Hydrochloric Acid → 1-(ethoxymethyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole

HRID 46328

반응식

HRID 46328 반응식
C([Li])CCC.[CH2:6]([O:8][CH2:9][N:10]1[CH:14]=[CH:13][CH:12]=[N:11]1)[CH3:7].C(O[B:19]1[O:23][C:22]([CH3:25])([CH3:24])[C:21]([CH3:27])([CH3:26])[O:20]1)(C)C.[Cl-].[NH4+].Cl>O1CCCC1.C(OC)(C)(C)C.O>[CH2:6]([O:8][CH2:9][N:10]1[C:14]([B:19]2[O:23][C:22]([CH3:25])([CH3:24])[C:21]([CH3:27])([CH3:26])[O:20]2)=[CH:13][CH:12]=[N:11]1)[CH3:7]

참가 물질

9

반응물 5

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 157143991-(ethoxymethyl)-1H-pyrazoleHCID 178418339Butyllithium

생성물 1

HCID 594366031-(ethoxymethyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole수율 78%

시약·촉매·용매 3

HCID 962Water용매HCID 8028Tetrahydrofuran용매HCID 15413tert-Butyl methyl ether용매

반응 조건

온도
-78 °C

실험 절차

Butyl lithium (2.5 M in hexanes, 32.4 mL, 0.0811 mol) was added slowly via syringe to a solution of 1-(ethoxymethyl)-1H-pyrazole (Preparation 338, 9.3 g, 0.074 mol) in anhydrous tetrahydrofuran (100.0 mL) at 0° C. and stirred under nitrogen for 15 minutes and then at room temperature for 30 minutes. The mixture was cooled to −78° C. and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (16.5 mL, 0.0811 mol) was added via syringe. The mixture was warmed to room temperature and stirred under nitrogen for 60 hours. Saturated aqueous ammonium chloride solution (50.0 mL) was added followed by water (150.0 mL). The mixture was poured into tert-butylmethylether (200.0 mL) and the biphasic mixture stirred vigorously for 30 minutes. The aqueous layer was acidified to pH 6 with hydrochloric acid (6.0 M aqueous solution) and extracted with tert-butylmethylether (3×200.0 mL). The combined organics were washed with saturated aqueous sodium chloride solution (100.0 mL) and then stirred with activated charcoal (1 g) for 30 minutes. Magnesium sulphate was added and the mixture filtered through a pad of Celite™, washing with tert-butylmethylether (1 L). Concentration in vacuo afforded the title compound as a brown oil, 14.5 g, 78% yield.

후처리

  1. waitat room temperature for 30 minutes
  2. temperatureThe mixture was warmed to room temperature
  3. stirringstirred under nitrogen for 60 hours
  4. stirringthe biphasic mixture stirred vigorously for 30 minutes
  5. extractionextracted with tert-butylmethylether (3×200.0 mL)
  6. washThe combined organics were washed with saturated aqueous sodium chloride solution (100.0 mL)
  7. stirringstirred with activated charcoal (1 g) for 30 minutes
  8. additionMagnesium sulphate was added
  9. filtrationthe mixture filtered through a pad of Celite™
  10. washwashing with tert-butylmethylether (1 L)
  11. concentrationConcentration in vacuo

출처 및 근거

ORD 기록
ord-12afca548d304101a082beedf6949f74
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08541588B2

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