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Chemical Structure| 850144-81-9 Chemical Structure| 850144-81-9

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Chemical Structure| 850144-81-9

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Product Details of [ 850144-81-9 ]

CAS No. :850144-81-9
Formula : C10H12BrNO
M.W : 242.11
SMILES Code : CC(C)(C1=CC=C(Br)C=C1)C(N)=O
MDL No. :MFCD07700230

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* 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 [ 850144-81-9 ]

[ 850144-81-9 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 850144-81-9 ]
  • [ 2712-78-9 ]
  • [ 75-65-0 ]
  • [ 214973-83-8 ]
YieldReaction ConditionsOperation in experiment
60% (Referential Example 4) Synthesis of 1-bromo-4-(1-tert-butoxycarbonylamino-1-methylethyl)benzene (referential compound 4-1) In an argon stream, 260 g (600 mmol) of [bis(trifluoroacetoxy)iodo]benzene was added, at room temperature with stirring, to a solution of 99 g (410 mmol) of 4-(1-aminocarbonyl-1-methylethyl)-1-bromobenzene (referential compound 2-1) in 1,000 ml of tert-butanol and the mixture was stirred for 30 minutes under a condition of heating to reflux. After that, 100 ml (1,200 mmol) of pyridine was added thereto and the mixture was stirred for 1 hour under the condition of heating to reflux. After the reaction was finished, the reaction solution was concentrated in vacuo, 500 g of a 10 weight% aqueous solution of citric acid was added to the resulting residue and the mixture was extracted with 2,000 ml of toluene. The organic layer was successively washed with a saturated aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate and concentrated in vacuo. n-Hexane (200 ml) was added to the resulting residue and the resulting solid was filtered off and washed with 400 ml of cold n-hexane to give 77 g of the title compound as light brown powder (yield: 60%). Melting point: 92 to 93C Rf value: 0.56 (n-hexane: ethyl acetate = 4:1 (v/v)) Mass spectrum (EI, m/z): 313, 315 (M+) 1H-NMR spectrum (CDCl3, delta ppm): 1.36 (brs, 9H), 1.59 (s, 6H), 4.90 (brs, 1H), 7.24-7.29 (m, 2H), 7.39-7.45 (m, 2H)
60% (Reference Example 4) Synthesis of 1-bromo-4-(1-tert-butoxycarbonylamino-1-methylethyl)benzene (Reference compound 4-1) 260 g (600 mmol) of [bis(trifluoroacetoxy)iodo]benzene was added to a solution of 99 g (410 mmol) of 4-(1-aminocarbonyl-1-methylethyl)-1-bromobenzene (Reference compound 2) in 1000 ml of tert-butanol at room temperature in an argon stream with stirring, and the mixture was stirred for 30 minutes under a condition of heating to reflux. Then, 100 ml (1200 mmol) of pyridine was added thereto and the mixture was stirred for 1 hour under a condition of heating to reflux. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and 500 g of an aqueous solution of 10% by weight of citric acid was added to the resulting residue, and then the mixture was extracted with 2000 ml of toluene. The organic layer was successively washed with a saturated aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure. 200 ml of n-hexane was added to the resulting residue and the resulting solid was collected by filtration and washed with 400 ml of cold n-hexane, whereby 77 g of the title compound was obtained as light brown powder (yield: 60%). Melting point: 92 to 93C Rf value: 0.56 (n-hexane: ethyl acetate = 4: 1 (v/v)) Mass spectrum (EI, m/z): 313, 315 (M+) 1H-NMR spectrum (CDCl3, deltappm): 1.36 (brs, 9H), 1.59 (s, 6H), 4.90 (brs, 1H), 7.24-7.29 (m, 2H), 7.39-7.45 (m, 2H)
  • 2
  • [ 850144-81-9 ]
  • [ 75-65-0 ]
  • [ 214973-83-8 ]
YieldReaction ConditionsOperation in experiment
84% Step 3: Preparation of tert-butyl[1-(4-bromophenyl)-1-methylethyl]carbamate To a suspension of 2-(4-bromophenyl)-2-methylpropanamide (3 g) in tert-butanol (31 mL) was added [bis(trifluoroacetoxy)iodo]benzene (8 g) portionwise at room temperature. The reaction mixture was stirred at reflux temperature for 30 min Pyridine (3 mL) was added to the mixture. After being stirred at reflux temperature for 1 h, the reaction mixture was concentrated to dryness. The residue was dissolved in benzene and washed with 1 M citric acid aqueous solution (2 times), sodium bicarbonate aqueous solution (5 times) then brine. The organics were dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by column chromatography (0-20% ethyl acetate in hexanes) gave the product (3.29 g, 84%). 1HNMR (CDCl3) 400 MHz delta: 7.43 (d, J=8.6 Hz, 2H), 7.27 (d, J=8.6 Hz, 2H), 1.59 (br s, 6H), 1.48-1.05 (m, 9H).
60% 260 g (600 mmol) of [bis(trifluoroacetoxy)iodo]benzene was added to a solution of 99 g (410 mmol) of 4-(1-aminocarbonyl-1-methylethyl)-1-bromobenzene (Reference Compound 2) in 1000 ml of tert-butanol at room temperature in an argon stream with stirring, and the mixture was stirred for 30 minutes under a condition of heating to reflux. Then, 100 ml (1200 mmol) of pyridine was added thereto and the mixture was stirred for 1 hour under a condition of heating to reflux. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and 500 g of an aqueous solution of 10% by weight of citric acid was added to the resulting residue, and then the mixture was extracted with 2000 ml of toluene. The organic layer was successively washed with a saturated aqueous solution of sodium hydrogen carbonate and a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure. 200 ml of n-hexane was added to the resulting residue and the resulting solid was collected by filtration and washed with 400 ml of cold n-hexane, whereby 77 g of the title compound was obtained as light brown powder (yield: 60%). Melting point: 92 to 93 C. Rf value: 0.56 (n-hexane:ethyl acetate=4:1 (v/v)) Mass spectrum (EI, m/z): 313, 315 (M+) 1H-NMR spectrum (CDCl3, deltappm): 1.36 (brs, 9H), 1.59 (s, 6H), 4.90 (brs, 1H), 7.24-7.29 (m, 2H), 7.39-7.45 (m, 2H)
1.2 g With copper(l) chloride; In N,N-dimethyl-formamide; at 20℃; for 5h; To a mixture of tert-butanol (3.5 mL) and CuCl (0.74 g) in DMF (30 mL) there is added a solution of the intermediate obtained above (1.8 g, 7.5 mmoles) in DMF (10 mL). The mixture is stirred at ambient temperature for 5 hours. The reaction mixture is extracted with Et2O. The organic phase is washed with a saturated NaCl solution, dried and concentrated in vacuo. The residue is chromatographed on silica gel (eluant CH2Cl2/AcOEt (100/0 to 95/5)). Intermediate 601 (1.2 g) is obtained in the form of a white solid. 1H NMR (300 MHz; CDCl3): delta 7.45 (d, 2H); 7.30 (d, 2H); 4.90 (m, 1H); 1.60 (s, 6H); 1.35 (broad s, 9H). IR (cm-1): 3265; 1698
 

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