868-26-8

Basic information

• Product Name: DIMETHYL BROMOMALONATE
• Synonyms: Dimethyl 2-bromomalonate;Propanedioic acid, bromo-, dimethyl ester;DIMETHYL BROMOMALONATE;DIMETHYL BROMOMALONATE, TECH., 90%;Dimethyl bromomalonate ,98%;Dimethyl bromomalonate, 90%, tech.;2-Bromomalonic acid dimethyl ester;Bromomalonic acid dimethyl ester
• CAS NO: 868-26-8
• Molecular Formula: C₅H₇BrO₄
• Molecular Weight: 211.01
• EINECS: 212-775-4
• Product Categories: Pharmaceutical Intermediates;C2 to C5;Carbonyl Compounds;Esters
• Mol File: 868-26-8.mol
• Article Data: 9

Chemical Properties

• Boiling Point: 105-108 °C11 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: Clear colorless to light yellow/Liquid
• Density: 1.601 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0627mmHg at 25°C
• Refractive Index: n20/D 1.460(lit.)
• PKA: 9.25±0.46(Predicted)
• BRN: 971135
• CAS DataBase Reference: DIMETHYL BROMOMALONATE(CAS DataBase Reference)
• NIST Chemistry Reference: DIMETHYL BROMOMALONATE(868-26-8)
• EPA Substance Registry System: DIMETHYL BROMOMALONATE(868-26-8)

Safety Data

• Hazard Codes: C
• Statements: 34-37
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3265 8/PG 2
• WGK Germany: 3
• F: 19
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 868-26-8(Hazardous Substances Data)

Usage

Description

Dimethyl bromomalonate is a clear colorless to light yellow liquid that is involved in various chemical reactions and synthesis processes. It is known for its manganese(III)-promoted free-radical chain addition reaction with olefins, leading to the formation of dimethyl 2-bromoalkylmalonates. Additionally, it can undergo organocatalyzed Michael addition to nitrostyrenes, resulting in the production of synthetically useful nitrocyclopropanes. Dimethyl bromomalonate also reacts with arylnitroso compounds to form N-aryl-C,C-dimethoxycarbonylnitrones.

Uses

Used in Chemical Synthesis:
Dimethyl bromomalonate is used as a reagent in the enantioselective synthesis of nitrocyclopropanes, which are valuable intermediates in the preparation of various pharmaceuticals and agrochemicals. Its ability to undergo manganese(III)-promoted free-radical chain addition with olefins makes it a versatile component in organic synthesis.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, dimethyl bromomalonate is used as a key intermediate in the synthesis of biologically active compounds. Its involvement in the formation of nitrocyclopropanes and other synthetically useful products contributes to the development of new drugs and therapeutic agents.
Used in Organic Chemistry Research:
Dimethyl bromomalonate is utilized as a research compound in organic chemistry, where its unique reactivity and properties are studied to understand various reaction mechanisms and develop new synthetic methodologies. Its ability to participate in organocatalyzed Michael addition and reactions with arylnitroso compounds makes it an interesting subject for scientific investigation.

InChI:InChI=1/C5H7BrO4/c1-9-4(7)3(6)5(8)10-2/h3H,1-2H3

Upstream product

• 67-56-1 methanol 
• 600-31-7 2-bromomalonic acid 
• 108-59-8 malonic acid dimethyl ester 
• 1069-12-1 1,1,2,2-tetramethoxyethylene 
• 3294-60-8 phenyl(tribromomethyl)mercury(II) 
• 17610-29-6 2-Brom-3,3-dimethoxy-acrylsaeure-methylester 
• 6186-89-6 ethyl methyl malonate 
• 205114-96-1 2-Bromo-malonic acid allyl ester methyl ester 

Downstream Products

• 109012-83-1 dimethyl 2-(3-oxo-1,3-diphenylpropyl)malonate 
• 1733-15-9 Tetramethyl ethylenetetracarboxylate 
• 35757-92-7 dimethyl phenylaminomalonate 
• 5417-21-0 dimethyl [benzyl(methyl)amino]propanedioate 
• 62851-38-1 dimethyl (p-bromophenylamino)malonate 
• 53879-32-6 ((1R)-3-benzyl-7-oxo-(1rH,5cH)-4-thia-2,6-diaza-bicyclo[3.2.0]hept-2-en-6-yl)-malonic acid dimethyl ester 
• 77425-48-0 4-benzoylpyridinium bis(methoxycarbonyl)methylide 
• 95360-00-2 dimethyl (p-tolylamino)malonate 
• 111781-63-6 dimethyl 2-((4-nitrophenyl)amino)malonate 
• 87062-26-8 2-Cyan-1,1-cyclopropandicarbonsaeure-dimethylester 
• 22650-26-6 trimethyl cyclopropane-1,1,2-tricarboxylate 
• 95386-97-3 2-(4-Ethoxy-phenylamino)-malonic acid dimethyl ester 
• 59562-41-3 dimethyl 2,4-dinitrophenylmalonate 
• 86162-89-2 dimethyl (2,6-dinitrophenyl)malonate 

Relevant articles and documents

Lipophilic indole mediated chemoselective α-monobromination of 1,3-dicarbonyl compounds

A mild and efficient mono-selective bromination of 1,3-dicarbonyl compounds has been developed using lipophilic indole catalysts. Inexpensive and commercially available N-bromosuccinimide (NBS) was used as the brominating reagent. The selectivity was further enhanced when using stoichiometric amount of 3-bromoindole species. Mechanistic studies reveal that the indole catalyst has dual functions in the mono-bromination process.

Halogenation of carbonyl compounds by an ionic liquid, [AcMIm]X, and Ceric Ammonium Nitrate (CAN)

An ionic liquid, acetylmethylimidazolium halide ([AcMIm]X), in combination with ceric ammonium nitrate promotes halogenations of a wide variety of ketones and 1,3-keto esters at the ?-position. The ionic liquid acts here as reagent as well as reaction medium, and thus the reaction does not require any organic solvent or conventional halogenating agent. The reaction is completely arrested when the radical quencher TEMPO is used. A plausible radical mechanism is also suggested. CSIRO 2007.

Synthesis and decarboxylation of Δ2-cephem-4,4-dicarboxylic acids

Penicillin V was converted in 14 steps into Δ2-cephems having hydrogen at C-3, hydrogen or methyl at C-2, and two methoxycarbonyl, two benzyloxycarbonyl, or one methoxycarbonyl and one benzyloxycarbonyl substituent at C-4. Deprotection of these Δ2-cephem-4,4-dicarboxylic acid esters by alkaline hydrolysis (in the case of methyl esters) or hydrogenolysis (in the case of benzyl esters) led in all cases to rapid decarboxylation of the Δ2-cephem-4,4-dicarboxylic acid or Δ2-cephem-4,4-dicarboxylic acid monoester. With hydrogen at C-2, hydrolysis of the dimethyl ester with 1 equiv of base produced a Δ2-cephem. With 2 equiv of base, and with all compounds having methyl at C-2, hydrolysis or hydrogenolysis afforded 4α-substituted-Δ2-cephems. In contrast, simpler benzyl or methyl acetamidomalonates could be deprotected without difficulty to afford stable malonic acids. Reasons for the differences in ease of decarboxylation were examined using semiempirical (AM1) and ab initio (3-21G) molecular orbital calculations. The decarboxylation barriers of unionized cephem or acetamido malonic acids were found to be high (35-40 kcal mol-1). Although the monoanion of acetamidomalonic acid retained a high barrier, the epimeric monoanions of a Δ2-cephem malonic acid decarboxylated with barriers of only 2 kcal mol-1.