2'-Bromo-4-chlorophenylacetic acid methyl ester

A solution of 4-chlorophenylacetic acid methyl ester (14.6 g, 79.1 mmol), N-bromosuccinimide (14.4 g, 80.7 mmol), and benzoyl peroxide (1.91 g, 7.89 mmol) in carbon tetrachloride (100 mL) was heated at reflux for 3 h. After the mixture was cooled at room temperature, hexanes (500 mL) was added. The reaction mixture was filtered and the solvent was evaporated in vacuo. The crude material was purified by column chromatography on silica (EtOAc/Hexanes, 15:85) to give the title compound as colorless oil (16.9 g, 63percent): A solution of 4-chlorophenylacetic acid methyl ester (14.6 g, 79.1 mmol), N-bromosuccinimide (14.4 g, 80.7 mmol), and benzoyl peroxide (1.91 g, 7.89 mmol) in carbon tetrachloride (100 mL) was heated at reflux for 3 h. REFERENTIAL Referential Benzoyl peroxide (5 mg) was added to a mixture of methyl 2-(4-chlorophenyl)- acetate [CAS 52449-43-1 ] (5.0 g, 29.7 mmol) and NBS (4.82 g, 27.1 mmol) in CH3CN (80 mL). The mixture was heated under reflux for 48 h and the solvent was evaporated under reduced pressure. The mixture was taken up in cyclohexane/EtOAc 80/20 and the precipitate was filtered off and discarded (succinimide). The filtrate was concentrated under reduced pressure to give methyl 2-bromo-2-(4-chlorophenyl)acetate 3a (7.2 g). The compound was used as such in the next step.General procedure: Methyl 2-hydroxy-2-phenylacetate 7a (5.00 g, 30 mmol) was dissolved in CHClStep A: The initial compound listed in Scheme 1, i.e., 4-chlorophenylacetic acid, is readily available from several commercial sources (e.g., Aldrich and Fluka).fO247f A 5-L Morton reactor equipped with a magnetic stirrer, a pot temperature control, and addition funnel was vented through a gas scrubber and charged with p- chlorophenylacetic acid (720 gm, 4.2 moles) and SOClGeneral procedure: Methyl 2-hydroxy-2-phenylacetate 7a (5.00 g, 30 mmol) was dissolved in CHCl3 (50 ml) and 2 equivalents of PBr3 (8.09 ml, 60 mmol). This was then stirred at r.t. for 4 days. Upon completion the reaction was washed with water (50 ml), dried (MgSO4) and then passed through a silica pad. The CHCl3 was removed to give the title compound as a clear oil, 5.00 g (26 mmol, 75%).REFERENCE Preparation of methyl-(4-chlorophenyl)-bromoacetate Methyl-(4-chlorophenyl)-acetate (102 g, 0.55 mol) was dissolved in carbon tetrachloride (100 ml) and thereto was added N-bromosuccinimide (97.9 g, 0.55 mol). The mixture was refluxed and irradiated with 500W bromo lamp for 5 hours. Then, the mixture was cooled and filtered and the filtrate was concentrated to dryness to obtained methyl-(4-chlorophenyl)bromoacetate (150 g, yield 103%). NMR (CDCl3) deltappm: 3.79 (3H, s), 5.31 (1H, s), 7.3-7.7 (4H, s).

Molecular Weight:263.51
XLogP3:3.2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:3
Exact Mass:261.93962
Monoisotopic Mass:261.93962
Topological Polar Surface Area:26.3
Heavy Atom Count:13
Complexity:179
Undefined Atom Stereocenter Count:1
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes