Sodium hypochlorite with amines

Sandford, P. A., A. J. Nafziger, and A. Jeanes. 1971. Reaction of sodium hypochlorite with amines and amides a new method for quantitating amino sugars in monomeric form. Anal. Biochem. 42 422-436. 

By treatment of an amide with sodium hypobromite or sodium hypochlorite solution (or with the halogen and alkali), the amine of one less carbon atom is produced, the net result being the elimination of the carbonyl group. An example is ... 

Hoffman Degradation. Polyacrylamide reacts with alkaline sodium hypochlorite [7681-52-9], NaOCl, or calcium hypochlorite [7778-54-3], Ca(OCl)2, to form a polymer with primary amine groups (58). Optimum conditions for the reaction include a slight molar excess of sodium hypochlorite, a large excess of sodium hydroxide, and low temperature (59). Cross-linking sometimes occurs if the polymer concentration is high. High temperatures can result in chain scission. 

Hexanitrostilbene may be prepared by a dding a solution of TNT ia tetrahydrofuran and methanol at 5°C to aqueous sodium hypochlorite. To this mixture a 20% solution of trimethyl amine hydrochloride is added at 5—15°C. Hexanitrostilbene precipitates, and is filtered and washed with methanol and... 

Oxidation of Aromatic Amines. The technically important dye Direct Yellow 28 (23) [10114-47-3] (Cl 19555) for cotton usage is manufactured by oxidation of dehydrothio- i ra-toluidinesulfonic acid sodium salt with sodium hypochlorite ia aqueous alkaline solutioa. 

The required A-chloroamines 9 can be prepared from the corresponding amine by treatment with sodium hypochlorite or A-chlorosuccinimide. 

Treatment with sodium hypochlorite or hypobromite converts primary amines into N-halo- or N,N-dihaloamines. Secondary amines can be converted to N-halo secondary amines. Similar reactions can be carried out on unsubstituted and N-substituted amides and on sulfonamides. With unsubstituted amides the N-halo-gen product is seldom isolated but usually rearranges (see 18-13) however, N-halo-N-alkyl amides and N-halo imides are quite stable. The important reagent NBS is made in this manner. N-Halogenation has also been accomplished with other reagents, (e.g., sodium bromite NaBr02) benzyltrimethylammonium tribromide (PhCH2NMe3 Br3"), and NCS. The mechanisms of these reactions involve attack by a positive halogen and are probably similar to those of 12-47 and 12-49.N-Fluorination can be accomplished by direct treatment of amines °° or... 

Primary aliphatic or aromatic amines react with calcium (or sodium) hypochlorite to form A-mono- or di-chloroamines which are explosively unstable, but less so than nitrogen trichloride. 

The flow-cell design was introduced by Stieg and Nieman [166] in 1978 for analytical uses of CL. Burguera and Townshend [167] used the CL emission produced by the oxidation of alkylamines by benzoyl peroxide to determine aliphatic secondary and tertiary amines in chloroform or acetone. They tested various coiled flow cells for monitoring the CL emission produced by the cobalt-catalyzed oxidation of luminol by hydrogen peroxide and the fluorescein-sensitized oxidation of sulfide by sodium hypochlorite [168], Rule and Seitz [169] reported one of the first applications of flow injection analysis (FTA) in the CL detection of peroxide with luminol in the presence of a copper ion catalyst. They... 

In summary, the reaction of osmium tetroxide with alkenes is a reliable and selective transformation. Chiral diamines and cinchona alkakoid are most frequently used as chiral auxiliaries. Complexes derived from osmium tetroxide with diamines do not undergo catalytic turnover, whereas dihydroquinidine and dihydroquinine derivatives have been found to be very effective catalysts for the oxidation of a variety of alkenes. OsC>4 can be used catalytically in the presence of a secondary oxygen donor (e.g., H202, TBHP, A -methylmorpholine-/V-oxide, sodium periodate, 02, sodium hypochlorite, potassium ferricyanide). Furthermore, a remarkable rate enhancement occurs with the addition of a nucleophilic ligand such as pyridine or a tertiary amine. Table 4-11 lists the preferred chiral ligands for the dihydroxylation of a variety of olefins.61 Table 4-12 lists the recommended ligands for each class of olefins. 

