59156-55-7

Upstream product

• 67-56-1 methanol 
• 29285-16-3 3-(4-nitrophenyl)-3-oxopropanoic acid 
• 838-57-3 ethyl 4-nitrobenzoylacetate 
• 112378-39-9 2,2-dimethyl-5-(4-nitrobenzoyl)-1,3-dioxane-4,6-dione 
• 105-45-3 acetoacetic acid methyl ester 
• 4231-71-4 1H-1,2,3-benzotriazol-1-yl-4-nitrophenylmethanone 
• 100-19-6 (4-nitrophenyl)ethanone 
• 616-38-6 carbonic acid dimethyl ester 
• 79-20-9 acetic acid methyl ester 
• 619-50-1 4-nitrobenzoic acid methyl ester 
• 38330-80-2 monomethyl monopotassium malonate 
• 62-23-7 4-nitro-benzoic acid 
• 124-38-9 carbon dioxide 
• 74-88-4 methyl iodide 

Downstream Products

• 106098-23-1 (Z)-3-chloro-3-(4-nitrophenyl)acrylaldehyde 
• 106098-40-2 (E)-β-chloro-p-nitrocinnamaldehyde 
• 106098-04-8 (E)-β-chloro-α-(methoxycarbonyl)-p-nitrocinnamaldehyde 
• 106098-08-2 (Z)-β-chloro-α-(methoxycarbonyl)-p-nitrocinnamaldehyde 
• 56377-30-1 Methyl (Z)-β-chloro-p-nitrocinnamate 
• 106098-10-6 methyl (E)-β-chloro-p-nitrocinnamate 
• 106098-09-3 (E)-β-chloro-α-(methoxycarbonyl)-p-nitrocinnamic acid 
• 106098-17-3 (Z)-β-chloro-α-(methoxycarbonyl)-p-nitrocinnamic acid 
• 619-50-1 4-nitrobenzoic acid methyl ester 
• 1203647-62-4 dimethyl 2-hydroxy-2-(4-nitrophenyl)malonate 
• 1361254-03-6 8-(4-nitrophenyl)-2,3,5,6-tetrahydro-1H,4H-11-oxa-3a-aza-benzo[de]anthracen-10-one 
• 25755-90-2 5-methoxy-3-(4-nitrophenyl)isoxazole 
• 39214-83-0 3-(4-nitrophenyl)isoxazol-5(4H)-one 

Relevant academic research and scientific papers

Cu-Catalyzed Synthesis of Benzoxazole with Phenol and Cyclic Oxime

A Cu-catalyzed straightforward synthesis of benzoxazoles from free phenols and cyclic oxime esters is reported. The mild reaction conditions tolerate various electron-withdrawing and electron-donating functional groups on both substrates, affording benzoxazoles in moderate to good yields. With this protocol, large-scale syntheses of Ezutromid and Flunoxaprofe in one or two steps are demonstrated. A catalytic mechanism, which includes Cu-catalyzed amination via inner-sphere electron transfer and consequent annulation, is proposed.

Chiral Vanadyl(V) Complexes Enable Efficient Asymmetric Reduction of β-Ketoamides: Application toward (S)-Duloxetine

High-valent chiral oxidovanadium(V) complexes derived from 3,5-substituted-N-salicylidene-l-tert-leucine were used as catalysts in asymmetric reduction of N-benzyl-β-ketoamides. Among six different solvents, three different alcohol additives, and two different boranes examined, the use of pinacolborane in tetrahydrofuran (THF) with a t-BuOH additive led to the best results at -20 °C. The corresponding β-hydroxyamides can be furnished with yields up to 92percent and an enantiomeric excess (ee) up to 99percent. We have successfully extended this catalytic protocol for the synthesis of an (S)-duloxetine precursor.

Switchable Synthesis of Pyrroles and Pyrazines via Rh(II)-Catalyzed Reaction of 1,2,3-Triazoles with Isoxazoles: Experimental and DFT Evidence for the 1,4-Diazahexatriene Intermediate

4-Aminopyrrole-3-carboxylates and pyrazine-2-carboxylates were synthesized from 5-alkoxyisoxazoles and 1-sulfonyl-1,2,3-triazoles by tuning the Rh(II) catalyst and the reaction conditions. The reaction in chloroform at 100 °C under Rh2(OAc)4 catalysis provides 4-aminopyrrole-3-carboxylates in good yields. The use of Rh2(Piv)4 in refluxing toluene results in the formation of 1,2-dihydropyrazine-2-carboxylates as the main products, which can be converted by a one-pot procedure to pyrazine-2-carboxylates by heating with catalytic amounts of TsOH. According to the NMR and DFT investigations of the reaction mechanism, pyrroles and dihydropyrazines are formed, respectively, via 1,5- and 1,6-cyclization of common (5Z)-1,4-diazahexa-1,3,5-triene intermediates. The influence of the nature of the catalyst on the product distribution is rationalized in terms of the Rh-catalyzed isomerization of a pyrrolin-2-ylium-3-aminide zwitterion, the primary product of 1,4-diazahexatriene 1,5-cyclization.

