2350-10-9

Upstream product

• 640-61-9 N-methyl-p-toluenesulfonylamide 
• 420-37-1 trimethoxonium tetrafluoroborate 
• 127-65-1 chloroamine-T 
• 20607-12-9 sodium salt of N-methyl toluenesulfonamide 

Downstream Products

• 112497-43-5 N-allyl-N-methyl-4-toluene sulphonamide 
• 107-05-1 3-chloroprop-1-ene 
• 10523-77-0 1-chloromethyl-1-methylcyclopropane 
• 1610769-96-4 N-(2-chloro-2-phenylethyl)-N-4-dimethylbenzenesulfonamide 

Relevant academic research and scientific papers

Generation and Reactivity of Amidyl Radicals: Manganese-Mediated Atom-Transfer Reaction

A simple and efficient protocol to generate amidyl radicals from amine functionalities through a manganese-mediated atom-transfer reaction has been developed. This approach employs an earth-abundant and inexpensive manganese complex, Mn2(CO)su

A general and atom-efficient continuous-flow approach to prepare amines, amides and imines via reactive N-chloramines

Chloramines are an important class of reagents, providing a convenient source of chlorine or electrophilic nitrogen. However, the instability of these compounds is a problem which makes their isolation and handling difficult. To overcome these hazards, a continuous-flow approach is reported which generates and immediately reacts N-chloramines directly, avoiding purification and isolation steps. 2-Chloramines were produced from the reaction of styrenes with N-alkyl-N-sulfonyl-N-chloramines, whilst N-alkyl or N,N’-dialkyl-N-chloramines reacted with anisaldehyde in the presence of t-BuO2H oxidant to afford amides. Primary and secondary imines were produced under continuous conditions from the reaction of N-chloramines with base, with one example subsequently reduced under asymmetric conditions to produce a chiral amine in 94% ee.

Continuous formation of N-chloro-N,N-dialkylamine solutions in well-mixed meso-scale flow reactors

The continuous flow synthesis of a range of organic solutions of N,N-dialkyl-N-chloramines is described using either a bespoke meso-scale tubular reactor with static mixers or a continuous stirred tank reactor. Both reactors promote the efficient mixing of a biphasic solution of N,N-dialkylamine in organic solvent, and aqueous sodium hypochlorite to achieve near quantitative conversions, in 72-100% in situ yields, and useful productivities of around 0.05 mol/h with residence times from 3 to 20 minutes. Initial calorimetric studies have been carried out to inform on reaction exotherms, rates and safe operation. Amines which partition mainly in the organic phase require longer reaction times, provided by the CSTR, to compensate for low mass transfer rates in the biphasic system. The green metrics of the reaction have been assessed and compared to existing procedures and have shown the continuous process is improved over previous procedures. The organic solutions of N,N-dialkyl-N-chloramines produced continuously will enable their use in tandem flow reactions with a range of nucleophilic substrates.

Intermolecular addition reactions of N-alkyl-N-chlorosulfonamides to unsaturated compounds

N-Alkyl-N-chlorosulfonamides add to alkenes under copper(I) catalysis. In reactions of styrene derivatives with terminal double bonds the addition products were obtained in excellent yield and high regioselectivity. Lower yields are obtained in addition r

A versatile metal-free intermolecular aminochlorination of alkenes

New reaction conditions for the rapid and productive intermolecular aminochlorination reaction of alkenes using a combination of chloramine-T and a Br?nstedt acid are described. Upon simple protonation of chloramine-T, conditions for a mild and selective aminochlorination are obtained. In addition, the reaction can proceed to form either of the two possible regioisomers, depending on whether a stoichiometric amount of such an acid activator or acetic acid is used as solvent. The reaction is operative for all different classes of alkenes. A total of over 50 examples is presented to illustrate this concept.

