101671-00-5

Basic information

• Product Name: (Z)-1-methyl-4-(2-nitrovinyl)benzene
• Synonyms: (Z)-1-methyl-4-(2-nitrovinyl)benzene
• CAS NO: 101671-00-5
• Molecular Weight: 163.176
• Mol File: 101671-00-5.mol
• Article Data: 101

Chemical Properties

• CAS DataBase Reference: (Z)-1-methyl-4-(2-nitrovinyl)benzene(CAS DataBase Reference)
• NIST Chemistry Reference: (Z)-1-methyl-4-(2-nitrovinyl)benzene(101671-00-5)
• EPA Substance Registry System: (Z)-1-methyl-4-(2-nitrovinyl)benzene(101671-00-5)

Safety Data

• Hazardous Substances Data: 101671-00-5(Hazardous Substances Data)

Upstream product

• 930-88-1 N-methylmaleimide 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 101671-00-5 (E)-2-(4-methylphenyl)-1-nitroethene 
• 5153-67-3 nitrostyrene 
• 3179-10-0 (E)-1-methoxy-4-(2-nitrovinyl)benzene 
• 75-52-5 nitromethane 
• 589-18-4 4-Methylbenzyl alcohol 
• 104-87-0 4-methyl-benzaldehyde 
• 622-96-8 4-methylethylbenzene 
• 766-97-2 4-n-methylphenylacetylene 
• 1133396-08-3 2-(1-(4-methylphenyl)-2-nitroethyl)malononitrile 
• 2826-25-7 2-(4-methylbenzylidene)malononitrile 
• 36393-42-7 4-(4-methylphenyl)benzaldehyde 
• 97585-04-1 ethyl (E)-3-(4-methylphenyl)acrylate 

Downstream Products

• 23211-39-4 rac-(S,S)-1-(1,2-dibromo-2-nitroethyl)-4-methylbenzene 
• 135923-56-7 trans-2-nitro-3-(4-methylphenyl)cyclopropane-1,1-dicarboxylate de diethyle 
• 131001-56-4 4-(4-Methylphenyl)-5-nitropent-1-ene 
• 3261-62-9 2-(p-tolyl)ethylamine 
• 850696-11-6 2-amino-3-(p-tolyl)benzofuran-4-yl acetate 

Relevant articles and documents

Poly(ethylene glycol) supported metal nitrates as well-organized reagents for hunsdiecker conversion of α,β-unsaturated acids to β-nitrostyrenes under solvent and acid-free conditions

Poly(ethylene glycol) (PEG) supported metal nitrates such as ferric nitrate and manganese nitrate were accomplished as well-organized reagents for Hunsdiecker conversion of α,β-unsaturated acids to β-nitrostyrenes under acid-free and solvent free conditions using grindstone technique. However, in the case of unsaturated aliphatic acids, nitro alkene derivatives were obtained as products. PEG-400 was found the best among the other PEGs (PEG-200,300, 400, 600, 3000 and 6000) used in this protocol.

Metal-free, room temperature, acid-K2S2O8 mediated method for the nitration of olefins: An easy approach for the synthesis of nitroolefins

Here, we have developed a simple, room temperature method for the nitration of olefins by using inexpensive sodium nitrite as a source of nitro groups in the presence of trifluoroacetic acid (TFA) and potassium persulfate (K2S2O8) under an open atmosphere. Styrenes and mono-substituted olefins give stereo-selective corresponding E-nitroolefins under optimized conditions, however, 1,1-bisubstituted olefins give a mixture of E- and Z-nitroolefins. The optimized conditions work well with electron-donating, electron-withdrawing, un-substituted and heterocyclic styrenes and mono-substituted olefins and give corresponding nitroolefins with good to excellent yields.

Silica grafted polyethylenimine as heterogeneous catalyst for condensation reactions

Primary amine groups were attached to a silica surface by using α,ω-diamines derivatives and (3-glycidyloxypropyl)-trimethoxysilane activation. The same activation was used to graft polyethylenimine, which also contains secondary and tertiary amine groups. These silica aminated structures were tested as heterogeneous catalysts in nitroaldol condensation with nitromethane, the derivative with the polyethylenimine moiety being the more active catalyst. This catalyst also showed efficiency in the Knoevenagel condensation of benzaldehydes with ethyl cyanoacetate under very mild reaction conditions and showed much the same efficiency when used in consecutive reaction runs. A reaction mechanism with participation of the several amine groups of the catalysts is discussed.

