Structure of 409110-31-2
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CAS No. : | 409110-31-2 |
Formula : | C8H6BrClO |
M.W : | 233.49 |
SMILES Code : | O=C(Cl)C1=CC(C)=CC=C1Br |
MDL No. : | MFCD09833296 |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxalyl dichloride;N,N-dimethyl-formamide; In dichloromethane; at 0 - 20℃; for 2h; | To a suspension of <strong>[6967-82-4]2-bromo-5-methyl benzoic acid</strong> (1.0 g, 0.00465 mole) in dry dichloromethane (10 mL ) was added oxalylchloride (1.22 mL, 0.013 mole) dropwise at 00C followed by 1-2 drops of N,N-dimethyl formamide. The reaction mixture was then stirred for 2 hours at room temperature and the solvents were evaporated and the product dried under vacuum to yield 2-bromo-5-methylbenzoyl chloride which was used for the next step. To a precooled solution of 2-bromo-5-methyl benzoyl chloride in toluene (5mL) was slowly added a pre-cooled solution of triethylphosphite (1.05 mL, 0.00604 mole) in toluene. The reaction EPO <DP n="85"/>was then left at room temperature for overnight. The solvents were then evaporated on a rotovap. The resultant product was diluted with dichloromethane (50 mL), washed with saturated sodium bicarbonate (NaHCO3, 25 mL), and then dried over magnesium sulfate (MgSO4). Filtration and solvent evaporation provided l .lg of product. Flash chromatography on silica gel using 0%-5% ethyl acetate/dichloromethane followed by drying of the product under high vacuum afforded 0.900 g of (2-bromo-5-methylbenzoyl)phosphonic acid diethyl ester. | |
With oxalyl dichloride; N,N-dimethyl-formamide; In tetrahydrofuran; at 20℃; for 0.75h;Inert atmosphere; | General procedure: To a 100-mL round-bottom flask, flame-dried and cooled under argon containing 40 mL THF was added 2-bromobenzoic acid (1.98 g, 8.25 mmol), followed by 2-3 drops of DMF. Oxalyl chloride (1.02 mL, 11.8 mmol) was then slowly added over 15 min, causing bubbling and the formation of a bright yellow solution. The reaction was stirred for 30 min. To this was added cyclopropylamine (0.8 mL, 11.8 mmol). After 10 min, triethylamine (3.40 mL, 24.6 mmol) was added slowly, forming a faint yellow precipitate. The reaction was stirred overnight (16 h) at ambient temperature. It was then quenched with 10% HCl (50 mL), dissolving the white precipitate, and then transferred to a 250-mL separatory funnel. The layers were separated, and the aqueous layer was extracted with dichloromethane (3×'s, 50 mL each). The combined organics were then washed with brine (50 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give the desired product as an off-white solid. It was used crude in the subsequent methylation step. | |
With thionyl chloride; for 2h;Reflux; Inert atmosphere; | Formylbenzamide 81. A solution of <strong>[6967-82-4]2-bromo-5-methylbenzoic acid</strong> (156 mg, 0.73 mmol, 1.0 equiv) in SOCI2 (5 mL) was stirred at reflux for 2 h. The reaction mixture was concentrated under N2 and the residue was coevaporated with toluene (2 5 mL) to remove all traces of SOCI2. The crude product was dissolved in CH2CI2 (5 mL) and the reaction mixture was cooled to 0 C. A solution of diethylamine (97 mg, 0.14 mL, 1.31 mmol, 1.8 equiv) in CH2CI2 (0.2 mL) was added dropwise, the ice bath was removed and the reaction mixture was stirred at ambient temperature for 2 h. The reaction was quenched with IN aq. HCl (1.5 mL), and the resulting mixture was extracted with CH2CI2 (2 5 mL). The combined organic layers were washed with brine (5 mL), dried over MgS04 and concentrated. Flash column chromatography (silica gel, hexanes:EtOAc 3 : 1 to 2: 1) yielded benzamide 80 as a yellowish solid (194 mg, 0.72 mmol, 98% yield). To a stirred solution of z-PrMgBr (0.85 mL, 1.0 M in THF, 0.85 mmol, 1.2 equiv) in THF (1.0 mL) at 0 C was added -BuLi (0.68 mL, 2.50 M in hexanes, 1.70 mmol, 2.4 equiv). The resulting yellow solution was cooled to -78 C and a solution of bromide 80 (234 mg, 0.72 mmol, 1.0 equiv) in THF (1.0 mL) was added dropwise. After stirring for 1 h at -78 C, DMF (0.23 mL, 2.88 mmol, 4.0 equiv) was added. After stirring for 3 h at -78 C, saturated aq. NH4CI (5 mL) was added and the resulting mixture was allowed to reach ambient temperature. The mixture was extracted with EtOAc (10 mL), the organic layer was dried over MgSO t, concentrated, and purified by column chromatography (silica gel, hexanes:EtOAc = 1 :1) to provide aldehyde 81 (156 mg, 0.71 mmol, 99% yield) as a white powder. 