Phenyl chloramine

The phenyl-chloramine formed by the action of hydrochloric acid on phenyl-hydroxylamtne changes, by molecular rearrangement, into o- and p-chlor-aniline. 

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). 

The reaction of the thiolated PVC with Chloramine T carried out and the structure ( ) of the resultant polymer was examined (1 ). In the case of phenyl-thioether, the sulfilimine structure (2) was mainly produced accompanied with, in part, the sulfenamide structure (8,) binded to the main chain with N atom, the case of allyl thioether derivative containing C=C moiety in the pendent group, the sulfilimine (9) formed rearranged exclusively in Claisen type to the sulfenamide structure (10) connected to the main chain with S atom. 

Correlate method reaction of alkyl phenyl tellurides with chloramines-T... 

The reaction of alkyl phenyl tellurides with excess chloramine-T (A -chloro-A -sodium-p-tolysulphonamide) in refluxing THF leads to olefins, presumably through a tellurosul-phimino intermediate. Owing to the high yields obtained, this method seems to be highly competitive with the telluroxide elimination. 

Olefins by reaction of alkyl phenyl tellurides with chloramine-T (typical procedure). A solution of 1-dodecyl phenyl telluride (0.198 g, 0.52 mmol) and commercial chloramine-T trihydrate (0.300 g, 1.0 mmol) in THF (5 mL) is refluxed for 40 min under Nj. After evaporation of the solvent, the residue is treated with hexane (20 mL), and then fdtered. The filtrate is passed through a short Si02 column with hexane, giving, after evaporation, 1-dodecene as a colourless oil (0.068 g (78%)). 

Iodine becomes incorporated into proteins either oxidatively, or enzymatically, or electrochemically. Oxidative incorporation uses organochemical oxidants, such as, for example, chloramine T or lodo-gen (l,3,4,6-tetrachloro-3a,6a-diphenyl glycouril). Enzymatic incorporation is done by means of lactoperoxidase. By these methods iodine is introduced into phenyl (tyrosyl) residues of the protein. 

Chloramine-T reacts with (2-oxo-3-phenyl-27/-[l,8]naphthyridine-l-yl)acetic acid arylidenehydrazides to generate 1-(5-aryl-[1,3,4]-oxadiazol-2-ylmethyl)-3-phenyl-17/-[l,8]naphthyridin-2-ones <2004IJB2014>. 

Japanese chemists (96) have reported the chemical conversion of kobusine into the chloramine (95). The latter was treated with sodium methoxide in methanol to afford compound 96 in which the bridged C-14-C-20 bond was cleaved. Reduction of kobusine with sodium in n-propanol, followed by acetylation afforded compound 88. Treatment of 88 with excess phenyl chloroformate in refluxing o-dichlorobenzene gave the carbamate 89. The latter was hydrogenated over Pd-C in methanol to obtain compound 90 in 94% yield. Further hydrogenation of 90 in the presence of platinum in acidic solution gave 91. Acidic hydrolysis of 91 afforded compound 92. The carbamate 92 was converted to the benzyl derivative 93 by treating with... 

The chloramine derivatives (ArS02NClNa) of a variety of other aryl-sulfonamides (Ar = phenyl, o-tolyl, p-chlorophenyl,/>-nitrophenyl, and o-carboalkoxyphenyl) have been used successfully in these catalytic oxy-aminations. Since only chloramine-T (Ar = p-tolyl) and chloramine-B (Ar = phenyl) are commercially available, we have developed a convenient procedure for generating the chloramines in situ for use in the modification involving phase-transfer catalysis. One simply stirs a suspension of the arylsulfonamide with an equivalent of sodium hypochlorite (Clorox) until a homogeneous solution is obtained. When this solution is used in the PTC method (see Ref. 2 for experimental details), the yields of oxyaminated product are comparable with those obtained with isolated chloramine salts. 

Sharpless and co-workers first reported the aminohydroxyIation of alkenes in 1975 and have subsequently extended the reaction into an efficient one-step catalytic asymmetric aminohydroxylation. This reaction uses an osmium catalyst [K20s02(OH)4], chloramine salt (such as chloramine T see Chapter 7, section 7.6) as the oxidant and cinchona alkaloid 1.71 or 1.72 as the chiral ligand. For example, asymmetric aminohydroxylation of styrene (1.73) could produce two regioisomeric amino alcohols 1.74 and 1.75. Using Sharpless asymmetric aminohydroxylation, (IR)-N-ethoxycarbonyl-l-phenyl-2-hydroxyethylamine (1.74) was obtained by O Brien et al as the major product and with high enantiomeric excess than its regioisomeric counterpart (R)-N-ethoxycarbonyl-2-phenyl-2-hydroxyethylamine (1.75). The corresponding free amino alcohols were obtained by deprotection of ethyl carbamate (urethane) derivatives. 