NCC Pincer Ni (II) Complexes Catalyzed Hydrophosphination of Nitroalkenes with Diphenylphosphine

An efficient NCC pincer Ni (II)-catalyzed hydrophosphination of nitroalkenes with diphenylphosphine has been developed. Under the optimized conditions, both (hetero)aromatic and aliphatic nitroalkenes were well tolerated, irrespective of electronic effect, to provide the corresponding products in up to 99% yield.

Catalytic Asymmetric Construction of Tertiary Carbon Centers Featuring an α-Difluoromethyl Group with CF2H-CH2-NH2as the "building Block"

We report here for the first time a novel difluoromethylated ketimine building block condensed by thioisatin and difluoroethylamine, offering efficient access to a broad range of enantioenriched products bearing difluoroethylamine units (27 examples, ≤98% yield, >99% ee) in the presence of quinine-derived squaramide. Further transformation of the intermediate would generate a variety of versatile functional blocks like α-difluoromethyl amines, β-amino acid, and β-diamine with retention of the enantiomeric excess at the difluoromethyl-bound carbon.

Copper-Promoted Regioselective Synthesis of Polysubstituted Pyrroles from Aldehydes, Amines, and Nitroalkenes via 1,2-Phenyl/Alkyl Migration

The facile copper-catalyzed synthesis of polysubstituted pyrroles from aldehydes, amines, and β-nitroalkenes is reported. Remarkably, the use of α-methyl-substituted aldehydes provides efficient access to a series of tetra- and pentasubstituted pyrroles via an overwhelming 1,2-phenyl/alkyl migration. The present methodology is also accessible to non α-substituted aldehydes, yielding the corresponding trisubstituted pyrroles. On the contrary, the use of ketones, in place of aldehydes, does not promote the organic transformation, signifying the necessity of α-substituted aldehydes. The reaction proceeds under mild catalytic conditions with low catalyst loading (0.3-1 mol %), a broad scope, very good functional-group tolerance, and high yields and can be easily scaled up to more than 3 mmol of product, thus highlighting a useful synthetic application of the present catalytic protocol. Based on formal kinetic studies, a possible radical pathway is proposed that involves the formation of an allylic nitrogen radical intermediate, which in turn reacts with the nitroalkene to yield the desired pyrrole framework via a radical 1,2-phenyl or alkyl migration.

Synthesis of pyrimidine-2,4,6-trione derivatives: Anti-oxidant, anti-cancer, α-glucosidase, β-glucuronidase inhibition and their molecular docking studies

This paper describes a facile protocol, efficient, and environmentally benign for the synthesis a series of barbiturate acid substituted at C5 position 3a–o. The desired compounds subjected in vitro for different set of bioassays including against anti-oxidant (DPPH and super oxide scavenger assays), anti-cancer, α-glucosidase and β-glucuronidase inhibitions. Compound 3m (IC50?=?22.9?±?0.5?μM) found to be potent α-glucosidase enzyme inhibitors and showed more activity than standard acarbose (IC50?=?841?±?1.73?μM). Compound 3f (IC50?=?86.9?±?4.33?μM) found to be moderate β-Glucuronidase enzyme inhibitors and showed activity comparatively less than the standard D-saccharic acid 1,4-lactone (IC50?=?45.75?±?2.16?μM). Furthermore, in sillico investigation was carried out to investigate bonding mode of barbiturate acid derivatives.

Supported organic catalysts: Synthesis of (E)-nitrostyrenes from nitroalkanes and aromatic aldehydes over propylamine supported on MCM-41 silica as a reusable catalyst

MCM-41-supported propylamine showed high catalytic efficiency in the nitroaldol condensation between nitroalkanes and aromatic aldehydes.

Synthesis of (E)-nitroolefins via decarboxylative nitration using t-butylnitrite (t-BuONO) and TEMPO

Nitroolefins are usually synthesized using the Henry reaction. Here we report an alternative metal-free decarboxylative nitration protocol for the preparation of the nitroolefins from α,β-unsaturated carboxylic acids using t-butylnitrite (t-BuONO) and TEMPO. α,β-Unsaturated carboxylic acids bearing β-aromatic and β-heteroaromatic substituents gave (E)-nitroolefins exclusively under mild conditions. A radical based pathway has been proposed for this decarboxylative nitration reaction. The Royal Society of Chemistry 2013.

One-Step, Effective, and Cascade Syntheses of Highly Functionalized Cyclopentenes with High Diastereoselectivity

Tetrabutylammonium fluoride works as an effective organocatalyst for the cycloaddition between phenacylmalononitriles and electron-deficient olefins (having substituent groups of NO2, CHO, and COR), providing a facile synthetic route to versatile multifunctionalized cyclopentenes having an allylic quaternary carbon center bearing both cyano and carboxamide groups with high yields and high diastereoselectivity. Preliminary studies reveal that these functionalized cyclopentenes are convenient precursors for making α-cyano-functionalized cyclopentadienone oximes.

