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Chemical Structure| 494773-35-2 Chemical Structure| 494773-35-2

Structure of 494773-35-2

Chemical Structure| 494773-35-2

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Product Details of [ 494773-35-2 ]

CAS No. :494773-35-2
Formula : C15H21BrN2O2
M.W : 341.24
SMILES Code : O=C(N1CCN(C2=CC=CC=C2Br)CC1)OC(C)(C)C
MDL No. :MFCD08064040

Safety of [ 494773-35-2 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501

Application In Synthesis of [ 494773-35-2 ]

* 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 [ 494773-35-2 ]

[ 494773-35-2 ] Synthesis Path-Downstream   1~4

  • 1
  • [ 494773-35-2 ]
  • [ 628692-15-9 ]
  • [ 1253936-62-7 ]
YieldReaction ConditionsOperation in experiment
54% With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In water; N,N-dimethyl-formamide; at 100℃; for 0.5h;Inert atmosphere; 4-(2-Bromophenyl)-piperazine-l-carboxylic acid, t-butyl ester (10 g, 29.30 mmol) and 2- methoxypyrimidine-5-boronic acid (5 g, 32.48 mmol) are dissolved in DMF (200 mL) under a stream of nitrogen. To this mixture is added a 2M aqueous solution of sodium carbonate (73.26 mL, 150 mmol) followed by bis(triphenylphosphine) palladium (II) chloride (2.06 g, 2.93 mmol). The resulting mixture is allowed to stir at 100 0C for 30 min. A precipitate forms. Water is added and the resulting mixture is filtered to provide a gray colored solid which is air dried. The solid is then re-dissolved in dichloromethane (20 mL) and loaded on a 34Og Biotage SNAP column and eluted with 35percent ethyl acetate in hexanes to provide 4-[2-(2-methoxy-pyrimidin-5-yl)-phenyl]-piperazine-l-carboxylic acid t-butyl ester (5.87 g, 54percent yield).
  • 2
  • [ 494773-35-2 ]
  • [ 480424-70-2 ]
  • [ 1450591-88-4 ]
YieldReaction ConditionsOperation in experiment
59% With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In 1,2-dimethoxyethane; water; at 80℃; for 2.5h;Inert atmosphere; A mixture of 8 (282 mg, 0.83 mmol), <strong>[480424-70-2]4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl acetate</strong> (260 mg, 0.99 mmol), Na2CO3 (261 mg, 2.46 mmol) and Pd(PPh3)2Cl2 (18 mg, 3 mol % Pd) in DME/water (8 mL, 3/1, v/v) was heated at 80 C for 2.5 h under N2 gas. The reaction mixture was poured into saturated aqueous NaHCO3 and extracted with ether. The organic layer was washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure. Purification of the residue by silica gel column chromatography (EtOAc/n-hexane, 1/10, v/v) yielded 10 (193 mg, 59%) as a colorless crystal; mp, 123-124 C. 1H NMR (300 MHz, CDCl3): delta 1.43 (9H, s), 2.31 (3H, s), 2.77 (4H, br), 3.31 (4H, br), 7.01 (1H, d, J = 7.7 Hz), 7.06-7.16 (3H, m), 7.23-7.31 (2H, m), 7.63 (2H, d, J = 8.4 Hz). 13C NMR (75 MHz, CDCl3): delta 21.2, 28.4, 44.1 (br), 51.2, 79.7, 118.7, 121.3, 123.4, 128.6, 129.9, 131.5, 134.4, 138.3, 149.6, 149.7, 154.8, 169.5. FAB-MS: m/z 397 (M+H).
  • 3
  • [ 494773-35-2 ]
  • [ 13616-83-6 ]
  • [ 960203-42-3 ]
YieldReaction ConditionsOperation in experiment
