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Chemical Structure| 39959-54-1 Chemical Structure| 39959-54-1

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Chemical Structure| 39959-54-1

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Product Details of [ 39959-54-1 ]

CAS No. :39959-54-1
Formula : C7H9BrClN
M.W : 222.51
SMILES Code : NCC1=CC=CC(Br)=C1.[H]Cl
MDL No. :MFCD00012856
InChI Key :UGEQUCUBWNAUJS-UHFFFAOYSA-N
Pubchem ID :2724980

Safety of [ 39959-54-1 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 39959-54-1 ]

* 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 [ 39959-54-1 ]

[ 39959-54-1 ] Synthesis Path-Downstream   1~3

  • 1
  • [ 24424-99-5 ]
  • [ 39959-54-1 ]
  • [ 171663-13-1 ]
YieldReaction ConditionsOperation in experiment
100% With triethylamine; In dichloromethane; at 20℃; for 16h; Example 19Synthesis of (E)-3-{3'-[(benzoylmethylamino)methyl]-2-butoxybiphenyl-4-yl}-2-methylacrylic acid a-tert-Butyl (3-bromobenzyl)carbamateA solution of 25 g (110 mmol) of 3-bromobenzylamine hydrochloride and 24.5 g (110 mmol) of tert-butyl dicarbonate in 250 mL of dichloromethane in the presence of 15.6 mL (110 mmol) of triethylamine is stirred at room temperature for 16 hours. The reaction medium is washed with water, the phases are separated by settling and the organic phase is dried over sodium sulfate. The solvent is evaporated off and 32.4 g (100%) of tert-butyl (3-bromobenzyl)carbamate are obtained in the form of crystals.
100% In dichloromethane; at 20℃; for 16h; A solution of 25.0 g (0.11 mol, 1 eq.) of 3-bromobenzylamine hydrochloride and of 24.52 g (0.11 mol, 1 eq.) of di(tert-butyl) dicarbonate in 250 ml of dichloromethane in the presence of 15.6 ml (0.11 mol, 1 eq.) of triethylamine is stirred at ambient temperature for 16 hours. The reaction medium is washedwith water and separated by settling, and the organic phase is dried over sodium sulphate. The solvent is evaporated and 32.41 g of tert-butyl (3-bromobenzyl)carbamate are obtained in the form of crystals. Yield = 100%
100% With triethylamine; In dichloromethane; at 20℃; To 224 3-bromobenzylamine hydrochloride (1.0 g, 4.5 mmol) and 212 di-tert-butyl dicarbonate (0.98g, 4.5 mmol) were added 12 dichloromethane (10 mL) and 14 triethylamine (0.63 mL, 4.5 mmol), andthe mixture was stirred at room temperature overnight. To the reaction mixture was added 52 water andthe mixture was extracted with dichloromethane. The organic layer was dried over sodium sulfate, thedesiccant was filtered off, and the solvent was evaporated to give the 225 title compound ( 1.3 g , 4.5mmol, 100%). MS(ESI) m/z 286 (M+H)+
100% With triethylamine; In dichloromethane; at 20℃; To a solution of (3-bromophenyl)methanamine hydrochloride (5.0 g, 23 mmol) and di-fer/-butyl dicarbonate (5.0 g, 24 mmol) in DCM (50 mL) was added triethylamine (3.2 mL, 23 mmol). The reaction was stirred overnight at room temperature. The mixture was washed with H20, and the organic layer was dried Na2S04), filtered, and concentrated to afford Intermediate 19A (6.5 g, quant.). lH NMR (CDC13): delta 7.43 (br s, 1H), 7.41-4.38 (m, 1H), 7.21-7.17 (m, 2H), 4.88 (br s, 1H), 4.30-4.29 (m, 2H), 1.47 (s, 9H).
90% With triethylamine; In methanol; at 20℃; Example 1.1.79: 3-(aminomethyl)benzonitrile; To (3-bromophenyl)methanamine hydrochloride (Aldrich, 4.0 g, 17.97 mmol) in MeOH (35 ml) , triethylamine (5.45 g, 53.91 mmol) was added followed by (Boc)2O (4.7 g, 21.6 mmol). Reaction mixture was stirred overnight at RT and the volatiles are removed on a rotavap under reduced pressure. Then the crude residue was column chromatographed (10% Ethyl acetate/Hexanes) to yield tert-butyl 3-bromobenzylcarbamate in 90% yield.
88% With triethylamine; In dichloromethane; at 20℃; for 18h; 40 g (183 mmol) of di-tert-butyl dicarbonate are added portionwise, at room temperature, to a mixture of 40.7 g (183 mmol) of 3-bromobenzylamine hydrochloride, 26 ml of triethylamine (183 mmol) and 450 ml of dichloromethane. After stirring for 18 hours, the reaction medium is poured into ice-cold water and extracted with dichloromethane. The organic phase is separated out by settling of the phases, dried over magnesium sulphate and evaporated. 46 g of tert-butyl (3-bromobenzyl) carbamate are obtained in a yield of 88%