Silver(I)-catalyzed denitrative trifluoromethylation of β-nitrostyrenes with CF3SO2Na

A novel and convenient approach to the synthesis of substituted β-trifluoromethyl styrenes via a silver(I)-catalyzed denitrative trifluoromethylation with CF3SO2Na under relatively mild conditions has been developed. This protocol delivered excellent stereoselectivity and showed wide substrate tolerance.

Solid-phase organic synthesis of (E)-1-nitroalkenes based on polystyrene-supported selenonitromethane

A facile method for solid-phase organic synthesis of (E)-1-nitroalkenes from polystyrene-supported selenonitromethane has been developed. Polymer-supported organic reagents are useful for the rapid preparation of small organic molecules.

K2S2O8-mediated nitration of alkenes with NaNO2 and 2,2,6,6-tetramethylpiperidine-1-oxyl: Stereoselective synthesis of (E)-nitroalkenes

A transition-metal-free nitration of alkenes with NaNO2 in the presence of K2S2O8 and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is developed. The transformation exhibits a broad substrate scope and good functional group tolerance, thus providing a new and expedient protocol for stereoselective synthesis of (E)-nitroalkenes with moderate to good yields. Moreover, the nitration processes of (E)- and (Z)-stilbene are also studied: even though the proportion of substrates is different, the E/Z ratio of the products is basically the same. Based upon experimental observations, a possible reaction mechanism is proposed.

The yeast-mediated reduction of nitrostyrenes in organic solvent systems

A range of nitrostyrenes have been reduced with dried baker's yeast in an organic solvent system. It was found that the reduction proceeded smoothly to give the corresponding nitroalkanes in good yield and with higher efficiency than the corresponding aqueous reaction system. No evidence for reduction of the nitro group was observed. In the case of β-methyl nitrostyrenes, racemic mixtures were formed, and it was shown that this is not due to racemization of the product.

Cu(NO3)2-catalyzed nitrodecarboxylation of α,β-unsaturated acids: facile synthesis of (E)-nitroolefins under additive-free conditions

Abstract: An additive-free, facile, efficient, and ecofriendly protocol for synthesis of (E)-nitroolefins via nitrodecarboxylation of α,β-unsaturated acids has been developed. Cu(NO3)2 was used as both nitrating agent and catalyst. Furthermore, the presented methodology offers several advantages such as easily accessible and stable substrates, inexpensive catalyst, high to excellent yield, short reaction time, and simple posttreatment procedure. Graphical Abstract: [Figure not available: see fulltext.]

Stereoselective Synthesis of Alkenyl Silanes, Sulfones, Phosphine Oxides, and Nitroolefins by Radical C-S Bond Cleavage of Arylalkenyl Sulfides

A radical-mediated approach has been introduced for the C-S bond activation of arylalkenyl sulfides. The protocol provides an efficient approach for the generation of various alkenes including alkenyl silanes, sulfones, phosphine oxides, and nitroolefins. In most cases, these radical substitutions are performed under metal-free conditions with stereospecificity.

Metal-free radical trifluoromethylation of β-nitroalkenes through visible-light photoredox catalysis

A catalytic method for functional group interconversion is immensely important in modern sciences. Here, we report an efficient catalytic conversion of nitroalkenes to highly stereoselective 1-trifluoromethylalkenes at room temperature. This unprecedented metal-free photocatalytic strategy is simple and operates under visible-light irradiation using the commercially available CF3 source.

Clay-supported copper nitrate (claycop): A mild reagent for the selective nitration of aromatic olefins

A straightforward and highly selective method has been developed for the nitration of a wide variety of aromatic and aliphatic olefins by using a clay-supported copper nitrate (Claycop) and a catalytic amount of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, an inexpensive and mild reagent system. High conversions and exclusive E-selectivity, together with the environmentally benign nature of the Claycop reagent, make this a green method and an attractive alternative to established methods. Georg Thieme Verlag Stuttgart. New York.

Skeletally Tunable Seven-Membered-Ring Fused Pyrroles

We describe a copper-mediated method that enables the synthesis of seven-membered-ring fused pyrroles (7-mrFPs). The protocol proceeds via an in situ spiro-intermediate ring expansion and tolerates a library of 7-mrFP derivatives with a broad range of functional groups in a simple step with tangible parameters and substrate adaptations. These rare 7-mrFPs are now accessible on a millimolar scale, and selected examples exhibit high antioxidant activity.