Use of N-chloro-N-methyl-p-toluenesulfonamide in N-chlorination reactions

Second-order rate constants (k2) were determined for the addition of ten nitrogenous organic compounds (benzylamine, 2,2,2- trifluoethylamine chlorhidrate, methylamine chlorhidrate, glycine ethyl ester chlorhidrate, glycine, glycylglycine chlorhidrate, morpholine, pyperidine, pyperazine and dimethylamine) to the N-chloro-N-methyl-p-toluenesulfonamide (NCNMPT) in the formation reaction of N-chloramines in aqueous solution at 25 °C and ionic strength 0.5 M. The series of nucleophiles considered is structurally very varied and covers five pKa units. The kinetic behaviour is similar for all compounds, being the elementary step the transfer of chlorine from the NCNMPT molecule to the nitrogen of the free amino group. These reactions were found first order in both reagents. The values of the rate constants indicate that the more basic amines produce N-chloramines more readily. Rate constants for the nucleophilic attack are shown to correlate with literature data for some of these nitrogenous organic compounds in their reaction with N-methyl-N-nitroso-p-toluenesulfonamide. Both reactions involve that the rate determining step is the attack of nitrogenous compounds upon electrophilic centre (Cl or else NO group). NCNMPT is a particularly interesting substrate, for which has not hitherto been published kinetic information, that allows us to assess the efficiency and the competitiveness of this reaction and compare it with other agents with a Cl+ atom. Copyright 2013 John Wiley & Sons, Ltd. N-chloro-N-methyl-p-toluensulfonamide is a particularly chlorinating agent. The kinetic behaviour has been studied in the formation reaction of N-chloramines using ten nitrogenous compounds. Copyright

HOMOLYTIC DISPLACEMENT AT CARBON CENTRES. XII. REGIOSPECIFIC FORMATION OF N-ALLYL AND N-CYCLOPROPYLCARBINYL SULPHONAMIDES AND OF ALLYL AND CYCLOPROPYL HALIDES IN THE REACTION OF N-HALOGENO COMPOUNDS WITH ORGANOCOBALOXIMES

Several but-3-enyl and allylcobaloximes react regiospecifically with N-chloro-N-methyl sulphonamides to give N-cyclopropylcarbinyl- or rearranged N-allyl-N-methyl sulphonamides, by a process which is believed to take place by the attack of an N-centred radical at the terminal unsaturated carbon of the organic ligand, with displacement of cobaloxime(II).In contrast, N-bromoacetamide and several other N-halogenoimides react regiospecifically to the cyclopropylcarbinyl halide or the rearranged allyl halide by a process in which a halogen-containing free radical species attacks the terminal unsaturated carbon of the organocobaloxime.

Pseudomolecular Rearrangement of O-Ethyl N-Methyl Toluene-4-sulphonimidate to N-Ethyl-N-methyltoluene-4-sulphonamide and its Relevance to the Nucleophilic Properties of Neutral Sulphonamides

Kinetic studies are reported for the pseudo-molecular rearrangement of O-ethyl N-methyl toluene-4-sulphonimidate to N-ethyl-N-methyltoluene-4-sulphonamide in organic solvents at 34-100 deg C.Without catalysts, the rearrangement follows the equation rate = krearr 2, which is indicative of an intermolecular SN2 transalkylation via an ion-pair intermediate: it is accompained by concurrent E2 elimination to N-methyltoluene-4-sulphonamide.The rearrangement is catalysed by electrophilic reagents such as alkyl halides, ZnI2, and HBr where rate = k2 .For alkyl halides, a two-step mechanism via an ionic intermediate applies in which formation of the intermediate by an SN2 reaction between the substrate and alkyl halide is rate limiting.Other catalysts effect rearrangement by forming alkyl halides in an initial rapid reaction with the substrate.The results are discussed in relation to the ambident nucleophilic properties of sulphonamides.It is suggested that, like carboxylic acid amides and phosphinylamides, alkylation occurs most readily at the O-atom of neutral sulphonamides to give a sulphonimidate (kinetic product), which then rearranges in the presence of electrophilic catalysts to give an N-substituted sulphonamide (thermodynamic product).Rearrangement is normally too fast for the isolation of O-alkyl sulphonimidates, but O-aryl analogues can be obtained.