60826-12-2

Basic information

• Product Name: methyl 3-(4-chlorophenyl)-2-nitropropionate
• Synonyms: methyl 3-(4-chlorophenyl)-2-nitropropionate
• CAS NO: 60826-12-2
• Molecular Weight: 243.647
• Mol File: 60826-12-2.mol
• Article Data: 4

Chemical Properties

• CAS DataBase Reference: methyl 3-(4-chlorophenyl)-2-nitropropionate(CAS DataBase Reference)
• NIST Chemistry Reference: methyl 3-(4-chlorophenyl)-2-nitropropionate(60826-12-2)
• EPA Substance Registry System: methyl 3-(4-chlorophenyl)-2-nitropropionate(60826-12-2)

Safety Data

• Hazardous Substances Data: 60826-12-2(Hazardous Substances Data)

Upstream product

• 2483-57-0 methyl 2-nitroacetate 
• 622-95-7 4-chlorobenzyl bromide 
• 104-88-1 4-chlorobenzaldehyde 
• 420100-57-8 α-nitro-β-(4-chlorophenyl)acrylic acid methyl ester 

Downstream Products

• 114858-65-0 2-[(E)-Benzyloxyimino]-3-(4-chloro-phenyl)-propionic acid methyl ester 
• 114858-64-9 2-Benzyl-3-(4-chloro-phenyl)-2-nitro-propionic acid methyl ester 

Relevant articles and documents

Formation of 4H-1,2-benzoxazines by intramolecular cyclization of nitroalkanes. Scope of aromatic oxygen-functionalization reaction involving a nitro oxygen atom and mechanistic insights

In this paper, we deal with the scope and mechanism of the strong Bronsted acid-catalyzed intramolecular cyclization reaction of methyl 3-aryl-2-nitropropionates to give 4H-1,2-benzoxazines. This reaction can be regarded as an oxygen functionalization of the aromatic ring wherein the oxygen atom is derived from the nitro group in the molecule, and it is favored by the presence of electron-withdrawing groups on the benzene ring. The reaction rate is strongly influenced by the acidity of the reaction medium, and the methyl ester group on the α-carbon atom with respect to the nitro group facilitates deprotonation at the α-position to give aci-nitro species in situ. Some correlation was found between the electron-withdrawing ability of the substituents on benzene, represented in terms of Hammett's σp value of the substituents, and the rate of disappearance of the starting substrate leading to the product in trifluoromethanesulfonic acid (TFSA)/trifluoroacetic acid (TFA) medium. This would be because the acidity of the α-proton with respect to the nitro group is influenced by the substituents on the benzene ring. Experimentally, we excluded the 6π electrocyclization mechanism involving deprotonation of the benzyl proton of the protonated aci-nitro species. Alternative cyclization mechanisms involving equilibrating monocationic aci-nitro species bearing O-protonated ester carbonyl group and O-protonated aci-nitro species were calculated to be highly energetically unfavorable. Diprotonated or protosolvative species can reduce the activation energy significantly, and this is consistent with the observed acidity-dependent nature of the cyclization.

4H-1,2-benzoxazines with electron-withdrawing substituents on the benzene ring: Synthesis and application as potent intermediates for oxygen-functionalized aromatic compounds

A new general method for synthesizing functionalized 4H-1,2-benzoxazine derivatives is described. Although 4H-1,2-benzoxazine is one of the fundamental structure of the oxazine group, no general synthetic method for the heterocycle has been established. We found that 3-methoxycarbonyl-4H-1,2-benzoxazine was obtained in good yield when methyl 2-nitro-3-phenylpropionate was treated with an excess amount of trifluoromethanesulfonic acid. This methodology was also applicable for the synthesis of 4H-1,2-benzoxazine rings functionalized with various electron-withdrawing substituents on the benzene ring. Furthermore, we also show that the resulting 4H-1,2-benzoxazines can be used as precursors of functionalized o-quinone methides and multisubstituted phenols. This type of heterocycle can be a potent intermediate to oxygen-fuctionalized aromatic compounds. Copyright