88% With triethylamine; In dichloromethane; at 20℃; for 18h; 40 g (183 mmol) of di-tert-butyl dicarbonate are added portionwise, at room temperature, to a mixture of 40.7 g (183 mmol) of 3-bromobenzylamine hydrochloride, 26 ml of triethylamine (183 mmol) and 450 ml of dichloromethane. After stirring for 18 hours, the reaction medium is poured into ice-cold water and extracted with dichloromethane. The organic phase is separated out after settling of the phases, dried over magnesium sulphate and evaporated. 46 g of tert-butyl (3-bromobenzyl) carbamate are obtained in a yield of 88%.
86% With sodium hydrogencarbonate; In ethanol; at 20℃; Step a) (3-Bromo-benzyl)-carbamic acid tert-butyl ester (A-25a); 3-Bromo-benzyl amine hydrochloride( 3g, 13,5 mmol) and NaHCO3 (2.3g, 27 mmol) were mixed in ethanol (20 ml). BoC2O (4.4 g, 20.3 mmol) was added and the resulting reaction mixture stirred at room temperature over night. The solvent was evaporated under vacuum and the residue dissolved in EtOAc. The mixture was washed with brine, dried (Na2SOs), filtered and concentrated in vacuo. The crude product was purified by chromatography on a silica column (EtOAc in hexane 1 :10), which gave the title compound (3.3 g, 86%). LCMS m/z 287.22 (M+H)+
76% To a stirred solution of (3- bromophenyl)methanamine hydrochloride (2.0 g, 0.089 mol) in dichloromethane was added triethylamine (1.39 mL, 0.010 mol) and stirred for 10 minutes. After 10 minutes Di-tert- butyldi carbonate (2.35 g, 0.010 mol) was added and stirred for 6h. The reaction mixture was diluted with water and extracted in to dichloromethane. The combined organic layer was washed with water (10 mL), brine (10 mL), dried over anhydrous sodium sulfate and evaporated under reduced pressure. The crude product was purified by combiflash purifier with 18 % ethyl acetate in hexane as an eluent give the title compound as semi solid m/z = 187.9 [M + H]+; Yield: (2.2 g, 76 %).
With triethylamine; In dichloromethane; (a) tert-butyl (3-bromobenzyl)carbamate 40.7 g (183 mmol) of 3-bromobenzylamine hydrochloride, 26 ml of triethylamine (183 mmol) and 450 ml of dichloromethane are introduced into a round-bottomed flask and under a nitrogen stream. 40 g (183 mmol) of di-tert-butyl dicarbonate are added in small quantities at room temperature and the mixture is stirred overnight. The reaction medium is poured into ice-cold water, extracted with dichloromethane, the organic phase decanted off, dried over magnesium sulphate and evaporated off. 46 g (88%) of the expected product are recovered.
With triethylamine; In dichloromethane; (a) tert-Butyl (3-bromo benzyl)carbamate 15 g (67 mmol) of 3-bromobenzylaminehydrochloride, 9.4 ml of triethylamine (67 mmol) and 150 ml of dichloromethane are introduced into a round-bottomed flask under a stream of nitrogen. 15.5 ml (67 mmol) of di-tert-butyl dicarbonate are added portionwise at room temperature and the mixture is stirred for three hours. The reaction medium is poured into ice-cold water and extracted with dichloromethane, and the organic phase is separated out after settling of the phases has taken place, dried over magnesium sulfate and evaporated. 19.3 g (100%) of the expected product are collected.
Preparation 11: tert-Butyl (3-bromobenzyl)carbamate; Triethylamine (6.57L; 46.7 mol) was added to 3-bromobenzylamine hydrochloride (9.9 Kg; 44.5 mol) in ethyl acetate (39.6 L) and the resulting mixture was stirred for 30 minutes at 20 to 25C and was then cooled to 0C. A solution of di-ferf-butyl dicarbonate (10.7 Kg; 49 mol) in ethyl acetate (19.8L) was then added over 30 minutes at such a rate as to maintain the temperature between 0C and 20C. The reaction mixture was then stirred at 20 to 25C for 2 hours, water (29.7 L) was then added and the mixture was stirred vigorously for 10 minutes and then the phases were separated. The ethyl acetate phase was distilled and replaced with heptane under reduced pressure at 35 to 45C to a final volume of approximately 4OL and then the solution was cooled to 00C over 2 hours. The resulting suspension was stirred at O0C for 12 hours, then the product was collected by filtration, washing with heptane (2 x 3.37L) to provide the title compound as a white solid (10.26 Kg).1H NMR (400MHz, CDCI3) delta: 1.46 (s, 9H), 4.25-4.32 (m, 2H), 4.75-4.90 (bs, 1H), 7.16-7.22 (m, 2H), 7.39 (dt, 1H), 7.43 (bs, 1H) ppm.

