65547-99-1

Upstream product

• 105-56-6 ethyl 2-cyanoacetate 
• 89-61-2 2,5-dichloronitrobenzene 

Downstream Products

• 160292-76-2 3-Amino-4-(4-chloro-2-nitro-phenyl)-2H-isoxazol-5-one 
• 100821-50-9 ethyl 6-chloro-1H-indole-3-carboxylate 
• 17422-33-2 6-chloroindole 
• 160292-71-7 (4-Chloro-2-nitro-phenyl)-(N-hydroxycarbamimidoyl)-acetic acid ethyl ester 
• 154373-06-5 5-Amino-4-(4-chloro-2-nitro-phenyl)-1H-pyrazol-3-ol 

Relevant academic research and scientific papers

Kinetics of proton transfer from 2-nitro-4-X-phenylacetonitriles to piperidine and morpholine in aqueous Me2SO. Solvent and substituent effects on intrinsic rate constants. Transition state imbalances

Rate constants (k1(B)) for the deprotonation of 2-nitro-4-X-phenylacetonitrile, 2-X (X = NO2, SO2CH3, CN, CF3, Br, and Cl) by piperidine and morpholine and for the reverse reaction (k-1(BH)) have been determined in 90% Me2SO- 10% water, 50% Me2SO-50% water, and water (X = NO2, SO2CH3, CN only). Bronsted β(B) values (dlog k1(B)/dpK(a)(BH)), Bronsted α(CH) values (dlog k1(B)/dlog K(a)(CH)), and intrinsic rate constants (log k(o) = log(k1/q) for pK(a)(BH)-p K(a)(CH) + log(p/q) = 0) were calculated from these data. α(CH) is smaller than β(B), implying an imbalance wnich is consistent with a transition state in which delocalization of the negative charge into the 2-nitrophenyl moiety lags behind proton transfer. A consequence of this imbalance is that the intrinsic rate constant decreases with increasing electron withdrawing strength of X. For π-acceptor substituents (NO2, SO2CH3, CN) there is a further decrease in k(o) due to a lag in the delocalization of the charge into X. The intrinsic rate constants depend very little on the Me2SO content of the solvent which is shown to be the result of compensation of mainly two competing factors. One is the stabilization of the polarizable transition state by the polarizable Me2SO which increases k(o); the other is attributed to a lag in the solvation of the developing carbanion behind proton transfer at the transition state which leads to a decrease in k(o).

Active and Recyclable Catalytic Synthesis of Indoles by Reductive Cyclization of 2-(2-Nitroaryl)acetonitriles in the Presence of Co-Rh Heterobimetallic Nanoparticles with Atmospheric Hydrogen under Mild Conditions

A cobalt-rhodium heterobimetallic nanoparticle-catalyzed reductive cyclization of 2-(2-nitroaryl)acetonitriles to indoles has been achieved. The tandem reaction proceeds without any additives under the mild conditions (1 atm H2 and 25 °C). This procedure could be scaled up to the gram scale. The catalytic system is significantly stable under these reaction conditions and could be reused more than ten times without loss of catalytic activity.