12413-18-2

Basic information

• Product Name: phenylnitromethane carbanion
• Synonyms: phenylnitromethane carbanion
• CAS NO: 12413-18-2
• Molecular Weight: 136.13
• Mol File: 12413-18-2.mol

Chemical Properties

• CAS DataBase Reference: phenylnitromethane carbanion(CAS DataBase Reference)
• NIST Chemistry Reference: phenylnitromethane carbanion(12413-18-2)
• EPA Substance Registry System: phenylnitromethane carbanion(12413-18-2)

Safety Data

• Hazardous Substances Data: 12413-18-2(Hazardous Substances Data)

Upstream product

• 622-42-4 1-nitro-1-phenylmethane 
• 154077-82-4 C₁₄H₁₂NO₃^(1-) 

Downstream Products

• 1215-07-2 (E)-(1-nitroethene-1,2-diyl)dibenzene 
• 67765-80-4 (+/-)-1,2-dinitro-1,2-diphenylethane 
• 124286-40-4 3-Nitro-1,3-diphenyl-propan-1-one 
• 622-42-4 1-nitro-1-phenylmethane 
• 622-43-5 phenylnitromethane nitronic acid 
• 49595-23-5 dichlorophenylnitromethane 
• 28627-67-0 succinimide anion 
• 104330-12-3 2,2-dimethyl-1-phenyl-1-nitropropane 

Relevant articles and documents

Hydrolysis of substituted α-nitrostilbenes: Dissection of rate coefficients for individual steps in the four-step mechanism. Estimates of intrinsic rate constants and transition-state imbalances

A kinetic study of the hydrolysis of substituted α-nitrostilbenes (NS-Z with Z = 4-Me, H, 4-Br, 3-NO2, and 4-NO2) in 50% Me2SO-50% water (v/v) at 20 °C is reported. The mechanism consists of four steps: nucleophilic addition to NS-Z of water (k1H2O) and OH- (k1OH) to form PhCH(OH)C(Ar)NO2- (TOH-); carbon protonation of TOH- by water (k2H2O), H3O+ (k2H), and buffer acids (k2BH) to form PhCH(OH)CH(Ar)NO2 (TOH0); rapid oxygen deprotonation of TOH0 (KaOH) to form PhCH(O-)CH(Ar)NO2 (TO-); collapse of TO- (k4) into benzaldehyde and arylnitromethane anion. The aci-form of TOH0, PhCH(OH)CH(Ar)NO2H (TOH,aci0), can also be generated as a transient by reaction of TOH- with strong acid. A combination of kinetic experiments involving the reaction of the olefin with water and OH-, the reaction of TOH- with acid, and the reaction of independently synthesized TOH0 with base allowed the dissection of the rate coefficients of most of the individual steps. From the substituent dependence of these rate coefficients, it is concluded that water and OH- addition to NS-Z (k1H2O and k1OH) as well as the collapse of TO- to benzaldehyde and ArCH=NO2- (k4) is characterized by substantial transition-state imbalances, reminiscent of the imbalance observed in the deprotonation of ArCH2NO2. It is also shown that the intrinsic rate constants for the k1OH and k4 steps are low compared to those for the corresponding steps in the hydrolysis of other olefins of the type PhCH=CXY (XY = (H, NO2), (CO)2C6H4, (COO)2C(CHj)2, and (CN)2). This again parallels the behavior in the deprotonation of ArCH2NO2.

Radical and Ionic Reactions of (Benzoylmethyl)mercurials

Photolysis of PhCOCH2HgCl or (PhCOCH2)2Hg yields benzoylmethyl radicals which can be trapped by anions such as Me2C=NO2-, RC(CO2Et)2-, RC(O-)=CH2 or by other electron-rich systems such as (RO)3P, N-methylpyrrole, enamines, or norbornene.Electron transfer from the adduct radicals to the mercurials yields PhCOCH2A from the anions A-, PhCOCH2P(O)(OR)2 from P(OR)3, and the phenacyl derivative from N-methylpyrrole or enamines.Easily oxidized anions such as PhCOCPh2- or PhC(CH3)=NO2- react with PhCOCH2* by electron transfer to yield the dimer derived from the anion.Addition of PhCOCH2* to norbornene yields a substituted 3-benzoylpropyl radical which cyclizes at the ortho position of the benzoyl group to give the α-tetralone derivative.