89979-04-4

Usage

Structure

Consists of a benzene ring with a chloro substituent at the 4-position and a nitromethyl group attached to the alpha carbon

Uses

Building block in organic synthesis, pharmaceutical manufacturing, production of pesticides and agricultural chemicals

Safety precautions

Considered harmful if swallowed, inhaled, or comes into contact with skin

Upstream product

• 75-52-5 nitromethane 
• 104-88-1 4-chlorobenzaldehyde 
• 5468-33-7 1-(4-chlorophenyl)-2-nitroethan-1-one 
• 563-70-2 bromonitromethane 
• 74-11-3 para-chlorobenzoic acid 
• 10364-95-1 1-(4-chloro-benzoyl)-1H-imidazole 
• 555-16-8 4-nitrobenzaldehdye 

Downstream Products

• 85078-25-7 1,1-bis-(4-chloro-phenyl)-2-nitro-ethane 
• 101671-01-6 1-nitro-2-(4-chlorophenyl)ethylene 
• 63701-56-4 (+)-Baclofen hydrochloride 
• 123632-35-9 (R)-(-)-4-(4-chlorophenyl)pyrrolidin-2-one 
• 7099-88-9 4-chlorophenylglyoxylic acid 
• 5468-33-7 1-(4-chlorophenyl)-2-nitroethan-1-one 

Relevant academic research and scientific papers

Revisit to Henry reaction by non conventional heterogeneous and efficient catalyst for nitroalcohol synthesis

A sustainable, green and efficient process for the synthesis of 2-nitro alcohol derivatives from different substituted aromatic aldehydes with nitroalkane by stirring at ambient temperature with high product yield is reported. Adoption of very mild reaction conditions, use of Calcined Eggshell (CES) as natural catalyst and simple workup are expected to contribute to the development of environmentally benign synthetic method for Henry (nitroaldol) reaction. CES is ecologically safe, inexpensive, and attractive heterogeneous base catalyst obtained from renewable resources, thus opening a new perspective for this process. Graphical abstract: [Figure not available: see fulltext.]

Metal-Free Deoxygenation of Chiral Nitroalkanes: An Easy Entry to α-Substituted Enantiomerically Enriched Nitriles

A metal-free, mild and chemodivergent transformation involving nitroalkanes has been developed. Under optimized reaction conditions, in the presence of trichlorosilane and a tertiary amine, aliphatic nitroalkanes were selectively converted into amines or nitriles. Furthermore, when chiral β-substituted nitro compounds were reacted, the stereochemical integrity of the stereocenter was maintained and α-functionalized nitriles were obtained with no loss of enantiomeric excess. The methodology was successfully applied to the synthesis of chiral β-cyano esters, α-aryl alkylnitriles, and TBS-protected cyanohydrins, including direct precursors of four active pharmaceutical ingredients (ibuprofen, tembamide, aegeline and denopamine).

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.

One-Pot Enzyme Cascade Catalyzed Asymmetrization of Primary Alcohols: Synthesis of Enantiocomplementary Chiral β-Nitroalcohols

Biocatalytic asymmetrization of inexpensive and stable primary alcohols to prepare enantioenriched β-nitroalcohols is an important development in green chemistry for the production of chiral pharmaceutical intermediates. Herein, we report a one-pot, two-step cascade reaction sequence in which first benzylic alcohols were oxidized to produce corresponding benzaldehydes using horse liver alcohol dehydrogenase (HLADH). The in situ generated aldehydes were then reacted in a biphasic medium with nitromethane by Arabidopsis thaliana hydroxynitrile lyase (AtHNL) or Baliospermum montanum HNL (BmHNL) catalyzed Henry reaction to produce stereoselective β-nitroalcohols with (R) or (S) configuration, respectively. Using HLADH-AtHNL, (R)-β-nitroalcohols were obtained in up to 64% conversion, and HLADH-BmHNL, (S)-β-nitroalcohols in up to 70% conversion, while in both cases excellent stereoselectivity (up to >99% ee) was achieved. The concept was proven by functionalization of sp3 C?H bond of ten simple achiral benzylic alcohols to enantiocomplementary chiral β-nitroalcohols. (Figure presented.).

Henry type reaction method and product of iron-mediated aldehyde and bromo-nitromethane

The invention discloses a Henry type reaction method and product of iron-mediated aldehyde and bromo-nitromethane. The method comprises the following steps: sequentially adding iron powder and ultra-dry MeCN, and then sequentially adding 1,2-dibromoethane and trimethylchlorosilane to activate the iron powder; adding a catalyst, an additive, bromo-nitromethane and an aldehyde compound, and stirring; performing quenching with a saturated NH4Cl solution, and performing extraction with ethyl acetate; performing washing the extract with a saturated saline solution, drying with anhydrous sodium sulfate, and removing the extract through rotary evaporation to obtain a crude product; and purifying the crude product through silica gel column chromatography to obtain a target product. The method has the advantages of mild reaction conditions, good regioselectivity, easiness in operation, economy and practicability, and no need of preparing an organic metal reagent sensitive to water in advance.