Primary amino acids will react with o-phthalaldehyde in the presence of the strongly reducing 2-mercaptoethanol (pH 9-11) to yield a fluorescent product (emission maximum, 455 nm excitation maximum, 340 nm). Peptides are less reactive than a-amino acids and secondary amines do not react at all. As a result, proline and hydroxyproline must first be treated with a suitable oxidizing agent such as chloramine T (sodium A-chloro-p-toluene-sulphonamide) or sodium hypochlorite, to convert them into compounds which will react. Similarly cystine and cysteine should also be first oxidized to cysteic acid. 

IV-Chloroalkylamines R HCl (R1 = Me, Bu, C7H15, etc.), generated from primary amines and sodium hypochlorite, react with the alkyldimethylboranes R2BMe2 (R2 = CgHi3, cyclopentyl or cyclohexyl) to give the secondary amines R1R2NH in 50-68% yields179. 

An Arbuzov reaction of triethyl phosphite with A-chloroamines RNHC1 (R = i-Pr, cyclohexyl or PhCH2), prepared from the corresponding amines and aqueous sodium hypochlorite, leads to the phosphoramides 357 with the elimination of ethyl chloride395. 

Oxidation of 2-thiopyrimidines 595 with sodium hypochlorite at —25°C has been used to prepare pyrimidine-2-sulfonyl chlorides 596 which were then reacted with amines in situ to prepare sulfonamides 597 <2006JOC1080>. Alternatively, reaction of the chlorides with KHF2 and a quaternary ammonium can be used to prepare sulfonyl fluorides, which are stable enough to isolate <2006JOC1080>. 

This route to the a-nitroso derivatives of the 7r-deficient heterocycles has permitted an exploration of their chemistry. They are extremely reactive and condense readily with 1,3-dienes to give 3,6-dihydro-l,2-oxazines (e.g. 99), and with aromatic amines in the presence of acid to give azo compounds (Scheme 86). This latter reaction is particularly useful in view of the instability of the corresponding 2-pyridinediazonium salts referred to above, which limits conventional access. The a-nitroso heterocycles are oxidized by ozone or sodium hypochlorite to the a-nitro compounds (Scheme 86) (82JOC553). 

Sodium hypochlorite reacts with (1) to give the 1-chloro derivative, which gives rise to a variety of products, including the bicyclic amine, pyrrolizidine, when treated with silver salts (72CJCH67). Quaternary salts derived from (3) react with sodium methoxide to give mostly the acyclic Hofmann elimination product (83%) minor amounts of (3) (14%) are also formed, together with a trace (2%) of the product of 5N2 attack on the a-methylene carbon (80JOC3952). 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

As indicated above (Ohme and Schmitz [38a, p. 339]) primary amines converted into the alkylamides of sulfuric acid can be oxidized with sodium hypochlorite to azo compounds. The reaction appears to proceed by way of an intermediate hydrazine, which is ultimately oxidized [38a], The reaction is suitable for the formation of symmetrically substituted azoalkanes. Highly branched primary aliphatic amines have been oxidized with sodium hypochlorite in an aqueous dioxane medium [77],... 

A very flexible method of preparing unsymmetrical azo compounds makes use of the condensation of C-nitroso compounds with amines. Thionylamines have also been condensed with substituted hydroxylamines to produce azo compounds not usually accessible by other means. Treatment of dialkylsulfuric diamides with sodium hypochlorite is one means of preparing aliphatic azo compounds. Aromatic amines and aromatic nitro compounds at high temperature produce azo compounds. 

Ready addition of 2-nitrosopyridine to 1,3-dienes gives 3,6-dihydro-1,2-oxazines, e.g. (774) — (773), and condensation with aromatic amines gives azo compounds, e.g. (774) — (775). Nitroso compounds are oxidized by ozone or sodium hypochlorite to the corresponding nitro compounds. 5-Nitrosopyrimidines can be reduced to the 5-amino derivatives or condensed with activated methylene groups. 

Aniline may be made (I) hy Ihe reduction, with iron or tin in HOI, of nitrobenzene, and (2) by the amination of chlorobenzene by healing with ammonia to a high temperature corresponding to a pressure of over 200 atmospheres in the presence of a catalyst (a mixture of cuprous chloride and oxide). Aniline is the end-point of reduction of most mono-nitrogen substituted benzene nuclei, as nitrosobenzene, beta-phenylhydroxylamine. azoxybenzene, azobenzene, hydrazobenzene. Aniline is detected by the violet coloration produced by a small amount of sodium hypochlorite. 

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