Cuprous amide

It has been stated that many halogen-free compounds, e.g., certain derivatives of pyridine and quinoline, purines, acid amides and cyano compounds, when ignited on copper oxide impart a green colour to the dame, presumably owing to the formation of volatile cuprous cyanide. The test is therefore not always trustworthy. The test is not given by duorides. 

The addition of copper to a boiling solution of benzenesulphonyl azide in methanol gave benzenesulphonamide 18 (80%) as the major product together with minor amounts of methylenebis(benzenesulphon-amide) 22 and 1,3,5-tris (benzenesulphonyl) hexahydro-s-triazine 23, resulting from condensation of 18 with the formaldehyde formed in the reaction 33>. Cuprous chloride was even more effective, but cuprous... 

Starting with bromoallenes 133, nucleophilic substitution supported by the use of cuprous cyanide lead to cyanoallenes of type 134 (Scheme 7.22) [126, 131, 181]. Pro-pargyl precursors and also cumulenes of type 133 can be utilized for palladium-catalyzed aminocarbonylation to give allenic amides 135 (cf. Section 7.2.6) [182]. 

Copper salts, cupric or cuprous also will catalyze the carbonylation of amines. Piperidine, for example, gives a urea derivative with carbon monoxide, and it, too, is probably a metal amide—carbon monoxide insertion reaction. 

The side chain for fiiran derivatives yet further removed structurally from the nitro-fiirans is obtained by internal amide-ester interchange of the A -aminoglycine derivative (3-6) with resulting cycUzation to the rmidazolinedione derivative (3-5). Cuprous... 

In the investigation of catalyst-solvent systems it was found that not only tertiary amines but also N N-disubstituted amides such as dimethyl acetamide (3) or hexamethyl phosphortriamide (HPT) yield catalytically active cupric-cuprous complexes. Some results obtained with these catalysts are shown in Table II. 

Although nitriles lack an acyl group, they are considered acid derivatives because they hydrolyze to carboxylic acids. Nitriles are frequently made from carboxylic acids (with the same number of carbons) by conversion to primary amides followed by dehydration. They are also made from primary alkyl halides and tosylates (adding one carbon) by nucleophilic substitution with cyanide ion. Aryl cyanides can be made by the Sandmeyer reaction of an aryldiazonium salt with cuprous cyanide. a-Hydroxynitriles (cyanohydrins) are made by the reaction of ketones and aldehydes with HCN. 

Alkali chlorites, NaCl20, in the presence of cuprous salts, can also be used for this oxidation. Oxidation of thioureas with dichlorodicyanobenzoquinone in the presence of sodium hydroxide also affords carbodiimides. Reaction of dialkylthioureas with sodium amide in refluxing toluene affords carbodiimides 25. The use of sodium hydride instead of sodium amide gives higher yields. 

The patended method of preparation of the blue dye (120) cuprous cyanide in dimethyl form amide or IV-methylpyrrolidinone... 

The preparation of alkyl, alkenyl, and aryl derivatives of cyanoacetylene (1) poses no particular problems. In most cases a terminal acetylene is metalated or converted into an alkynyl Grignard reagent, and these intermediates are subsequently intercepted by a cyano source , which in most cases is either cyanogen chloride or bromide and sometimes cuprous cyanide or phenyl cyanate. Of course, dehydration of an acetylenic amide as described for the parent molecules is also possible and has occasionally been employed. 

A highly efEcient amidation reaction of furans with iV-fluorobenzene-sulfonimide (NFSI) was developed, presumably proceeding via C-H bond activation. Cuprous iodide was employed as the catalyst, and various a-amidated furan derivatives were generated in good-to-excellent yields. This chemistry enables an economic method of synthesis of valuable ami-dated furans through a direct C-N bond-coupling process (140E5648). 

Zinc chloride (cuprous bromide jhexamethylphosphor amide ZnCl2lCuBrl(Me2N)2PO Syntheses via zinc homoenolates <-... 

A chloroform solution of XII containing a catalytic amount of cuprous chloride was oxygenated to give progesterone, XIII and N-formylmorpholine, XIV, in quantitative yield. Reaction was complete in 4.5 hr at O C. Cyclic enamines are readily cleaved to give a product which contains both a keto group and an amide function, equation (108). 

Amides may be converted to iV-alkyl and iV-acyl derivatives by appropriate condensation reagents. C-Alkylations of amides can also be carried out to modify the carbon skeleton of a compound. N-arylamides may be prepared by the Goldberg reaction of an amide with an aryl halide in the presence of potassium carbonate and cuprous iodide. 

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