  • 2
  • [ 39959-54-1 ]
  • [ 171663-13-1 ]
YieldReaction ConditionsOperation in experiment
(a) tert-Butyl (3-bromo benzyl)carbamate In a manner similar to that of Example 1(a), starting with 50 g (220 mmol) of 3-bromobenzylamine hydrochloride, 65.1 g (100%) of the expected product are obtained in the form of a pale brown solid.
  • 3
  • [ 24424-99-5 ]
  • [ 39959-54-1 ]
  • [ 33513-42-7 ]
  • [ 170853-04-0 ]
YieldReaction ConditionsOperation in experiment
[0262] To a solution of 2.0 g of 3-bromobenzylamine hydrochloride in 20 ml of dioxane-water (1:1) was added 1.5 g of NaHCO3 and a solution of 2.2 g of di-t-butyl dicarbonate in 10 ml of dioxane in order at room temperature, and the mixture was stirred at room temperature for 1 day. Water was added to the reaction mixture and the reaction mixture was extracted with EtOAc. The organic layer was dried over anhydrous sodium sulfate and evaporated under reduced pressure to give 3.0 g of a bromo-derivative. The bromo-derivative (3.0 g) was dissolved in 30 ml of THF, to which was added 14 ml of 1.5M butyllithium/hexane solution at -78 C., and the mixture was stirred at the same temperature for 30 minutes. To the resulting solution was added a solution of 1.7 ml of DMF in 10 ml of THF at -78 C., and the mixture was warmed up to -15 C. over 1.5 hours. An aqueous ammonium chloride solution was added to the reaction mixture and extracted with EtOAc. The resulting organic layer was dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography to give 0.89 g of t-butyl 3-formylbenzylcarbamate.
 

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