46417-99-6

Upstream product

• 3156-41-0 1-nitro-4-[(E)-2-nitroeth-1-enyl]benzene 
• 99-81-0 4-Nitrophenacyl bromide 
• 62-23-7 4-nitro-benzoic acid 
• 555-16-8 4-nitrobenzaldehdye 
• 18731-47-0 1-(4-nitrophenyl)-2-nitroethanol 
• 75-52-5 nitromethane 
• 10364-96-2 N-(4-nitrobenzoyl)imidazole 
• 4231-71-4 1H-1,2,3-benzotriazol-1-yl-4-nitrophenylmethanone 
• 955558-85-7 4-nitro-3-(4-nitro-phenyl)-5-phenyl-isoxazole 
• 7559-38-8 1-(2-bromo-2-nitrovinyl)-4-nitrobenzene 
• 7647-01-0 hydrogenchloride 
• 509-14-8 tetranitromethane 
• 74812-79-6 1-(4-nitrophenyl)-1-trimethylsilyloxyethylene 

Downstream Products

• 75-52-5 nitromethane 
• 62-23-7 4-nitro-benzoic acid 
• 563-70-2 bromonitromethane 
• 1313263-26-1 (R,Z)-1-methoxy-5-nitro-1-oxo-4-phenylpent-2-en-2-yl 4-nitrobenzoate 
• 619-50-1 4-nitrobenzoic acid methyl ester 

Relevant academic research and scientific papers

Efficient Synthesis of α-Ketothioamides From α-Nitroketones, Amines or DMF and Elemental Sulfur Under Oxidant-Free Conditions

We have developed a practical, general protocol for denitration of readily available α-nitroketones with sulfur and amines to access a broad range of α-ketothioamides under mild conditions. Such a reaction proceeds under metal-, oxidant-, and catalyst-free conditions to provide synthetically useful α-ketothioamides. Furthermore, the mild reaction conditions tolerate a wide range of substrates especially for the synthesis of aliphatic α-ketothioamides which are rarely reported.

Imidazolium-Based Ionic Network as a Robust Heterogeneous Catalyst in Synthesis of Phenacyl Derivatives

A new imidazolium-based poly(ionic liquid) has been synthesized and used as a robust heterogeneous catalyst for the preparation of phenacyl derivatives by an SN2 reaction of different phenacyl bromides with a broad range of nucleophiles. The products are obtained in high yields under mild conditions. The catalyst can be recycled efficiently.

Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones

We report here the stereoselective bioreduction of α-nitro ketones catalyzed by ketoreductases (KREDs) with publicly known sequences. YGL039w and RasADH/SyADH were able to reduce 23 class I substrates (1-aryl-2-nitro-1-ethanone (1)) and ten class II substrates (1-aryloxy-3-nitro-2-propanone (4)) to furnish both enantiomers of the corresponding β-nitro alcohols, with good-to-excellent conversions (up to >99%) and enantioselectivities (up to >99% ee) being achieved in most cases. To the best of our knowledge, KRED-mediated reduction of class II α-nitro ketones (1-aryloxy-3-nitro-2-propanone (4)) is unprecedented. Select β-nitro alcohols, including the synthetic intermediates of bioactive molecules (R)-tembamide, (S)-tembamide, (S)-moprolol, (S)-toliprolol and (S)-propanolol, were stereoselectively synthesized in preparative scale with 42% to 90% isolated yields, showcasing the practical potential of our developed system in organic synthesis. Finally, the advantage of using KREDs with known sequence was demonstrated by whole-cell catalysis, in which β-nitro alcohol (R)-2k, the key synthetic intermediate of hypoglycemic natural product (R)-tembamide, was produced in a space-time yield of 178 g L?1 d?1 as well as 95% ee by employing the whole cells of a recombinant E. coli strain coexpressing RasADH and glucose dehydrogenase as the biocatalyst.

Formation of new C-O and C-N bonds via base promoted Csp2-Csp3 bond cleavage of α-nitro ketone

A catalyst free protocol has been developed for nucleophilic Csp2-Csp3 bond cleavage of α-nitroketone in the presence of potassium carbonate to create new C-O and C-N bonds. A series of different substituted α-nitroketones could be selectively cleaved and converted into corresponding esters and tosylamides in the presence of alcohols and bromamine-T, respectively.

