the corresponding 5-benzoylthio-1,2,3,4-thiatriazole is formed. The reaction product is (apparently) incorrectly assigned by the authors to 4-benzoyl-1,2,3,4-thiatriazole-5-thione based upon comparison with the product obtained from direct acylation of thiatriazol-5-thiol and citation of the older incorrect structure assignments. The thiothiatriazolato-copper(I) complexes are formulated as Cu-N(4) complexes. However, this assignment is based upon an IR band at 1200 cm attributed to a thiocarbonyl group, again upon comparison with the older literature. Further characterization therefore seems necessary. 

The compound dissociates in concentrated hot ethyl or methyl alcohol solution, also on warming with water, and on addition of a few drops of benzoyl chloride to its ether solution. It only partly dissociates in warm acetonitrile, and not at all in chloroform, benzene or light petroleum. The copper derivative,... 

Yield.—66% theoretical (10 gms.). Colourless crystals insoluble in water M.P. 61° gives a deep violet coloration with ferric chloride and a bluish-green crystalline precipitate of copper benzoyl acetone with alcoholic copper acetate. This shows the compound to be tautomeric, a little of the enol form being present at ordinary temperatures. The acidity of the hydroxyl group in the enol form is not so marked as it is in the case of the hydroxymethylene compounds nevertheless, the metallic salts of benzoyl acetone and such di-ketones are remarkably stable, and on account of their great crystallising power have been used for the determination of the valency and atomic weight of the rare elements. They are also of importance in the modern theory of co-ordination. (C., 1900,1., 588 B., 34, 2584.)... 

Compounds with acidic hydrogen atoms react rapidly with cuprates. Phenylacetylene has been mentioned as one example (223). Another is diethyl phenylmalonate (144), which on addition to lithium dimethylcuprate gave a rapid evolution of methane and the formation of a methyl-copper-like precipitate which did not redissolve. Subsequent to the addition of benzoyl chloride and the customary work-up, only acetophenone and the phenylmalonate were isolated. The reaction may be summarized by Eq. (23). The failure to isolate the acylated product may be ascribed to the formation of the enolate, (II). 

Violent reaction with benzoyl chloride combined with KOH, Bt2, barium carbonate, CS2, Cr(OCl)2, Cu, Pb, HNO3, BaCOs, H2SO4, hot water, (CH3)2S04, dibromomalononitrile, sulfuric acid. Incompatible with acids, ammonium chloride + trichloroacetonitrile, phosgene, cyanuric chloride, 2,5-dinitro-3-methylbenzoic acid + oleum, trifiuroroacryloyl chloride. Reacts with heavy metals (e.g., brass, copper, lead) to form dangerously explosive heavy metal azides, a particular problem in laboratory equipment and drain traps. When heated to decomposition it emits very toxic fumes of NOx and Na20. See also AZIDES. 

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