Cupric hydride

Cupric hydride.—Attempts to prepare cupric hydride have not led to the isolation of any definite compound.13... 

Tin tetrachloride has been used to prepare the stericaHy hindered triisopropylchlorosilane [13154-24-0] (119). Organobromosdanes are obtained under similar conditions through reaction with cupric and mercuric bromide. These reactions are most suitable for stepwise displacement of hydrogen to form mixed hydridochlorosilanes or in systems sensitive to halogen (120). Hydrides have also been displaced using organic bromides. Heating triethylsilane and... 

A fascinating study on the surface science of copper hydride on Si02, as well as on AI2O3, ceria (cerium oxide), and ZnO, has appeared [50]. Pure, yet thermally unstable, CuH can be precipitated as a red-brown solid from aqueous cupric sulfate and hypophosphorous acid in the presence of H2SO4, and has been characterized by powder X-ray diffraction (PXRD) (Eq. 5.25). Transmission electron microscopy (TEM) data suggest that it is most stable when deposited on acidic Si02. 

Aliphatic and aromatic sulfides undergo desulfurization with Raney nickel [673], with nickel boride [673], with lithium aluminum hydride in the presence of cupric chloride [675], with titanium dichloride [676], and with triethyl phosphite [677]. In saccharides benzylthioethers were not desulfurized but reduced to toluene and mercaptodeoxysugars using sodium in liquid ammonia [678]. This reduction has general application and replaces catalytic hydrogenolysis, which cannot be used [637]. 

Treatment of 1,3-dimethyl-1,2,3-triazolium tosylate (490) with sodium hydride in dimethylformamide gives the ylide (491). Oxidation of this ylide (491) using oxygen and cupric chloride catalyst gave the meso-ionic l,2,3-triazol-4-one 176, Ri = R = Me, R - H. ... 

Jack Halpera I wish to comment on two points that arise directly from Dr. Anbar s remarks. The first concerns the oxidation of ethylenediamine by copper. It seems to me that in the oxidation of organic ligands by copper (I I) one mechanism that ought to be considered seriously is that involving transfer of a hydride ion to the metal. We have shown unequivocally that in the reactions of H2, catalyzed by copper (I I), a relatively stable species, CuH+, is formed by transfer of a hydride from molecular hydrogen to cupric—i.e.,... 

According to H. Rose, the blue soln. of cupric hydroxide in cold hypophosphorous acid may remain unaltered for a long time and if very dil., it may even be heated without decomposition. If the soln. be evaporated in vacuo at a low temp., the copper is completely reduced as soon as the liquid is highly concentrated. C. A. Wurtz found that the soln. obtained by double decomposition of barium hypophosphite and copper sulphate at about 60° precipitates copper hydride— vide supra. Once blue crystals of copper hypophosphite, Cu(H2P02)2, were obtained they decomposed abruptly at 65°. According to R. Engel, this salt... 

This elimination is reminiscent of the last step in the aqueous palladium chloride oxidation mentioned above and this reaction also may involve multiple hydride addition-elimination steps. Minor amounts of the normal products and Markovnikov products are also generally found in these reactions. Cupric chloride can be used as a reoxidant although the yields are generally lower than with an all acetate, non-catalytic reaction. 

A very unstable copper hydride of unknown composition has been prepared in the form of a dark-brown powder by Stock and Kuss 8 by the interaction of cupric sulphate and potassium hypoborate, KHsOB. It decomposes readily, evolving hydrogen, and leaving a brown residue of metallic copper. 

With excess of cupric sulphate reduction with hypophosphorou acid yields metallic copper, but with excess of the acid cuprous hydrid is precipitated.7 Cupric sulphate is also reduced by hydroxylamine.8... 

Cushman and Dekow (SO) performed a synthesis of ( )-canadine (246) by oxidative decarboxylation on LTA treatment (Scheme 28). Thus, LTA oxidation in a mixture of AcOH and dimethylformamide of ( )-cis-2,3-methylenedioxy- 8-oxo- 9,10- dimethoxy-13- carboxytetrahydroprotober-berine (244) in the presence of cupric acetate gave berlambine (245) in 65% yield. Aluminum hydride reduction of 245 afforded ( )-canadine (246) in 63% yield. 

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