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CAS No. : | 262587-05-3 | MDL No. : | MFCD00236233 |
Formula : | C7H5BrF2O | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | NWBDGKNKAFGQQL-UHFFFAOYSA-N |
M.W : | 223.02 | Pubchem ID : | 2737006 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* 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 |
---|---|---|
palladium diacetate; (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl; In toluene; for 16h;Heating / reflux; | A mixture of commercially available 1-boc piperazine (500.1 mg, 2.685 mmol) and commercially available <strong>[262587-05-3]3-difluoromethoxybromobenzene</strong> (598.8 mg, 2.685 mmol) in toluene (20 ml) is placed in a 50 ml three-necked round-bottomed flask made inert with argon, and then the ligand (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (56.850 mg, 91.2 mumol) and palladium(II)acetate (20.4 mg, 91.2 mumol) are added. The reaction mixture is stirred and brought to reflux for 16 hours. After returning to 20 C., the reaction mixture is diluted with water (20 ml) and then extracted with ethyl acetate (2*30 ml). The organic extracts are combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The compound obtained is purified by chromatography on silica gel (AIT cartridge, Ref. FC-25 Si-BP-SUP, 20-40 mum, eluent dichloromethane, flow rate 20 ml/min). The fractions containing the expected compound are combined and then evaporated under reduced pressure. The expected tert-butyl 4-(3-difluoromethoxyphenyl)piperazin-1-ylcarboxylate is isolated (253 mg), the characteristics of which are as follows: LC/MS analysis: tr=4.18 min, M+H+ 329.31 | |
palladium diacetate; (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl; In toluene; for 16h;Heating / reflux; | Step1: A mixture of 500.1 mg of 1-boc piperazine and 598.8 mg of commercial <strong>[262587-05-3]3-difluoromethoxybromobenzene</strong> is placed in 20 ml of toluene in a 50 ml three-necked flask under an inert atmosphere of argon, followed by addition of 56.85 mg of (R)(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and 20.4 mg of palladium(II) acetate. The reaction mixture is stirred at reflux for 16 hours. After cooling to 20 C., the reaction mixture is diluted with water (20 ml) and then extracted with ethyl acetate (2×30 ml). The organic extracts are combined, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The compound obtained is purified by chromatography on silica gel (AIT cartridge, ref. FC-25 Si-BP-SUP, 20-40 mum, dichloromethane eluent, flow rate of 20 ml/min). The fractions containing the expected compound are combined and then evaporated under reduced pressure. 253 mg of tert-butyl 4-(3-difluoromethoxyphenyl)piperazine-1-carboxylate are thus isolated, the characteristics of which are as follows: LC/MS: RT=4.18 min, M+H+ 329.31 (Micromass machine, LCT model, connected to an HP 1100 machine, HP G1315A diode array detector (200-600 nm), Sedex 65 light-scattering detector; data analyzed with the Micromass MassLynx software; separation on a Hypersil BDS C18, 3 mum (50×4.6 mm) column, eluting with a linear gradient of from 5% to 90% of acetonitrile containing 0.05% (v/v) of trifluoroacetic acid (TFA) in water containing 0.05% (v/v) TFA, over 3.5 minutes at a flow rate of 1 ml/min). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With caesium carbonate; In N,N-dimethyl-formamide; at 100℃; for 2h; | Intermediates T18A and T18BT18.1 [0412] l-Bromo-3-(difluoromethoxy)benzene (T18.1). To a solution of 3- bromophenol (commercially available from Sigma- Aldrich, St. Louis, MO, USA) (1.28 g, 7.39 mmol) in DMF (12.0 mL) was added sodium 2-chloro-2,2-difluoroacetate (commercially available from Sigma-Aldrich, St. Louis, MO, USA) (2.82 g, 18.49 mmol) and Cs2CO3 (4.82 g, 14.79 mmol). The reaction mixture was heated at 100C. Gas was released from the reaction so care should be taken. After 2 hours, the reaction was cooled to room temperature then diluted with EtOAc, washed with water and then brine and re- extracted three times with EtOAc. The combined organic layers were dried over magnesium sulfate and then filtered, concentrated, and purified with silica gel chromatography (0-5% EtOAc in hexanes) to yield T18.1 as an oil that was used without further purification (yield 61%). |
61% | With caesium carbonate; In N,N-dimethyl-formamide; at 100℃; for 2h; | l-Bromo-3-(difluoromethoxy)benzene (T7.1). To a solution of 3- bromophenol (available from Sigma Aldrich) (1.28 g, 7.39 mmol) in DMF (12.0 mL) was added sodium 2-chloro-2,2-difluoroacetate (available from Sigma Aldrich )(2.82 g, 18.49 mmol) and cesium carbonate (4.82 g, 14.79 mmol). The reaction mixture was heated at 100C. Gas was released from the reaction so care should be taken. After 2 hours, the reaction was cooled to room temperature then diluted with EtOAc, washed with water and then brine and re-extracted three times with EtOAc. The combined organic layers were dried over magnesium sulfate and then filtered, concentrated, and purified with silica gel chromatography (0-5% EtOAc in hexanes) to yield T7.1 as an oil that was used without further purification (yield 61%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 100℃; for 21h;Inert atmosphere; | 2-(3-(Difluoromethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2- dioxaborolane (T18.2). A stirred mixture of T18.1 (1.00 g, 4.50 mmol), bis(pinacolato)diboron (1.26 g, 4.95 mmol), potassium acetate (1.34 g, 13.70 mmol), and dichloro[l,l'-bis(diphenylphosphino)ferrocene]dichloride palladium(II) DCM adduct (0.17 g, 0.23 mmol) in dry 1,4-dioxane (10.0 mL)was purged three times with argon and placed under vacuum three times. The mixture was heated to 100C and monitored with LC-MS and TLC. After 21 hours, the reaction was cooled to room temperature and then filtered through Celite filter aid. The organic solvent was removed under reduced pressure, and the residue was purified on silica gel (0-10% EtOAc in hexanes) to yield T18.2 as a colorless oil (0.41 g, 34%). 1H NMR (400 MHz, CDCl3) delta ppm 7.67 (1 H, d, J=7.4 Hz), 7.56 (1 H, d, J=2.3 Hz), 7.41 (1 H, m), 7.22 (1 H, dd, J=7.8, 2.3 Hz), 6.73 (1H, t, J= 74 Hz), 1.36 (12 H, s). |
34% | With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 100℃; for 21h;Inert atmosphere; | 2-(3-(Difluoromethoxy)phenyl)-4,4,5,5-tetramethyI-1,3,2- dioxaborolane (T7.2). A stirred mixture of T7.1 (1.00 g, 4.50 mmol), bis(pinacolato)diboron (1.26 g, 4.95 mmol), potassium acetate (1.34 g, 13.70 mmol), and dichloro[l,r-bis(diphenylphosphino)ferrocene]dichloride palladium(II) DCM adduct (0.17 g, 0.23 mmol) in dry 1,4-dioxane (10.0 mL)was purged three times with argon and placed under vacuum three times. The mixture was heated to 100C and monitored with LC-MS and TLC. After 21 hours, the reaction was cooled to room temperature and then filtered through Celite filter aid. The organic solvent was removed under reduced pressure, and the residue was purified on silica gel (0-10% EtOAc in hexanes) to yield T7.2 as a colorless oil (0.41 g, 34%). 1H NMR (400 MHz, CDCl3) delta ppm 7.67 (1 H, d, J=7.4 Hz), 7.56 (1 H, d, J=2.3 Hz), 7.41 (1 H, m), 7.22 (1 H, dd, J=7.8, 2.3 Hz), 6.73 (1H, t, J= 74 Hz), 1.36 (12 H, s). |
With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 90℃; for 21h;Inert atmosphere; | A stirred mixture of l-bromo-3-(difluoromethoxy)benzene (0.56 mL, 4 mmol), bis(pinacolato)diboron (1.21 g, 4.8 mmol), l,l'-bis(diphenylphosphino)ferrocene- palladium dichloride (0.32 g, 0.4 mmol), and potassium acetate (1.18 g, 12 mmol) in dry 1,4-dioxane (10.0 mL) was purged three times with argon and placed under vacuum three times. The mixture was heated to 90 C and monitored with LC- MS and TLC. After 21 h, the reactions were cooled to rt then filtered through celite. The organic solvent was removed under reduced pressure, and the residue was purified on silica gel (0-10% EtOAc in hexanes) to yield a yellow liquid as 2- (3-(difluoromethoxy)phenyl)-4,4,5,5-tetramethyl-l ,3,2-dioxaborolane. 1H NMR (400 MHz, CDC13) delta ppm 7.66 (1 H, d, J=7.2 Hz), 7.54 (1 H, d, J=2.3 Hz), 7.38(1 H, t, J=7.7 Hz), 7.25 (1 H, m), 6.54 (1 H, t), 1.36 (12 H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride;copper; copper(l) chloride; In N,N-dimethyl-formamide; at 0 - 150℃; for 1h; | EXAMPLE 1; Preparation of 2-nitro-5- (3-difluoromethoxyphenylthio) - p-xylene [nitroderivative of formula (III) ]; 4.36 g (0.109 moles) of sodium hydride are sus? pended in 80 ml of N, N-dimethylformamide at 0C. 20 g of 4-nitro-2 , 5-dimethylthiophenol (0.109 moles) dis? solved in 67 ml of N, N-dimethylformamide are added dropwise under stirring. 24.4 g of l-bromo-3- (difluoromethoxy) benzene (0.109 moles) dissolved in 20 ml of N, N-dimethylformamide are then added dropwise; catalytic Cu and CuCl are subsequently added and the reaction temperature is brought to 150 C for 1 h.After GC control, the reaction mixture is cooled to room temperature, filtered on a celite bed, diluted with water and extracted with ethyl acetate. The or? ganic phase is anhydrified with sodium sulfate, and then filtered and evaporated.The product thus obtained is purified on silica gel eluting with hexane/ethyl acetate 9:1. 30 g of the desired product are obtained. GC-MS : M+ = 325 | |
30 g | With copper; sodium hydride; copper(l) chloride; In N,N-dimethyl-formamide; mineral oil; at 0 - 150℃; for 1h; | EXAMPLE 1 Preparation of 2-nitro-5-(3-difluoromethoxyphenylthio)-p-xylene [nitroderivative of formula (III)] 4.36 g (0.109 moles) of sodium hydride are suspended in 80 ml of N,N-dimethylformamide at 0 C. 20 g of 4-nitro-2,5-dimethylthiophenol (0.109 moles) dissolved in 67 ml of N,N-dimethylformamide are added dropwise under stirring. 24.4 g of <strong>[262587-05-3]1-bromo-3-(difluoromethoxy)benzene</strong> (0.109 moles) dissolved in 20 ml of N,N-dimethylformamide are then added dropwise; catalytic Cu and CuCl are subsequently added and the reaction temperature is brought to 150 C. for 1 h. After GC control, the reaction mixture is cooled to room temperature, filtered on a celite bed, diluted with water and extracted with ethyl acetate. The organic phase is anhydrified with sodium sulfate, and then filtered and evaporated. The product thus obtained is purified on silica gel eluting with hexane/ethyl acetate 9:1. 30 g of the desired product are obtained. GC-MS: M+=325 |
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