A mild titanium-catalyzed synthesis of functionalized amino coumarins as fluorescence labels

In contrast to Bronsted and other Lewis acids ClTi(OiPr)3 is especially suited to catalyze the formation of amino-substituted coumarins from aminophenols and functionalized β-oxo esters in a Pechmann condensation. This straightforward protocol allows the synthesis of fluorescence labels and false fluorescent neurotransmitters.

Ambient carboxylation on a supported reversible CO2 carrier: Ketone to β-keto ester

A reversible CO2 carrier (RCC) has been developed to perform carboxylation of ketone to β-ketoester under ambient CO2 pressure and temperature. RCC has been synthesized by immobilizing 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) on methylhydrosiloxane support and reacting with CO2 with 100% degree of functionalisation. RCC is found to be recyclable and shows retention of activity in 5 recycles. CO2 absorption under ambient temperature and desorption at 120°C renders the material suitable for carrying out carboxylation reactions at 25°C with excellent yields. The yield of the reaction can reach up to 100% with TON 200 in 4 h. The extent of the reaction primarily depends upon enol content of the substrate. β-Ketoacid produced during the reaction can be isolated and converted to its corresponding methyl ester derivative by reacting with methyl iodide.

Substitution of acyl for acetyl with N-acylbenzotriazoles catalyzed by samarium triiodide

Catalyzed by samarium triiodide (SmI3), substitution of acyl with N-acylbenzotriazoles for acetyl in acetoacetic esters and acetylacetone proceeds smoothly under neutral conditions in open air, affording the corresponding β-keto esters and β-diketones in good yields. Copyright Taylor & Francis Group, LLC.

Microwave assisted rapid and efficient synthesis of aryl methyl ketones and β-keto esters using Meldrum's acid

Microwave mediated rapid and efficient synthesis of aryl methyl ketones and β-keto esters from acyl Meldrum's acid by hydrolysis and alcoholysis, respectively, has been reported.

Nucleophilic Attacks on Carbon-Carbon Double Bonds. 33. Approaching the Retention Region from the Stereoconvergence Region in Nucleophilic Substitution of (E)- and (Z)-Methyl p-Substituted α-Formyl- and α-(tert-Butoxycarbonyl)-β-halocinnamates

The three E/Z pairs of the highly electrophilic vinyl halides β-chloro-α-(methoxycarbonyl)-p-nitrocinnamaldehydes (6), tert-butyl methyl β-bromo(p-methylbenzylidene)- (21) and β-bromo(p-nitrobenzylidene)malonates (26) were prepared and separated.The structures of (E)-6 and (E)-21 and of intermediates in their synthesis were determined by X-ray crystallography.The stereochemistry of the substitution of the halogen by p-toluenethiolate (TolS-) and p-cresolate (TolO-) ions was investigated by using 1H NMR as the stereochemical probe.Substitution of 6 in Me2SO-d6 by TolS- proceeds with nearly complete stereoconvergence, whereas substitution by TolO- proceeds with high extent of, but not complete, retention of configuration.Cl--assisted (E)-6(Z)-6 isomerization was observed.The substitution of (E)- and (Z)-21 in Me2SO-d6 and of (E)- and (Z)-26 in 95:5 CD3CN-Me2SO-d6 by TolS- proceeds with complete retention of configuration and by TolO- with nearly complete retention.The results are discussed in terms of the multistep route of vinylic substitution via an intermediate carbanion.They corroborate the predictions of the variable transition-state theory in nucleophilic vinylic substitution that stereoconvergence will be observed for highly activated systems and that the stereochemistry should be gradually changed to retention when the electrophilicity of the vinyl halide is decreased and near the borderline when the nature of the nucleophile is changed.Comparison with other systems for which stereoconvergence was observed raises the question of the structural borderline between stereoconvergence and retention, and predictions for the stereochemical outcome in substitutions ofsystems not yet studied are given.Some stereochemical aspects of the condensation, bromine addition, and HBr elimination in the reactions leading to 21 and 26 are briefly discussed.