The hydroxyamination of 2-phenyl-l-propene was carried out with the carbamates derived from ( )-9-(2,2,2-trihalo-l-hydroxyethyl)anthracene ( )-D and ( )-E and gave mixtures of regioisomers 3 and 4, each as a pair of diastereomers. It is surprising that the major regioisomer in these reactions is the primary alcohol 3. This is in contrast with the regioselectivity described for the catalyzed oxyamination reactions of 2-phenyl-l-propene with chloramine-T94, and 1-phenylcyclohexene with terf-butyl chloro(argento)carbamatc95. 

Two decades ago, Hori and Sharpless reported the reaction of 10-(phenyl-seleno)- -pinene with Chloramine T (TsNClNa) to afford the corresponding allylic amine [30] (Scheme 21). 

The one-pot three-component reaction of polyethylene glycol-supported acrylate 623 with aldehydes 621 and hydrazines 622 in the presence of chloramine-T followed by methanolysis afforded pyrazolines 624 in good yields and high purities (Scheme 77) <2003SL1467>. 1,3-Dipolar cycloaddition of resin-supported acrylic acid 625 with the nitrilimines generated in situ by oxidation of the aldehyde phenylhydrazones with (diacetoxy)iodobenzene under microwave irradiation gave 626, which was converted into l-phenyl-3-substituted-2-pyrazolinyl-5-carboxylates 627 (Scheme 78) <2004SC3521>. 

Animations in this area involve anions of both it-excessive and it-deficient heterocycles, which are generated from the halo compounds or by direct metalation. Most of the animating reagents seem to be applicable except that phenylthiomethyl azide (32) fails with the 2-lithium or 2-copper derivatives of furan, thiophene, N-methylpyrrolc, and (V-methylindole.274 Similarly, chloramine and O-methylhydroxylaminc, but not phenyl azide, fail to aminate 2-lithio-1-methylimidazole 66 and the MeN(Li)OMe nitrenoid does not react with 2-lithiothiophene.97 The reactions that appear to be most widely applicable to heterocyclic carbanions are shown in Eqs. 73,100,101 74,316 and 75.358... 

Allyl tosyl amides. Reaction of allyl phenyl tellurides which are obtained from the corresponding halides (in situ) with TsN=IPh (or chloramine T) furnishes the amides. 

The third reaction type to be discussed in this section is the Forster reaction. It was discovered by Forster in 1915, as he had obtained (benzoyl)(phenyl)diazomethane (2-diazo-l,2-diphenylethan-l-one, 2.62) by treatment of (Z)- and ( )-benzil monooxime ((Z) = 2.95) with sodium hypochlorite and ammonia (which readily forms chloramine). a-Keto-monoximes like 2.95 are obtained easily from a-methylene-con-taining ketones (e.g., 2.94) by the oximation reaction, i.e., a nitrosation with a nitrous acid ester followed by a C O proton shift (2-41). 

The chloramidation of tertiary amines by introducing gaseous chloramide (chloramine) into the anhydrous amine or a solution of the amine in an inert solvent results in the formation of 1,1,1-trisubstituted hydrazonium chlorides. It has been found that a similar chloramidation reaction with tertiary phosphines can be made to yield analogous compounds of the general formula [R3PNH2]C1, i.e., F,P,P-trisubstituted aminophosphonium chlorides. The following aminophosphonium chlorides were prepared by this reaction P,P,P-triphenyl P,P,P-tri-n-butyl P-phenyl-P,P-(cyclotetramethylene) and P-phenyl-P,P-(cyclopenta-methylene). The methodforthe preparation of (triphenyl)-aminophosphonium chloride is given as representative of the procedure. 

Barysheva (56) found that primidone showed a blue luminescence in the ultraviolet. Cooper (57) lists the colors formed by many drugs with p-dimethylamino-benzaldehyde primidone forms a primrose color. Ammonia is evolved when primidone is heated with anhydrous sodium carbonate (17). Haug and Panescu (58) describe a rapid color test for detecting small amounts of pheno-barbital or 5-phenyl-5-ethylthiobarbitur c acid in primidone. Kassau (59), Kuhnert-Brandstatter et al (4), and Penprase and Biles (7) describe microscopic tests for primidone. Shamotienko (60) developed a color test for primidone, in which the same is boiled with chloramine, copper sulfate, and sodium hydroxide primidone causes a reddish-violet color to develop. Lobanov and Gorbunova (6l) determined primidone interferometrically in tablets and powders. 

McLEAN With nontoxic chloramines generally what one is usually talking about is a phenyl-nitrogen ring. And these are the kind of materials we re examining. These are relatively stable, but what about the simple chloramines themselves ... 

---