2-Bromination with cyanogen bromide

Treatment of quinoline with cyanogen bromide, the von Braun reaction (17), in methanol with sodium bicarbonate produces a high yield of l-cyano-2-methoxy-l,2-dihydroquinoline [880-95-5] (5) (18). Compound (5) is quantitatively converted to 3-bromoquinoline [5332-24-1], through the intermediate (6) [66438-70-8]. These conversions are accompHshed by sequential treatment with bromine in methanol, sodium carbonate, or concentrated hydrochloric acid in methanol. Similar conditions provide high yields of 3-bromomethylquinoHnes. 

Carbon-sulfur bond formation by oxidative cyclization of a thiourea derivative using bromine will in the case of (521) furnish a thiazolo[/,/]quinoline (522 Z = NH). The same imine is obtained from 8-mercapto-l,2,3,4-tetrahydroquinoline on treatment with cyanogen bromide with phosgene the 2-oxo derivative (522 Z = 0) is formed (63JOC2581). 

The bromination of poly-DCH is of interest because the degree of bromine uptake can be controlled, by choice of experimental conditions, between 3 and 8 Br atoms per polymer repeat unit and because a crystal-to-crystal transformation is observed. Scheme 1 summarizes the reactions of liquid bromine with poly-DCH. Interaction of poly-DCH crystals with dense vapors of bromine or cyanogen bromide for months did not lead to detectable weight gain. By contrast, DCH monomer (2a), which has a crystal structure similar to the polymer (6), readily reacts with bromine vapor to give an eunor-phous material which has gainbd ca 12 Br atoms per molecule. 

Interest in cyanogen bromide as a brominating agent for imidazoles has been rekindled. It seems that bromo products can be made in this way, for example, 1-benzylimidazole reacts with cyanogen bromide in the presence of 4-dimethylaminopyridine to give l-benzyl-2-bromoimidazole, perhaps via an ylide mechanism. Cyanogen chloride and the pre-formed adduct of cyanogen bromide and... 

No detailed reports on halogenations of diazo compounds with molecular chlorine or bromine can be found in the literature. Chloro- and bromodiazomethane are obtained, however, by treatment of CH2N2 with r butyl hypochlorite or hypobromite, respectively, at — 100°C in a pentane-chlorotrifluoromethane mixture. These diazohalogenomethanes are very unstable. The bromination and iodination products of diazomethylphosphoryl compounds, which Regitz et al. (1979 c) obtained from the silver derivatives of these diazomethane derivatives with cyanogen bromide (BrCN) and molecular iodine, are somewhat more stable. 

Cyanogen bromide (Bromine cyanide) CNBr Extremely irritating and toxic vapours Contact with acids, acid fumes, water or steam can produce toxic and corrosive fumes Transparent crystals with a penetrating odour Melting point 52°C Boiling point 61 °C Vapour density 3.6 Water soluble... 

The solid disulfide reacts explosively with chlorine or bromine. At low temperatures in certain non-aqueous solvents, e.g. chloroform, CISCSN3 and BrSCSN3 are probably formed, but the extreme instability of these compounds has precluded their exact analysis and description. However, the reaction between cyanogen bromide and the potassium salt of the thiol yields the well-defined cyanide NCSCSN3,... 

Cyanide and thiocyanate anions in aqueous solution can be determined as cyanogen bromide after reaction with bromine [686]. The thiocyanate anion can be quantitatively determined in the presence of cyanide by adding an excess of formaldehyde solution to the sample, which converts the cyanide ion to the unreactive cyanohydrin. The detection limits for the cyanide and thiocyanate anions were less than 0.01 ppm with an electron-capture detector. Iodine in acid solution reacts with acetone to form monoiodoacetone, which can be detected at high sensitivity with an electron-capture detector [687]. The reaction is specific for iodine, iodide being determined after oxidation with iodate. The nitrate anion can be determined in aqueous solution after conversion to nitrobenzene by reaction with benzene in the presence of sulfuric acid [688,689]. The detection limit for the nitrate anion was less than 0.1 ppm. The nitrite anion can be determined after oxidation to nitrate with potassium permanganate. Nitrite can be determined directly by alkylation with an alkaline solution of pentafluorobenzyl bromide [690]. The yield of derivative was about 80t.with a detection limit of 0.46 ng in 0.1 ml of aqueous sample. Pentafluorobenzyl p-toluenesulfonate has been used to derivatize carboxylate and phenolate anions and to simultaneously derivatize bromide, iodide, cyanide, thiocyanate, nitrite, nitrate and sulfide in a two-phase system using tetrapentylammonium cWoride as a phase transfer catalyst [691]. Detection limits wer Hi the ppm range. 

Cyanogen bromide is obtained by the reaction of bromine with potassium cyanide or sodium cyanide ... 

A few syntheses of specific substituted 3,3 -bipyridines have been reported. 6,6 -Dialkyl-3,3 -bipyridines have been shown to be one of the products of the reaction of l-lithio-2-alkyl-l,2-dihydropyridines with perhalometh-anes, cyanogen bromide, or bromine. In an interesting double... 

A convenient and quick way to prepare 1-bromoalkynes consists of adding an ethereal solution of cyanogen bromide to a strongly cooled solution of a metallated (Li or MgX) [119] acetylene in an organic solvent (EtjO or THF). The method seems very general and excellent yields can be obtained provided that the ethereal solution of BrC N (which is prepared from an aqueous solution) is dried well. The advantage of this method over the introduction with elemental bromine is that CC double bonds in the acetylenic compounds do not react... 

Syntheses of 5-halogenotetrazoles from metallic derivatives have met with mixed fortunes. Lithiation of 1-methyltetrazole followed by reaction at -60°C with bromine, iodine, or cyanogen bromide gave the 5-bromo and 5-iodo compounds in 36-55% yields (71CJC2139). 1,2-Disubstituted tetrazolium tetraphenylborates were lithiated in the 5-position, but subsequent reaction with chlorine or bromine failed to trap the anion. Instead, oxidation produced a radical cation, which abstracted a hydrogen atom from the solvent [91 AG(E)1162]. 

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