N-Chlorosuccinimide

Acid to litmus. One gram dissolves in about 70 mL water, 150 mL alcohol, 50 mL benzene. Sparingly soluble in ether, chloroform, and carbon tetrachloride. Liberates iodine from potassium iodide solutions and bromine from sodium bromide solutions.1 

Alcohols. Extremely violent reaction with aliphatic alcohols.2 Benzylamine. Mixture reacts violently.2 

Dust contamination of the stored imide may cause smoldering.3 Hydrazine Hydrate. Mixture reacts violently.2 

Irritant.4 Avoid contact with skin and breathing dust.5 

Wear eye protection, laboratory coat, and nitrile rubber gloves. Scoop up and treat as for waste disposal. 

---

Synthetic procedures are available for the preparation of fluoro, chloro, bromo and iodo compounds from the corresponding lithio derivatives. Perchloryl fluoride (FCIO3), N-chlorosuccinimide, bromine and iodine are examples of reagents which can be used to introduce fluorine, chlorine, bromine and iodine, respectively. 

Oxidalion of alcohols lo kelones by means of N chlorosuccinimide (NCS) or NBS and Me2S... 

The oxidation of certain steroidal <5,e-unsaturated amines with either N-chlorosuccinimide or lead tetraacetate yields bridged aziridines, see structure (117)... 

Not surprising, the most prevalent synthetic utility is the assembly of the pyrrolidine ring. N-Chloroamine 27 was obtained by treatment of N-methyl-2-cyclopentylethylamine (26) with N-chlorosuccinimide. Under classic Hofmann-Loffler-Freytag reaction conditions, 27 was rearranged either thermally or by UV irradiation in sulfuric acid to bicyclic amine... 

The a -halosulfone, required for the Ramberg-Backlund reaction, can for example be prepared from a sulfide by reaction with thionyl chloride (or with N-chlorosuccinimide) to give an a-chlorosulfide, followed by oxidation to the sulfone—e.g. using m-chloroperbenzoic acid. As base for the Ramberg-Backlund reaction have been used alkoxides—e.g. potassium t-butoxide in an etheral solvent, as well as aqueous alkali hydroxide. In the latter case the use of a phase-transfer catalyst may be of advantage. ... 

Hydrolysis of the acetate ester with alkali, e.g., sodium methoxide in methanol, affords the free alcohol, 16/3-methyl-1,4,9( 11 )-pregnatriene-17o, 21-diol-3,20-dione. To a suspension of 3 grams of 16/3-methyl-1,4,9(11)-pregnatriene-17o,21-diol-3,20-dione-21-acetate in 40 ml of acetone is added at 0°C with stirring 2 grams of N-chlorosuccinimide and then 7 ml of a perchloric acid solution prepared by dissolving 0.548 ml of 70% perchloric acid in 33 ml of water. The resulting reaction mixture is stirred at 0°C for about 4 hours 45 minutes. 

The excess of N-chlorosuccinimide is destroyed by the addition of about 15 drops of allyl alcohol and 180 ml of water is then added with stirring. This mixture is held at 0°C for about one hour. The precipitated 16/3-methyl-1,4-pregnadiene-9o-chloro-11/3,17o,21-triol-3,20-dione-21-acetate is recovered by filtration. A solution of 250 mg of the chlorohydrin in 5 ml of 0.25N perchloric acid in methanol is stirred for about 18 hours at room temperature to produce 16/3-methyl-9o-chloro-11/3,17o,21-trihydroxy-1,4-pregnadiene-3,20-dione which is recovered by adding water to the reaction mixture and allowing the product to crystallize. Propionic anhydride is then used to convert this material to the dipropionate. 

A mixture of 20 g of 1. [p.((3.diethylaminoethoxy)phenyl]-1,2-diphenylethanol in 200 cc of ethanol containing an excess of hydrogen chloride was refluxed 3 hours. The solvent and excess hydrogen chloride were removed under vacuum, and the residue was dissolved in a mixture of ethyl acetate and methylene chloride. 1-[p-((3.diethylaminoethoxv)phenyl] -1,2-diphenylethylene hydrochloride was obtained, melting at 148° to 157°C. This hydrochloride salt was treated with N-chlorosuccinimide in dry chloroform under reflux. The product then obtained was converted to the free base and treated with citric acid. The dihydrogen citrate salt of 1-[p-((3-diethylaminoethoxy)phenyl]-1,2-diphenylchloroethylene was obtained, melting at 116.5° to 118°C. 

