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Chemical Structure| 142667-04-7 Chemical Structure| 142667-04-7

Structure of 142667-04-7

Chemical Structure| 142667-04-7

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Product Details of [ 142667-04-7 ]

CAS No. :142667-04-7
Formula : C10H9ClO3
M.W : 212.63
SMILES Code : O=C(OC)C1=CC=C(CC(Cl)=O)C=C1

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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 142667-04-7 ]

[ 142667-04-7 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 22744-12-3 ]
  • [ 142667-04-7 ]
YieldReaction ConditionsOperation in experiment
100% With oxalyl dichloride; In dichloromethane; at 20℃; for 4h; Step 2: Synthesis of methyl 4-(2-chloro-2-oxoethyl)benzoate. To a solution of <strong>[22744-12-3]2-(4-(methoxycarbonyl)phenyl)acetic acid</strong> (see Intermediate A, step 1 for synthesis) (5 g, 25.75 mmol) in DCM ( 60 ml) was added dropwise oxalyl chloride (6.6 ml, 77.25 mmol) at room temperature and the mixture was stirred for 4 hours. Concentration afforded product as golden oil (6 g, 109%), which was used directly for next step.
With oxalyl dichloride;N,N-dimethyl-formamide; In dichloromethane; at 20℃; [0271] Ex-12B: 4-Carboxymethyl-benzoic acid methyl ester obtained from Ex-12A (500 mg, 2.57 mmol) and CH2Cl2 (10 mL) were sequentially charged into a clean reaction vessel and the resulting solution was treated with oxalyl chloride (250 muL, 2.87 mmol). A catalytic amount of DMF (1 drop) was then added and the reaction was aged at room temperature overnight. The reaction was concentrated to dryness under reduced pressure and used without further purification.
With oxalyl dichloride; N,N-dimethyl-formamide; In dichloromethane; at 0 - 20℃; for 2h; To a solution of B-2 (15 g, 77.3 mmol) and DMF (1 drop) in anhydrous DCM (150 mL) was added dropwise oxalyl chloride (33 mL, 386.0 mmol) at 0~5C with stirring. After the addition was complete, the mixture was stirred at room temperature for 2 h. TLC (PE/EA = 3/1, quenched with MeOH) indicated that the reaction was complete, the volatiles were evaporated and the residue was diluted with DCM (20 mL), which was used directly for next step.[00166] To a suspension of aluminum trichloride (16.5 g, 123.7 mmol) in anhydrousDCM (80 mL) was added 1, 3-dimethoxybenzene (21.3 g, 154.6 mmol) at 5C, followed by Attorney Docket: 0322.13/PCT above acyl chloride solution. The mixture was stirred at room temperature overnight, poured carefully into icy 1 N HC1 (200 mL) and extracted with EA (150 mL x 3). The combined organic layers were washed with brine (200 mL), dried with anhydrous sodium sulfate, filtered and concentrated to obtain brown oil, which was purified by silica gel column (PE/EA = 5/1) to afford B-3 (12 g, 49.6%) as a yellow solid. MS (ESI): m/z 315.1 [M+l]+.
With oxalyl dichloride; In dichloromethane; at 20℃; Intermediate E: methyl 4-(2-(3-methoxyphenylthio)-2-oxoethyl)benzoate[00234] To a solution of <strong>[22744-12-3]2-(4-(methoxycarbonyl)phenyl)acetic acid</strong> (see IntermediateA, step 1 for synthesis) (3.88 g, 20 mmol) in dry DCM (50 ml) was added dropwise oxalyl chloride (8.4 ml, 100 mmol) at room temperature with stirring. The mixture was stirred at room temperature for 2 hours. The reaction was complete indicated by TLC (PE : EtOAc = 3 : 1, quenched with MeOH). The mixture was concentrated to afford methyl 4-(2-chloro-2- oxoethyl)benzoate (4.5 g) as yellow oil, which was used directly for next step.[00235] To a suspension of aluminum trichloride (2.93 g, 21.96 mmol) in dry CS2 (50 ml) was added 3-methoxybenzenethiol (3.1 g, 21.96 mmol) at 0-5 C, followed by a solution of methyl 4-(2-chloro-2-oxoethyl)benzoate (4.5 g, crude, 21.16 mmol) in dry CS2 (5 ml). The mixture was stirred at room temperature overnight and poured carefully into 1 N icy HC1 (200 ml) and extracted with EtOAc (100 ml x 3). The combined organic layers were washed with water (100 ml x 2) and brine (100 ml), dried over Na2S04, filtered and concentrated. The residue was purified by Combi-Flash (80 g silica gel, start PE/ EtOAc = 10/0 to 1/1 gradient, 50 ml/min, 40 min, 2.0 L total solvent volume) to afford Intermediate E as a yellow solid (2.7 g, 43%). 1H NMR (DMSO- 6 500 MHz TMS): delta 7.95 (d, J = 8.5 Hz, 2H), 7.49 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 8.0 Hz, 1H), 7.02-7.04 (m, 1H), 6.97-6.98 (m, 2H), 4.18 (s, 2H), 3.85 (s, 3H), 3.76 (s, 3H); MS (ESI): m/z 317.1 [M+l]+.
With thionyl chloride; N,N-dimethyl-formamide; In dichloromethane; at 0 - 20℃; for 0.5h; General procedure: The appropriate phenylacetic acid (1.1 mmol) was dissolved in dry DCM (10 mL) and few drops ofDMF were added. The mixture was cooled to 0C and thionyl chloride (160 muL, 2.2 mmol) was addeddropwise. Reaction mixture was stirred at r.t. for 30 minutes. Solvent was evaporated under reducedpressure to obtain the acyl chloride derivative. Acyl chloride (1.1 mmol) was dissolved in dry CH3CN(10 mL) and the solution was cooled to 0C. 2M trimethylsilyl diazomethane (1.5 mL) was addeddropwise. Reaction mixture was allowed warm to room temperature and reaction was monitored withTLC. After disappearing of the starting material (0.5-1 h) the mixture was cooled to 0 C and HBr 33%(1 mL) was added dropwise. The reaction was allowed to warm to room temperature and stirred for 2h.The mixture was poured in water and extracted with AcOEt. The organic phase was washed with water,dried over Na2SO4, filtered and concentrated under reduced pressure. The crude residue was purifiedwith flash chromatography on silica gel, eluting with 30% AcOEt/Hex to give pure compound.

 

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