Sodium Carbonate → 5-Nitro-2-(2,2,6,6-tetramethyl-3,6-dihydro-2H-pyran-4-yl)-pyridine

HRID 456003

반응식

HRID 456003 반응식
[CH3:1][C:2]1([CH3:19])[CH2:7][C:6](B2OC(C)(C)C(C)(C)O2)=[CH:5][C:4]([CH3:18])([CH3:17])[O:3]1.C([O-])([O-])=O.[Na+].[Na+].[Li+].[Cl-].Br[C:29]1[CH:34]=[CH:33][C:32]([N+:35]([O-:37])=[O:36])=[CH:31][N:30]=1>C(COC)OC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[N+:35]([C:32]1[CH:33]=[CH:34][C:29]([C:6]2[CH2:7][C:2]([CH3:1])([CH3:19])[O:3][C:4]([CH3:17])([CH3:18])[CH:5]=2)=[N:30][CH:31]=1)([O-:37])=[O:36]

참가 물질

7

반응물 4

HCID 10340Sodium CarbonateHCID 782402-Bromo-5-nitropyridineHCID 433294Lithium ChlorideHCID 467380002,2,6,6-Tetramethyl-3,6-dihydro-2H-pyran-4-boronic acid pinacol ester

생성물 1

HCID 576665155-Nitro-2-(2,2,6,6-tetramethyl-3,6-dihydro-2H-pyran-4-yl)-pyridine수율 83%

시약·촉매·용매 2

HCID 178418397HCID 178418397, 화합물촉매HCID 80711,2-Dimethoxyethane용매

반응 조건

온도
80 °C

실험 절차

2,2,6,6-Tetramethyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-3,6-dihydro-2H-pyran (as prepared in the previous step) (18.5 g, 0.069 mol) was dissolved in dimethoxyethane (DME) (350 mL). The resulting solution was treated with 2 M Na2CO3 (280 mL, 0.560 mol), LiCl (5.00 g, 0.110 mol) and 2-bromo-5-nitropyridine (14.0 g, 0.060 mol). The resulting mixture was degassed by sonication for 30 min under Ar and then Pd(PPh3)4 (8.00 g, 6.90 mmol) was added and the reaction heated at 80° C. under Ar overnight. The reaction mixture was allowed to cool to RT and extracted with EtOAc (3×150 mL). The residue was purified on silica gel with 2-10% EtOAc:hexane to obtain the title compound as a pale yellow solid (15.2 g, 83%). 1H-NMR (CDCl3; 400 MHz): δ 9.40 (d, 1H, J=2.8 Hz), 8.45 (dd, 1H, J=8.8, 2.8 Hz), 7.59 (d, 1H, J=8.8 Hz), 6.90 (t, 1H, J=1.6 Hz), 2.5 (d, 1H, J=1.6 Hz), 1.40 (s, 6H), 1.34 (s, 6H).

후처리

  1. customThe resulting mixture was degassed by sonication for 30 min under Ar
  2. temperatureto cool to RT
  3. extractionextracted with EtOAc (3×150 mL)
  4. customThe residue was purified on silica gel with 2-10% EtOAc

출처 및 근거

ORD 기록
ord-dd9cf3a83da04bdfa445c75036224dbb
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08497376B2

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