Chloramine amines

In the presence of a base, hydroxylamine-G-sulfonic acid or chloramine aminate carbonyl compounds nucleophilically (Schmitz 1961), e.g. ... 

In a variation of the Raschig process for making hydrazine, amines rather than ammonia ate reacted with chloramine to give the corresponding alkyl hydrazine ... 

Similar reactions occur with ammonia and HOBr (19—25), but since HOBr is a stronger electrophile than HOCl, formation rates are faster. Because of rapid bromine transfer between bromamines, equihbrium concentrations of the respective bromamines are obtained quickly. Mon ohrom amine predominates at basic pH at high N Br ratios. Below pH 8.5, NHBr2 and NBr predominate. Tribromamine formation is favored at lower pH and higher Br N ratios. The bromamines are less stable than chloramines but are better disinfectants. 

Protonated /V-chloroalkyl amines under the influence of heat or uv light rearrange to piperidines or pyrroHdines (Hofmann-Lriffler reaction) (88). The free-radical addition of alkyl and dialkyl-/V-chloramines to olefins and acetylenes yields P-chloroalkji-, P-chloroalkenyl-, and 8-chloroalkenylamines (89). Various N-hiomo- and N-chloropolyfluoroaLkylarnines have been synthesized whose addition products to olefinic double bonds can be photolyzed to fluoroazaalkenes (90). 

Two substituents on two N atoms increase the number of diaziridine structures as compared with oxaziridines, while some limitations as to the nature of substituents on N and C decrease it. Favored starting materials are formaldehyde, aliphatic aldehydes and ketones, together with ammonia and simple aliphatic amines. Aromatic amines do not react. Suitable aminating agents are chloramine, N-chloroalkylamines, hydroxylamine-O-sulfonic acid and their simple alkyl derivatives, but also oxaziridines unsubstituted at nitrogen. Combination of a carbonyl compound, an amine and an aminating agent leads to the standard procedures of diaziridine synthesis. 

Rearrangement of an enamine to a Sehiff s base through N- to C-alkyl migration was reported 729). These authors also found that enamines, rather than aminals, were formed from butyraldehyde and seeondary amines (730). Chloramines and aeetylenes reacted to give chloroenamine intermediates, which hydrolyzed on work-up of the reactions (731). 

The formation of chloramine as an intermediate, followed by reaction with nitric acid to produce the corresponding nitramine and HOC1, may explain the catalytic action of HC1 in the nitration of amines... 

Primary, secondary, and tertiary amines can be aminated by chloramine also, but pyridine nitrogens have been aminated only by hydrovylamine-O-sulfonic acid. 

Organoboranes react with a mixture of aqueous NH3 and NaOCl to produce primary amines. It is likely that the actual reagent is chloramine NH2CI. Chloramine itself,hydroxylamine-O-sulfonic acid in diglyme, and trimethyl-silyl azide " also give the reaction. Since the boranes can be prepared by the hydroboration of alkenes (15-16), this is an indirect method for the addition of NH3 to a double bond with anti-Markovnikov orientation. Secondary amines can be prepared by the treatment of alkyl- or aryldichloroboranes or dialkylchlorobor-anes with alkyl or aryl azides. 

Primary and secondary amines and amides are first chlorinated at nitrogen by the chlorine released by the gradually decomposing calcium hypochlorite. Excess chlorine gas is then selectively reduced in the TLC layer by gaseous formaldehyde. The reactive chloramines produced in the chromatogram zones then oxidize iodide to iodine, which reacts with the starch to yield an intense blue iodine-starch inclusion complex. 

Treatment with chlorine gas converts amines to chloramines, whose active chlorine oxidizes iodide to iodine. This then forms the well-known, deep blue iodine-starch complex [13]. 

Tetrasubstituted phosphinous amides of the type R2NPPh2 have been successfully arylated at phosphorus by the action of bromobenzene, in a process catalyzed by NiBr2, to give the aminophosphonium bromides [R2NPPh3] Br [109]. Other representative members of this class form phosphane-borane complexes [62], are aminated at phosphorus by chloramine to yield bis(amino)phos-phonium salts [110] and have been claimed to be protonated at phosphorus by ethereal tetrafluoroboric acid, as determined by NMR analysis [111]. 

Diamond LH, Audrieth LF (1955) Preparation of N-substituted hydrazines from amines and chloramine. J Am Chem Soc 77(11) 3131... 

Amines can give rise to chloramines during hypochlorite bleaching (Scheme 10.83). In addition to increasing AOX values, this can result in cellulose oxidative degradation by hypochlorite on subsequent hydrolysis of the chloramines (Scheme 10.84) [448]. 

Carbonylations of azoderivatives, chloramines, or aldimines are other ways of achieving amination, as shown by the last three examples in Table X. 

Interesting examples of the addition of N-nucleophiles to nitrile oxides are syntheses of chelated Z-amidoxime, N-[2-(dimethylaminomethyl)phenyl]mesitylene-carboamidoxime (118), and pyranosyl amidoximes (119) from the respective nitrile oxides and amines. Aromatic aldoximes undergo unusual reactions with chloramine-T (4 equiv, in refluxing MeOH). N-(p-toly 1 )-N-(p-tosy 1 )benzamides are formed via addition of 2 equiv of chloramine-T to the intermediate nitrile oxide followed by elimination of sulfur dioxide (120). 

M of ring substituted styrene or propenylbenzene in 30 ml tetrahydrofuran in V2L flask. Flush with N2 and add 33 ml 1 M borane in tetrahydrofuran (see procedure below for preparation). Stir one hour, add 3 ml water and 50 ml 3N NaOH, and then 215 ml 0.31 M fresh chloramine solution (prepared by treating dilute aqueous NH4OH with Na hypochlorite at 0° see BER 40,4586 (1907)). Keep at room temperature one hour, acidify with HCI, extract with ether, basify with NaOH and extract with ether and dry, evaporate in vacuum (or just basify and extract with ether and dry, evaporate in vacuum) to get the amine. 

To prepare the diborane in tetrahydrofuran, add 0.3 M NaBH4 (or LiBH4) and 0.4 M BF3 in total 200 ml tetrahydrofuran and keep dry in refrigerator, or generate the diborane in the reaction flask as follows To a well-stirred suspension of 3.4 g NaBH4 in 150 ml tetrahydrofuran and 0.3M of the styrene or propenylbenzene, add over one hour at room temperature, 15.1 ml BF3 in ether in 20 ml tetrahydrofuran (keep temperature at room temperature) let stand one hour at room temperature and decompose the excess hydride with water then add the NaOH and chloramine (or hydroxyl-amino-O-sulfonic acid) and proceed as above to get the amine. 

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