13432-70-7

Upstream product

• 104-87-0 4-methyl-benzaldehyde 
• 105-34-0 methyl 2-cyanoacetate 
• 203861-67-0 (Z)-N-(4-methylbenzylidene)methylamine N-oxide 
• 3395-83-3 4-methylbenzaldehyde dimethylacetal 
• 372-09-8 cyanoacetic acid 
• 7677-24-9 trimethylsilyl cyanide 
• 7515-16-4 methyl 3-(4-methylphenyl)prop-2-ynoate 
• 203861-67-0 N-methyl-4-tolylnitrone 

Downstream Products

• 135923-65-8 E-2-cyano-2-methoxycarbonyl-3-(4-methylphenyl)cyclopropane-1,1-dicarboxylate de diethyle 
• 120811-08-7 3-acetyl-5-amino-6-cyano-2-methyl-6-methoxycarbonyl-7-(p-methylphenyl)-4-phenyl-6,7-dihydro-4H-pyrano<2,3-b>pyridine 

Relevant academic research and scientific papers

Synthesis of (E)-α,β-unsaturated carboxylic esters derivatives from cyanoacetic acid via promiscuous enzyme-promoted cascade esterification/Knoevenagel reaction

A new enzymatic protocol based on lipase-catalyzed cascade toward (E)-α,β-unsaturated carboxylic esters is presented. The proposed methodology consists of elementary organic processes starting from acetals and cyanoacetic acid leading to the formation of desired products in a cascade sequence. The combination of enzyme promiscuous abilities gives a new opportunity to synthesize complex molecules in the one-pot procedure. Results of studies on the influence of an enzyme type, solvent, and temperature on the cascade reaction course are reported. The presented methodology provides meaningful qualities such as significantly simplified process, excellent E-selectivity of obtained products and recycling of a biocatalyst.

trans-Selective hydrocyanation of ynoates, ynones and ynoic acids catalyzed by nucleophilic phosphines

trans-Selective hydrocyanation of ynoates and ynones in the presence of TMSCN and an alcohol additive are catalyzed by nucleophilic phosphines. The trisubstituted E-olefin products of anti-addition of hydrogen cyanide to the alkyne are produced with high regio- and stereoselectivity. The alcohol additive reacts with TMSCN to produce hydrogen cyanide in situ. Ynoic acids undergo the phosphine catalyzed hydrocyanation in the presence of TMSCN under aprotic conditions only. In these reactions, TMSCN reacts with the acid to generate hydrogen cyanide and the silyl ester which, unlike the acid, undergoes phosphine catalyzed hydrocyanation and gives the stereo-defined E-2-cyano-acrylic acids after work up.

Aza-Wittig Reaction with Nitriles: How Carbonyl Function Switches from Reacting to Activating

Transformations of α-EWG-substituted (electron-withdrawing group, EWG) γ-azidobutyronitriles proceeding via unusual aza-Wittig reactions between the phosphazene and nitrile functions and affording pyrrole-derived iminophosphazenes were developed. α-EWGs w

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.

A convenient synthesis of pyrimidinone and pyrimidine containing bisheteroarenes and analogs

The synthesis of pyrimidinone containing bisheteroarenes (3) and related analogs (9 and 10) by the reaction of active methylenes or substituted methyl acrylate with nitrogen containing precursors viz. amidines, or thiourea in water as well as other organic solvents was studied. Synthesized compounds have further been explored for the synthesis of diversified pyrimidines 4, 6-8, 11, 12 and 14 through a sequential approach. This journal is the Partner Organisations 2014.

Tandem Knoevenagel-[3+2] cycloaddition-elimination reactions: One-pot synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles

Sodium azide has been found to catalyse Knoevenagel condensation between aromatic aldehyde and cyano compound with active methylene hydrogens and this has led to a successful route for the one pot synthesis of 4,5-disubstituted 1,2,3-(NH)-triazoles from a

Optically active mixed unsymmetric imine platinum(II) complexes - Utilization of the liberated imines for further syntheses of mixed imine-diazadiene complexes and of (E)-cyanoalkenes

Treatment of trans-[PtCl2(NCR)2] (1) {R = CH 2CO2Me (1a), Ph (1b)} with (R*)-camphor oxime (C9H16)C=NOH (2) gives access to the optically active mixed imine-nitrile complexes trans-(R*)-[PtCl2{NH=C(R)ON= C(C9H16)}(NCR)] (4), which, on reaction with ketoximes R1R2C=NOH (3) {R1 = R2 = Me (3a), C4H8 (3b)}, give the chiral unsymmetric bis(imine) complexes trans-(R*)-[PtCl2{NH=C(R)ON=C(C9H 16)}{NH=C(R)-ON=CR1R2}] (6) in moderate yields. An alternative route involves the reaction of the starting complexes 1 with ketoximes 3 to give the mixed imine-nitrile complexes trans-[PtCl 2{NH=C(R)ON=CR1R2}(NCR)] (5), followed by reaction of the latter with (R*)-camphor oxime (2) to afford products 6 in similar yields. Treatment of complexes 1 or 4 with two or one equivalent of 2, respectively, gives the symmetrical bis-(imine) complexes trans-[PtCl 2{NH=C(R)ON=C(C9H16)}2] (7). These reactions are accelerated by microwave irradiation to afford, in better yields (71-50%), the same products. The new optically active diimine compounds NH=C(R)ON=C-(C9H16) (8) are quantitatively liberated upon reaction of complexes 7 with a diphosphane. The chiral diimino ester 8a (R = CH2CO2Me) acts as a protic nucleophile and efficiently couples with the coordinated nitrile in 4 to give the new optically active, mixed, unsymmetric imine-1,3-diaza-1,3-diene complexes trans-(R*,R*) -[PtCl2{NH=C(R)ON=C(C9H16)}{NH= C(R)N=C(CH 2CO2Me)ON=C(C9H16)}] (9). Diimino ester 8a with an acidic α-methylene group also reacts with acyclic nitrones -O+N(Me)=C(H)R′ (10) to afford stereoselectively the (E)-cyanoalkenes (N≡C)C(CO2Me)=C(H) R′ (11) {R′ = 4-MeC6H4 (11a), 2,4,6-Me 3C6H2 (11b)}. All of these compounds were characterized by IR and NMR (1H, 13C, and 195Pt for metal complexes) spectroscopy, ESI-MS or FAB-MS, elemental analysis, and X-ray diffraction analysis (for 5c and 7b). Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Stereospecific synthesis of polysubstituted E-olefins by reaction of acyclic nitrones with free and platinum(II) coordinated organonitriles

(Chemical Equation Presented) Free nitriles NCCH2R (1a R = CO2Me, 1b R = SO2Ph, and 1c R = COPh) with an acidic α-methylene react with acyclic nitrones -O+N(Me)= C(H)R′ (2a R′ = 4-MeC6Hsub

CATALYSIS OF THE KNOEVENAGEL CONDENSATION.

Xonotlite alone or made more basic by doping of potassium t-butoxide catalyses the title reaction between aromatic aldehydes and malononitrile or alkyl cyanoacetates.At ambient temperatures, this procedure specifically gives high yields of E olefinic Knoe