Copper chloride carbonyl compounds

The allylation of aldehydes can be carried out using stannous chloride and catalytic cupric chloride or copper in aqueous media." In-situ probing provides indirect (NMR, CV) and direct (MS) evidence for the copper(I)-catalyzed formation of an allyltrihalostannane intermediate in very high concentration in water (Scheme 8.6). Hydrophilic palladium complex also efficiently catalyzes the allylation of carbonyl compounds with allyl chlorides or allyl alcohols with SnCl2 under aqueous-organic... 

Palladium catalysts, 10 42 14 49 16 250 Palladium-catalyzed carbonylation, 13 656 Palladium chloride/copper chloride, supported catalyst, 5 329 Palladium compounds, 19 650-654 synthesis of, 19 652 uses for, 19 653-654 Palladium films, 19 654 Palladium membranes, 15 813 Palladium monoxide, 19 651 Palladium oxide, 19 601... 

The solvent process involves treating phthalonitrile with any one of a number of copper salts in the presence of a solvent at 120 to 220°C [10]. Copper(I)chloride is most important. The list of suitable solvents is headed by those with a boiling point above 180°C, such as trichlorobenzene, nitrobenzene, naphthalene, and kerosene. A metallic catalyst such as molybdenum oxide or ammonium molybdate may be added to enhance the yield, to shorten the reaction time, and to reduce the necessary temperature. Other suitable catalysts are carbonyl compounds of molybdenum, titanium, or iron. The process may be accelerated by adding ammonia, urea, or tertiary organic bases such as pyridine or quinoline. As a result of improved temperature maintenance and better reaction control, the solvent method affords yields of 95% and more, even on a commercial scale. There is a certain disadvantage to the fact that the solvent reaction requires considerably more time than dry methods. 

In order to modulate the reactivity of intermediate 331, it was transformed into its copper derivative by treatment with copper(I) bromide or iodide in THF at —78 °C, and then was allowed to react with a,/3-unsaturated carbonyl compounds (to give compounds 343 resulting from a conjugated addition), acyl chlorides (to give ketones 344) and copper(II) chloride (to dimerize giving compounds 345) (Scheme 100)"° ". ... 

Ishihara and coworkers have reported that the reaction of 2-[(trimethylsilyl)methyl]-3-chloro-3,3-difluoropropene couples regioselectively with a variety of carbonyl compounds in the presence of zinc-copper chloride or silver acetate to give 2,2-difluoro-3-(trimethylsilyl)methyl-3-buten-l-ol derivatives (equation 87)81. Note again that the difluo-roallyl zinc species generated in situ reacts exclusively on the difluoromethylene terminus. 

Carbonylchlorocopper(I) is a colorless crystalline substance that decomposes rapidly in the absence of a carbon monoxide atmosphere to give copper(I) chloride and carbon monoxide. The compound is, however, stable for long periods of time if stored under carbon monoxide. Cu(CO)Cl has a polymeric structure,10 which may be described as layers of fused, six-membered, copper-chloride rings in the chair conformation, with terminally bonded carbonyl ligands. The infrared spectrum of Cu(CO)Cl (Nujol mull at 0°C) displays a characteristic large peak at 2127 cm -1 and a vibrational analysis has been reported.13... 

Many reagents convert primary amines into nitriles. Some of these have been mentioned above and represent serious limitations on methods for generating carbonyl compounds. Other ways of oxidizing amines to nitriles are the use of nickel peroxide,lead tetraacetate," copper(I) chloride plus oxygen and pyridine," iodine pentafluoride and benzeneseleninic anhydride. double bromination-dehy-drobromination can be effected for the preparation of nitriles with 2 equiv. of NBS and trimethyl-amine. Likewise, fluorination and elimination of HP gives nitriles." ... 

Nickel, palladium and copper catalysts can effect a variety of C — C bond-forming reactions P to the ester carbonyl via j8-zinc esters. These include 1,4-addition to a,jS-unsaturated carbonyl compounds (copper), arylation with aryl halides (palladium, nickel), allylation with allyl chloride (copper), and acylation with acyl chlorides (palladium, copper). " ... 

Still another powerful method for the regeneration of carbonyl compounds from dialkylhydrazones is copper-catalyzed hydrolysis. The reagents that have been tested for this purpose are 2% aqueous cop-per(II) acetate solution at pH 4, copper(II) chloride in 0.05M phosphate buffer and 75% tetrahydrofu-ran/water, and copper(II) sulfate pentahydrate . Under the conditions of the hydrolysis, no reaction is observed in the absence of the copper(II) ion. Typical yields are 85-100%. Other functional groups like a-dicarbonyl, a-tricarbonyl, acetal and aldehydic formyl groups were not affected by this hydrolysis procedure. Nitrile formation in the case of aldehyde dimethylhydrazones was not a significant side reaction. However, reaction times ranged from 1 to 15 h. The reaction is believed to be nonoxidative in nature rather, the copper is believed to activate the C=N bond and catalyze hydrolysis. The dimethylhydrazine produced during hydrolysis also complexes irreversibly with the copper(II) ion to drive the reaction to completion. 

Br/Mg exchange converts 1,2-dibromocyclopentene into the p-bromoalkenyl-magnesium chloride (LiCl complex), which reacts normally with carbonyl compounds. It is possible to peform a copper-mediated coupling at the p-carbon site while retaining the C-MgCl unit. ... 

General experimental details are as follows.697b It is usual first to mix the carbonyl component with the amine, which is presented as, e.g., hydrochloride or acetate. An appropriate hydrogen ion concentration must be maintained. For the preparation of aminoalkyl compounds that are liable to hydrolysis it is recommended that the water produced be removed by a drying agent or by azeotropic distillation. Dioxan is a suitable solvent, but it is often recommended that acetic acid be added to it. Ketones react better in alcohol with paraformaldehyde. Copper chloride or iron chloride is said to be a useful addition in reactions of acetylenes. Reactions of amines, phenols, and furans, even under mild conditions, may be accompanied by multiple condensation or resinification. 4-Hydroxybenzylamine is reported706 to be obtained in 92% yield when ammonia is led into a mixture of phenol and formaldehyde. 

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