83% Example 7: Preparation of te/t-butyl 4-(2-((2,4-dimethylphenyl)thio)phenyl)piperazine-1 - carboxylate (Mb) from te/t-butyl 4-(2-bromophenyl)piperazine-1 -carboxylate (If) To a solution of te/t-butyl 4-(2-bromophenyl)piperazine-1 -carboxylate If (1 .0 g, 2.93 mmol) in dry THF (10 mL) sBuLi (2.69 mL, 3.22 mmol) was added at -78qC. After stirring for 15 min, solution of Ilia (0.96 g, 3.52 mmol) in dry THF (5 mL) was added at -78C. Obtained reaction mixture was then stirred at room temperature for 18 h, then 20 mL water was added and product was extracted to EtOAc (2 x 10 mL). Combined organic layers were washed with brine (2 x 20 mL), dried over MgS04, and solvent was evaporated to give crude product, which was purified by chromatography (methylcyclohexane/EtOAc) to afford title compound lib as yellowish oil, which crystalized upon standing (0.96 g, 83% yield): H NMR (CDCI3, 500 MHz) δ 1 .51 (s, 9H), 2.33 (s, 3H), 2.37 (s, 3H), 3.02 (m, 4H), 3.63 (m, 4H), 6.53 (dd, J = 1 .4, 7.9 Hz, 1 H), 6.88 (m, 1 H), 7.02-7.05 (m, 2H), 7.08 (m, 1 H), 7.16 (m, 1 H), 7.38 (d, J = 7.8 Hz, 1 H); MS (ESI) mlz. 399 [MH]+.
83% Example 7 Preparation of tert-butyl 4-(2-((2,4-dimethylphenyl)thio)phenyl)piperazine-1-carboxylate (IIb) from tert-butyl 4-(2-bromophenyl)piperazine-1-carboxylate (If) To a solution of tert-butyl 4-(2-bromophenyl)piperazine-1-carboxylate If (1.0 g, 2.93 mmol) in dry THF (10 mL) sBuLi (2.69 mL, 3.22 mmol) was added at -78C. After stirring for 15 min, solution of IIIa (0.96 g, 3.52 mmol) in dry THF (5 mL) was added at -78C. Obtained reaction mixture was then stirred at room temperature for 18 h, then 20 mL water was added and product was extracted to EtOAc (2 x 10 mL). Combined organic layers were washed with brine (2 x 20 mL), dried over MgSO4, and solvent was evaporated to give crude product, which was purified by chromatography (methylcyclohexane/EtOAc) to afford title compound IIb as yellowish oil, which crystalized upon standing (0.96 g, 83% yield): 1H NMR (CDCl3, 500 MHz) δ 1.51 (s, 9H), 2.33 (s, 3H), 2.37 (s, 3H), 3.02 (m, 4H), 3.63 (m, 4H), 6.53 (dd, J = 1.4, 7.9 Hz, 1 H), 6.88 (m, 1 H), 7.02-7.05 (m, 2H), 7.08 (m, 1 H), 7.16 (m, 1 H), 7.38 (d, J = 7.8 Hz, 1 H); MS (ESI) m/z: 399 [MH]+.
  • 4
  • [ 170017-74-0 ]
  • [ 494773-35-2 ]
YieldReaction ConditionsOperation in experiment
74.9% Concentrated sulfuric acid (98%) (7.6 g, 0.077 mol) was dropped slowly into water (180 ml), stirred, and cooled to 0 to 5 C. 4-tert-butoxycarbonyl-1-(2-aminophenyl)piperazine (20.0 g, 0.072 mol) was added slowly into the system and stirred. Sodium nitrite (5.2 g, 0.077 mol) was added into water (20 ml), stirred until clarification, and then slowly dropped into the raw material system while controlling the temperature to 0 to 10 C. After the completion of dropping, the reaction system was raised to room temperature, and stirred for half an hour to form a diazonium salt system. Sodium bromide (41.6 g, 0.288 mol) and cuprous bromide (10.4 g, 0.072 mol) were added into water (80 ml), stirred mechanically, and heated to an internal temperature of about 80 C. Then the aforementioned obtained diazonium salt system was dropped slowly into the system. After the completion of dropping, the reaction was performed for 3 h while maintaining the temperature. Then heating was stopped, and the reaction system was cooled to room temperature. Ethyl acetate (200 ml) was added, stirred for half an hour, and filtered under reduced pressure. The filter cake was washed with ethyl acetate (50 ml). The obtained dark green filtrate was layered. Aqueous phase was extracted with ethyl acetate (200 ml) once. Organic phases were merged, dried with anhydrous sodium sulfate (10.0 g, 0.07 mol), and then filtered under reduced pressure to remove the solids. The filtrates were merged, and distilled to remove acetyl acetate. The residue was distilled under reduced pressure (2 mm Hg), and the distillate in the range of 70 to 80 C. was collected to obtain a pale yellow oil of 18.42 g. The yield was 74.9%; MS+=341.1.
 

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