208176-50-5

Upstream product

• 26772-93-0 N-(4-chlorophenyl)-N-methylformamide 
• 2386-64-3 ethylmagnesium chloride 
• 65006-97-5 [(1-chlorocyclopropyl)sulfinyl]benzene 
• 932-96-7 N-methyl(p-chloroaniline) 
• 411235-57-9 cyclopropylboronic acid 
• 208176-51-6 4-chloro-N-(1-ethoxycyclopropyl)-N-methylaniline 

Downstream Products

• 932-96-7 N-methyl(p-chloroaniline) 
• 257946-76-2 N-(p-chlorophenyl) cyclopropylamine 
• 1007-19-8 4-chloro-N-methyl-N-nitrosoaniline 

Relevant academic research and scientific papers

Copper-promoted N-cyclopropylation of anilines and amines by cyclopropylboronic acid

Reaction of anilines, primary and secondary aliphatic amines with cyclopropylboronic acid in dichloroethane in the presence of Cu(OAc)2 (1 equiv.), 2,2′-bipyridine (1 equiv.) and sodium carbonate or sodium bicarbonate (2 equiv.) under air atmos

Reaction of magnesium cyclopropylidene with N-lithio arylamines: a method for generation of α-amino-substituted cyclopropylmagnesiums and a study for their reactivity with electrophiles

Magnesium cyclopropylidene was generated from 1-chlorocyclopropyl phenyl sulfoxide with i-PrMgCl in THF at -78 °C in high yield by a sulfoxide-magnesium exchange reaction. The generated magnesium cyclopropylidene was found to be reactive with N-lithio ary

A mechanistic comparison between cytochrome P450- and chloroperoxidase-catalyzed N-dealkylation of N,N-dialkyl anilines

Most peroxidases use histidine as an axial ligand for heme, while chloroperoxidase (CPO) uses a thiolate, which is similar to the ligand employed by cytochrome P450 (P450). Several studies have also shown that, unlike other peroxidases, CPO is capable of carrying out monooxygenation reactions in a similar manner to P450 in addition to typical peroxidase-like reactions. These observations have been attributed to the similarities of the active-site architecture of the two enzymes. Both enzymes have been shown to efficiently catalyze the oxidative N-dealkylation of amines. The similar magnitudes of the kinetic isotope effects determined for P 450- and CPO-catalyzed N-dealkylation of N,N-dimethylaniline have been used to propose that these reactions proceed through similar mechanisms. In this study, we have examined the mechanism of CPO-catalyzed N-dealkylation using a series of radical probes, 4-chloro-N-cyclopropyl-N-alkylanilines 1-3, which we have recently used in the mechanistic studies of P450, and compared the results with those of P450-catalyzed reactions. The results show that P450- and CPO-catalyzed reactions proceed through distinctly different mechanisms. As previously reported, while P 450-catalyzed reactions appear to proceed through a C α-hydrogen abstraction mechanism, CPO-catalyzed reactions proceed through a single electron/proton transfer (SET/H+) mechanism, similar to reactions catalyzed by Horseradish peroxidase (HRP). Thus, CPO may not be a good mechanistic model for P450-catalyzed N-dealkylations. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

N-Alkyl-N-Cyclopropylanilines as Mechanistic Probes in the Nitrosation of N,N-Dialkyl Aromatic Amines

A group of N-cyclopropyl-N-alkylanilines has been synthesized, and their reaction with nitrous acid in aqueous acetic acid at 0°C was examined. All compounds reacted rapidly to produce the corresponding N-alkyl-N-nitrosoaniline by specific cleavage of the cyclopropyl group from the nitrogen. The transformations were unaffected by the nature of the alkyl substituent (Me, Et, iPr, Bn). The reaction of 4-chloro-N-2-phenylcyclopropyl-N-methylaniline with nitrous acid gave 4-chloro-N-methyl-N-nitrosoaniline (76%), cinnamaldehyde (55%), 3-phenyl-5-hydroxyisoxazoline (26%), and 5-(N-4-chlorophenylmethylamino)-3-phenylisoxazoline (8%). Both the selective cleavage of the cyclopropyl group from the aromatic amine nitrogen and nature of the products derived from the cyclopropane ring support a mechanism involving the formation of an amine radical cation. This step is followed by rapid cyclopropyl ring opening to produce an iminium ion with a C-centered radical which either combines with NO or is oxidized.

Evidence for radical cations in linked mechanisms of N,N-Dialkyl aromatic amine nitration and nitrosative dealkylation

N,N,-Dialkyl aromatic amines react rapidly with nitrous acid to competitively produced a nitrosamine and a nitro compound. The mechanism of nitro compound formation involves a reaction of an amine radical cation with NO2, while the nitrosamine