Reduction of 5//-6,7-dihydrodibenz[t, e]azepine-5,7-dione (31) with lithium aluminum deuteride followed successively by ring chlorination with N-chlorosuccinimide and dehydrochlorination. affords [5,5,7-2H3]-5//-dibenz[r, >]azepine (32).117... 

Trimethylsilyl halides can also be used for analogous reactions with arenediazo-nium tetrafluoroborates, as shown by Keumi et al. (1989). These authors treated 2-fluorenediazonium tetrafluoroborate in A/,Af-dimethylformamide or -acetamide with trimethylsilylchloride, -bromide, or -iodide in the presence of an excess of N-chlorosuccinimide, Af-bromosuccinimide, or methyl iodide, respectively, at 60 °C (Cl, Br) or at room temperature (I). The yields of the 2-halofluorenes were good in addition fluorene, the product of hydro-de-diazoniation, was obtained, if the reaction was run in tetrahydrofuran/Af,7V-dimethylformamide mixtures. The mechanism of these reactions, as well as that of the corresponding azido-de-diazoniation, is uncertain (see also Secs. 10.2 and 10.7). 

N-chlorosuccinimide, reaction+PhOH, 92 chrysene, bromination of, 405 —, hydrogen exchange with, 258 —, nitration of, 39 cinnamic acid, nitration of, 39 cinnanyl p-totyl ethers, Ciaisen rearrangement of, 472... 

It was reported earlier that even dialkyl sulphides are efficiently oxidized to sulphoxides without a concomitant C—S bond cleavage by NBS or N-chlorosuccinimide (NCS) when the reaction is performed in anhydrous methanol at low temperature103. iV-Chloro-Nylon-6,6 in methanol-water or dioxane-water104 and iV-bromo- -caprolactam in water or alcohols105 were also used successfully for oxidation of sulphides. 

Ribosomal protein L12 was oxidized with N-chlorosuccinimide as described by Schechter and coworkers28 and dialyzed. The complete system contained 33 mM Tris-HCI (pH 7.4), 13mM MgCI2,275 pmol Met(0)-L12,13mM dithiothreitol (or 2-mercaptoethanol where indicated), and enzyme. See the legend to Figure 5 for further details of the assay. 

Reduction of iV-(3-bromopropyl) imines gives a bromo-amine in situ, which cyclizes to the aziridine. Five-membered ring amines (pyrrolidines) can be prepared from alkenyl amines via treatment with N-chlorosuccinimide (NCS) and then BusSnH. " Internal addition of amine to allylic acetates, catalyzed by Pd(PPh3)4, leads to cyclic products via a Sn2 reaction. Acyclic amines can be prepared by a closely related reaction using palladium catalysts. Three-membered cyclic amines (aziridines)... 

When oxytetracycline (100) is reacted with N-chlorosuccinimide in dimethoxyethane, the active methine group at C la reacts and, apparently, there is formed a hemiketal bond between the C -OH and the C -ketogroup (101). Dehydration with anhydrous HF of the tertiary, benzylic C -OH group takes an exocyclic course, partially because aromatization to... 

Chlorination with N-chlorosuccinimide at the activated indole 2-position gives the corresponding chloro... 

Soufiaoui reported that arylnitrile oxides 10 can be generated under microwaves not only from aromatic oxime chlorides, such as 174, by the action of alumina (Method A) but also from aryloximes, such as 176, by the addition of a chlorination agent, N-chlorosuccinimide (NCS), supported on alumina (Method B) (Scheme 9.54) [29a]. Both methods afforded identical cydoadducts in similar yields - when indene was used as the dipolarophile the yield was 86%. In the absence of alumina, method B fails (reagents are less reactive and decompose) and method A does not yield any cydoadduct but a dimer of the dipole. 

Anthracenecarbonitrile oxide, prepared directly from 9-anthracenecarbald-oxime and N-chlorosuccinimide, reacts with dimethyl acetylenedicarboxylate to afford dimethyl 3-(9/-anthracenyl)isoxazole-4,5-dicarboxylate in good yield. Double activation reactions between this diester and hydrogenated lexitropsin 430, in a 1 2 molar ratio, produce a novel intercalating isoxazolyl bis-lexitropsin conjugate 431 as the major product (43). 

The process involves one technological step. Tetrabutyl- or triethylammonium fluorides can serve as reagents for the cleavage of cycloadducts (181). For this purpose, N-chlorosuccinimide in aqueous THF can also be used. 

---