81 : R = 0.42 (silica gel, hexanes:EtOAc 1:2); FontWeight="Bold" FontSize="10" H NMR (500 MHz, CDCI3): delta = 10.01 (s, 1 H), 7.77 (s, 1 H), 7.45 (d, J = 7.7 Hz, 1 H), 7.28 (d, J = 7.7 Hz, 1 H), 3.42 (m, 2 H), 3.13 (m, 2 H), 2.46 (s, 3 H), 1.32 (t, J = 7.1 Hz, 3 H), 1.08 (t, J = 7.2 Hz, 3 H) ppm; HRMS (ESI-TOF): calcd for C15H22 O/ [M+H+]: 280.1543, found 280.1540. |
With thionyl chloride; In N,N-dimethyl-formamide; toluene; at 0 - 80℃; for 2.25h; | General procedure: 2-bromobenzoic acid derivatives (8 mmol), toluene (40 mL) were added to a 100 mL round-bottom flask. After cooled to 0 oC, DMF (0.1 eq., 0.8 mmol) was added to the mixture. SOCl2 (1.2 eq., 9.6 mmol) was slowly added to the flask with more than 10 min. After performed at 0 oC for 5 min, the reaction was warmed to 23 oC for 10 min. At last the mixture was performed at 80 oC for 2 h. After evaporated the solvent and dried by vacuum pump, the crude product of 2,4-dibromobenzoyl chloride derivatives were provided as a oil. After 2,4-dibromobenzoyl chloride derivative (6 mmol) was added to it, the tube evacuated and recharged with N2 for 3 times. Before the mixture was cooled to -78 oC, THF (20 mL) was added to the tube. MeMgCl (6 mmol) was dropwised to the mixture. The reaction was performed for 1h at -78 oC, 2 h at 0 oC, 5 to 10 h at rt. 20 mL water was added to the tube and the mixture was extracted with Et2O (30 mL x 3),dried by anhydrous Na2SO4. Evaporation of the solvent followed by purification on silica gel provided 1-(2-bromophenyl)ethanone derivative, yield 60-70%. | |
With thionyl chloride; for 2h;Reflux; | General procedure: Substituted N'-acetyl-2-bromobenzohydrazides(1a-w) were synthesizedaccording to the procedures reported in theliteratures.[1,2]Thionyl chloride (10 mL) was added tosubstituted 2-bromobenzoic acid (5 mol) in a 50 mL round bottom flask, and the reaction mixturewas refluxed for 2 h. The excess amount of thionyl chloride was removed by distillation. Theresulted acid chloride was dissolved in MeOH (20 mL), and then 40% hydrazine hydrate (3 mL)was added. The mixture was refluxed for 2 h and then cooled to room temperature, and the resulting precipitate was collected, washed with distilled water and recrystallized fromethanol.Subsequently,another acylchloride (2 mmol) was added to a solution of substituted 2-bromobenzohydrazide (1 mmol) and pyridine (2 mmol) in NMP (6 mL), the mixture was stirred for12 h, and the resulting solution was poured into ice water. The solid product was filtered andcrystallized from EtOH to get pure 1a-w. | |
With thionyl chloride; N,N-dimethyl-formamide; for 2h;Reflux; | General procedure: 1 drop of DMF was added to a suspension of 2-bromobenzoic acid (2g, 9.95mmol) in 5ml SOCl2, the mixture was heated under reflux for 2h, then concentrated and diluted with DCM 20ml, concentrated again and re-diluted with DCM 20ml and concentrated. The residue was dissolved in 20ml DCM, added dropwise to a solution of 4-methoxy-2-methylaniline (1.4g, 9.95mmol) and triethylamine (3.43ml, 24.9mmol) in 10ml DCM, and then stirred for 2h. The mixture was concentrated to give brown solid, which was treated with EtOH/H2O (10ml/20ml) to give off-white solid 2.5g, yield: 78.4%. |
Tags: 409110-31-2 synthesis path| 409110-31-2 SDS| 409110-31-2 COA| 409110-31-2 purity| 409110-31-2 application| 409110-31-2 NMR| 409110-31-2 COA| 409110-31-2 structure
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