Simple route to multisubstituted tetrahydropyrimidines

Abstract As part of our ongoing investigation into the synthetic application of nitroenamines several new densely substituted pyrimidine and pyrrolo-pyrimidine derivatives were prepared. Thus, 2-nitromethylenepyrrolidine and some open chain nitroenamines of phenyl-(2-nitro-1-phenyl-vinyl)-amine type were reacted with ethyl glyoxylate and a substituted aniline usually in a one-pot procedure to furnish the key intermediates for a subsequent cyclization. These compounds including a molecular fragment of 1,3-diamine type were subjected to a simple ring closure with formaldehyde to give the title compounds in good yields. The protocol reported has the advantages of mild reaction conditions, easy workup and inexpensive reagents. In an attempted removal of the 4-methoxy-phenyl protecting group from the 4-methoxy-phenyl substituted hexahydropyrrolo[1,2-c]pyrimidine derivative, an unexpected periodic acid mediated ring cleavage and phenyl group migration was discovered. The structures of the synthesized new compounds were confirmed by spectral data, and, particularly, the hindered rotation and the unusual 1H NMR characteristics of 4-(4-nitro-phenyl)-but-3-enoic acid ethyl ester derivative were discussed.

Asymmetric Rh(II)-catalyzed cyclopropanation of alkenes with diacceptor diazo compounds: P -methoxyphenyl ketone as a general stereoselectivity controlling group

Different diacceptor diazo compounds bearing an α-PMP-ketone group were found to be effective carbene precursors for the highly stereoselective Rh2(S-TCPTTL)4-catalyzed cyclopropanation of alkenes (EWG = NO2, CN, CO2Me). The resulting products were readily transformed into a variety of biologically relevant enantiopure molecules, such as cyclopropane α- and β-amino acid derivatives. Different mechanistic studies carried out led to a rationale for the high diastereo- and enantioselectivity obtained, where the PMP-ketone moiety was found to play a critical role in the stereoinduction process. Additionally, the use of catalytic amounts of achiral Lewis bases to influence the enantioinduction of the reactions developed is documented.

Phenylation reaction of α-acylnitromethanes to give 1,2-diketone monooximes: Involvement of carbon electrophile at the position a to the nitro group

The generality and the effects of substituents on phenylation reactions of α-acylnitromethanes catalyzed by trifluoromethanesulfonic acid have been studied. α-Aroylnitromethanes afforded benzil monooximes in good yield. In the case of aliphatic α-acylnitromethane, a similar phenylation reaction proceeded, but the yield of the phenylated 1,2-dione monooxime was low. These phenylation reactions represent examples of the generation of carbocation electrophiles at the α-position of a nitro group. Georg Thieme Verlag Stuttgart - New York.

α-nitration of ketones via enol silyl ethers. Radical cations as reactive intermediates in thermal and photochemical processes

Highly colored (red) solutions of various enol silyl ethers and tetranitromethane (TNM) are readily bleached to afford good yields of α-nitro ketones in the dark at room temperature or below. Spectral analysis show the red colors to be associated with the intermolecular 1:1 electron donor-acceptor (EDA) complexes between the enol silyl ether and TNM. The formation of similar vividly colored EDA complexes with other electron acceptors (such as chloranil, tetracyanobenzene, tetracyanoquinodimethane, etc.) readily establish enol silyl ethers to be excellent electron donors. The deliberate irradiation of the diagnostic (red) charge-transfer absorption bands of the EDA complexes of enol silyl ethers and TNM at -40 °C affords directly the same α-nitro ketones, under conditions in which the thermal reaction is too slow to compete. A common pathway is discussed in which the electron transfer from the enol silyl ether (ESE) to TNM results in the radical ion triad [ESE?+, NO2?, C(NO2)3-]. A subsequent fast homolytic coupling of the cation radical of the enol silyl ether with NO2? leads to the α-nitro ketones. The use of time-resolved spectroscopy and the disparate behavior of theisomeric enol silyl ethers of α- and β-tetralones as well as of 2-methylcyclohexanone strongly support cation radicals (ESE?+) as the critical intermediate in thermal and photoinduced electron-transfer as described in Schemes 1 and 2, respectively.

Facile Preparation of α-Nitroketones from Enol Silyl Ethers

Treatment of enol silyl ethers with the mild nitrating agent tetranitromethane gives good yields of α-nitroketones at room temperature and below.

A New Method for the Preparation of α-Nitroacetophenones

Treatment of readily available substituted β-nitrostyrenes with tert-butyl hydroperoxide and butyllithium gives synthetically useful α-nitroacetophenones in good yield.