Method for preparing 2-nitroalkyl-1-alcohol compound and application thereof

The invention relates to a method for preparing a 2-nitroalkane-1-alcohol compound and application thereof, and particularly provides a method for preparing the 2-nitroalkane-1-alcohol compound from iron powder/lead dichloride. The process has the advantages of good yield, high diastereoselectivity, wide functional group tolerance and good compatibility.

Copper complexes of 1,4-diazabutadiene ligands: Tuning of metal oxidation state and, application in catalytic C-C and C-N bond formation

Reaction of 1,4-diazabutadiene (p-RC6H4N = C(H)(H)C = NC6H4R-p; R = OCH3, CH3, H and Cl; abbreviated as L-R) with CuCl2·2H2O in methanol at ambient temperature (25 °C) affords a group of doubly chloro-bridged dicopper complexes of type [{CuI(L-R)Cl}2], designated as 1-R. Similar reaction carried out in acetonitrile furnishes a family of doubly chloro-bridged dicopper complexes of type [{CuII(L-R)Cl2}2], designated as 2-R. Molecular structures of 1-OCH3 and 2-OCH3 have been determined by X-ray crystallography. While copper(I) is having a nearly tetrahedral N2Cl2 coordination sphere in 1-OCH3, the N2Cl3 coordination sphere around copper(II) is distorted square pyramidal in nature in 2-OCH3. Isolated 2-R complexes, on dissolution in methanol, are found to undergo facile reduction of the metal center to generate the corresponding 1-R complexes. The 1-R and 2-R complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the 1-R and 2-R complexes shows both metal-centered and ligand centered redox responses. The 1-R complexes are found to efficiently catalyze C-N cross-coupling reactions between arylboronic acids and aryl amines; while the 2-R complexes display notable catalytic efficiency for nitroaldol reactions.

Waste-to-useful: A biowaste-derived heterogeneous catalyst for a green and sustainable Henry reaction

Owing to the depletion of resources coupled with increasing waste generation, the conversion of waste biomass to value-added materials has gained interest. Here, we report for the first time the application of Musa acuminata (banana) peel ash (MAPA) as a heterogeneous catalyst for C-C bond formation via a Henry reaction under solvent-free conditions at ambient temperature. The catalyst was well characterized using different analytical techniques like FT-IR, SEM, TEM-EDS, XRD, XRF, XPS, BET and TGA, along with basicity determination by a Hammett indicator test and titration method. An excellent yield of nitroalcohol was obtained within 15-30 minutes. No dehydrated product was observed. The catalyst used in these studies has the advantage of being a waste material and is hence low-cost, easily prepared, recyclable and environmentally friendly. In addition, the use of a biogenic renewable catalyst, its atom economy, and room temperature and solvent-free reaction conditions and the avoidance of column chromatography make the protocol highly significant from green and sustainable chemistry perspectives.

Synthesis, Characterization and Catalytic Activity of Magnetic KI@Fe3O4 Nanoparticles for Henry Reaction Under Solvent Free Conditions

Abstract: In this paper, we, for the first time reported the synthesis of KI loaded Fe3O4 nanoparticles (KI@Fe3O4 NPs) and investigated its applications in the synthesis of β-nitroalcohol via Henry reaction at room temperature under solvent-free conditions. The synthesized KI@Fe3O4 nanoparticle was characterized by SEM, HRTEM, XRD, XPS, EDX, VSM and FT-IR spectroscopy techniques. The XRD peaks at 2θ = 21.9, 25.65, 33.54, 36.35, 40.97, 42.81, 44.79, 54.43, 57.37, 58.83 and 63.13° corresponds to the formation of crystalline KI@Fe3O4 NPs. The activity of the catalyst by varying the amount of KI loading on Fe3O4 NPs was also investigated. Mild reaction conditions, good yield, short reaction time, solvent-free conditions, easy recoverability and recyclability of the nanocatalysts are the major advantages of our method. Graphical Abstract: [Figure not available: see fulltext.].

Designing of a magnetically separable Fe3O4@dopa@ML nano-catalyst for multiple organic transformations (epoxidation, reduction, and coupling) in aqueous medium

A copper(II) macrocyclic Schiff base complex (ML) was synthesized by condensation between 2,2-dimethylpropane-1,3-diammine and 2,6-diformyl-4-butylphenol with the aim to modify the surface of widely used magnetically separable nanocatalyst Fe3O