3-Bromobenzamide

In a round-bottomed two-neck flask 820 mg 3-bromobenzoic acid (4.0 mmol) were suspended in 14 mL of a 6: 1 DCM/MeCN mixture under argon and 600 mg HOBt (4.44 mmol) and 861 mg EDOHCI (4.4 mmol) were added under stirring. After 10 min the mixture became clear and was cooled to 0°C in an ice bath. In a round-bottomed flask 1.64 g NaOH (40 mmol) were added to 2.8 mL of a 28 percent NHGeneral MW procedure: A mixture of Sc(OTf)General procedure: Under an argon atmosphere, liquid NH3 (25 mL) was condensedin a two-neck round-bottom flask immersed in a dry ice coolingbath and equipped with a dry ice reflux condenser. Aldehyde(7.34 mmol) was added, and the resulting solution (or suspension)was stirred for 1 h. KMnO4 (7.34 mmol, 1.16 g) was added, the cooling bath was removed, and the reaction mixture wasstirred for another hour with gentle reflux of NH3. Na2SO3 (22.0mmol, 2.78 g) was added, the reflux condenser was removed, and the NH3 was allowed to evaporate spontaneously. The darkbrownresidue was treated with 6 M HCl (30 mL), and theresulting precipitate was filtered, washed with H2O (100 mL)and sat. aq NaHCO3 (20 mL). All products were recrystallizedfrom EtOH.General procedure: Under an argon atmosphere, liquid NH3 (25 mL) was condensedin a two-neck round-bottom flask immersed in a dry ice coolingbath and equipped with a dry ice reflux condenser. Aldehyde (7.34 mmol) was added, and the resulting solution (or suspension)was stirred for 1 h. KMnO4 (7.34 mmol, 1.16 g) was added, the cooling bath was removed, and the reaction mixture wasstirred for another hour with gentle reflux of NH3. Na2SO3 (22.0mmol, 2.78 g) was added, the reflux condenser was removed, and the NH3 was allowed to evaporate spontaneously. The darkbrownresidue was treated with 6 M HCl (30 mL), and theresulting precipitate was filtered, washed with H2O (100 mL)and sat. aq NaHCO3 (20 mL). All products were recrystallizedfrom EtOH.General procedure: Aldehyde (0.5mmol), NHGeneral procedure: Aldoxime (0.25 mmol), cobalt acetate(II) tetrahydrate (6.2 mg, 0.025 mmol), 2-nitro-1-naphthol (9.5 mg, 0.05 mmol) and acetonitrile/H2O (0.01 + 0.24 mL, 4 v/vpercent of acetonitrile in water) were added to an oven-dried vial. The mixture was vigorously stirred at 80 °C for24 h and then diluted with ethyl acetate. Solvent was removed in vacuo, and the desired product was purified and isolated by silica gel column chromatography (ethyl acetate/n-hexane).General procedure: To a 45 mL glass-lined autoclave, 1 (0.5 mmol), Pd(OAc)General procedure: To a stirred solution of half-sandwich ruthenium complex (0.25molpercent) in 2.0mL of isopropanol were added NaOH (0.3mmol) and benzonitrile (0.3mmol) followed by stirring for 4h at 353K. After completion of the reaction (monitored by TLC), the resulting solution was evaporated to dryness at reduced pressure. The crude products loaded directly onto a column of silica gel and purified by column chromatography to yield the corresponding amides [15].Step 54a: 3-Bromobenzamide (Compound 0601-142)To a solution of m-bromobenzonitrile (2 g, 10 mol) in DMSO (6 mL) was added 30percent HStep 54a: 3-Bromobenzamide (Compound 0601-142)[0425]To a solution of m-bromobenzonitrile (2 g, 10 mol) in DMSO (6 mL) was added 30percent HTo a solution of DMSO (6mL) in m- bromobenzonitrile (2g, 10mol), with the addition of 30percent H2O2 (5g, 13mmol) and K2CO3 at 0 , and the mixture was stirred for 30 minutes at room temperature. The mixture was filtered and poured into water and the solid was washed with water, dried, The compound was prepared 0601-142 as a white solid solid (1.8g, 82percent).General procedure: Ni NPs/HT (0.05 g) is placed in a heavy-walled pressure tube, followed by the addition of water (4 ml) and benzonitrile (1 mmol), and the reaction mixture is vigorously stirred at 120 °C in an oil bath for the specified time in tables. The progress of the reaction in each case was monitored by TLC analysis. After completion of the reaction, the reaction mixture is extracted with ethyl acetate, after the extraction, the catalyst is removed by filtration, and the filtrate is cooled to 0 °C, and white crystals are precipitated from the filtrate. The crystalline product was obtained by simple filtration and dried in vacuo at room temperature to give analytically amide product. In cases where the product not precipitated out, the reaction mixture was extracted with ethyl acetate, subsequent purification by column chromatography on silica gel provided amide product.#10;#10;3-Bromobenzoic acid amide. To a solution [OF 3-BROMOBENZONITRILE (0. 91] g, 5 mmol) in dioxane (19 mL), [NABO3 4H2O] (2.12 g, 13.78 mmol) and [HA0] (19 mL) were added. The mixture was stirred at [80 C] 16 hours (h), cooled, added [OF H2O] and extracted with [CH2CK.] The combined organic layers were dried over [NA2S04] and evaporated. Purification of the residue by column chromatography (hexane/EtOAc 2: 8) and recrystallization gave the desired product as colorless tablets. Yield 80percent (EtOH). Mp: [156-7 C] (lit. [156 C)] (Pearson, D. E. et al., J. Org. [CLTEM., ] 28: 3147-3149, (1963) ). MS [(EI)] : mlz 199 (M+); 183 (100percent).General procedure: A sealed tube equipped with a magnetic stirring bar was charged with styrene 1 (1.0mmol), NBS (2.0 mmol) and water (2.0mL) at room temperature. The resulting mixture was heated to 80 °C for 2h. After disappearance of the reactant (monitored by TLC), reaction mixture was cooled to room temperature. To this reaction mixture molecular iodine (2.2 mmol) and 30percent aq. ammonia solution or n-butylamine (10 mmol) were added and it was heated to 80 °C for 1h. After completion of the reaction (monitored by TLC), saturated NaWater (10 ml), sodium carbonate (4.76 g) and tetrakistriphenylphosphine palladium (866 mg) were added in that order to a dimethoxyethane (50 ml) solution containing General procedure: Oxalylchloride (30 mmol) was added dropwise to a solution of 3 (10 mmol) in 1, 2-dichloroethane(25 mL) and the mixture was heated to reflux for 6h under nitrogen atmosphere.Excess oxalylchloride and 1, 2-dichloroethane was evaporated under reducedpressure to afford the crude intermediate4.In a round-bottomed two-neck flask 820 mg 3-bromobenzoic acid (4.0 mmol) were suspended in 14 mL of a 6: 1 DCM/MeCN mixture under argon and 600 mg HOBt (4.44 mmol) and 861 mg EDOHCI (4.4 mmol) were added under stirring. After 10 min the mixture became clear and was cooled to 0C in an ice bath. In a round-bottomed flask 1.64 g NaOH (40 mmol) were added to 2.8 mL of a 28 % NH4OH solution (20 mmol) and the resulting gaseous NH3 was bubbled into the reaction vessel after passing through a NaOH trap. After NH3-bubbling had ceased, the mixture was concentrated under reduced pressure, taken-up in AcOEt (60 mL), washed with 5 % KHSO4 (2x30 mL), H20 (20 mL), 5 % NaHC03 (3x20 mL) and brine (20 mL), dried over Na2SO4, filtered and evaporated to dryness under reduced pressure. 700 mg Into a 5000-mL -necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen was placed a solution of 3-bromobenz0ic sold (100 g, 497 mmol) in tetrahydrofuran (2000 mL), followed by the addition o£jV, N-carbonyldiimidazole (120.9 g, 746 mmol) in several batches ¾t 0G. The resulting solution was stirred overnight at room temperature, then NH3 (g) was bubbled slowly into the reaction mixture at <10C for about 6 hours. The resulting mixture was concentrated under vacuum. The residue was dissolved in DCM (2 L) then washed with 5% HCl (2x 1000 mL) and aqueous sodium carbonate (3x 1000 mL). The organic phase was dried over anhydrous sodium sulfate and concentrated under vacuum to give General procedure: 1 mmol of benzoic acid, 3 ml of 25-28% aqueous ammonia, and cesium carbonate were added to a microwave reactor.0.2 mmol and 0.01 mmolTetrabutylammonium bromide was reacted at a microwave power of 120 W for 20 min.Extracted with ethyl acetate, concentrated under reduced pressure, and the product was recrystallized from ethanol.A white solid was obtained in 97% yield.General procedure: Preparation of the general method: Add 0.5 mmol of olefin to water (3 mL) containing 1% (by volume of water) Tween-80.1, 3-Dibromo-5, 5-dimethylhydantoin 0.75 mmol was added under stirring.It was then heated to 60 degrees Celsius and stirred for 2 h.The reaction solution was cooled to room temperature.Thereto was added 1.25 mmol of iodine and 1.5 mL of aqueous ammonia(If it is to prepare a secondary or tertiary amide, The organic amine was used instead of ammonia water and stirring was continued for 1 h at room temperature.Add 10 mL saturated sodium sulfite solution was added to the reaction mixture, and then extracted three times with ethyl acetate, the organic layer was separated, concentrated under reduced pressure to remove the organic solvent, separation by column chromatography or by recrystallization, to give the product. Benzamide Using styrene as raw material, prepared by the general method, the yield is 83%;General procedure: To a slurry of 3-bromo-4-methylbenzoic acid (2.53 g, 85% purity; 10 mmol) in CH2Cl2(20 mL) at 0 C., under N2, was added oxalyl chloride (0.91 mL; 10.5 mmol), followed by dropwise addition of DMF (0.04 mL; 0.5 mmol). The mixture was stirred 5 min at 0 C., 15 min at rt, and then heated at reflux under N2for 1 h. The mixture was cooled, and poured into NH4OH (30 mL; ca. 30% NH3). Precipitated solids were collected by filtration and purified by flash chromatography (EtOAc/hexanes), affording the title compound as a colorless solid.

Molecular Weight:200.03
XLogP3:1.6
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:1
Exact Mass:198.96328
Monoisotopic Mass:198.96328
Topological Polar Surface Area:43.1
Heavy Atom Count:10
Complexity:138
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes