Sodium Carbonate → tert-Butyl [3-(pyridin-3-yl)prop-2-yn-1-yl]carbamate

HRID 1913366노트

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HRID 1913366 반응식
[CH2:1]([NH:4][C:5](=[O:11])[O:6][C:7]([CH3:10])([CH3:9])[CH3:8])[C:2]#[CH:3].C(=O)([O-])[O-].[Na+].[Na+].Br[C:19]1[CH:20]=[N:21][CH:22]=[CH:23][CH:24]=1>C(O)C.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.[Cu]I>[N:21]1[CH:22]=[CH:23][CH:24]=[C:19]([C:3]#[C:2][CH2:1][NH:4][C:5](=[O:11])[O:6][C:7]([CH3:8])([CH3:10])[CH3:9])[CH:20]=1

참가 물질

7

반응물 3

HCID 10340Sodium CarbonateHCID 122863-BromopyridineHCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamate

생성물 1

HCID 70832777tert-Butyl [3-(pyridin-3-yl)prop-2-yn-1-yl]carbamate수율 97.7%

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418397HCID 178418397, 화합물촉매HCID 20074477Dimethoxyethane ethanol용매

반응 조건

온도
90 °C

실험 절차

To a pressure tube containing a magnetic stir bar was added 46 (202 mg, 1.3 mmol) and the vial was purged with argon. To the tube is added a solution of tetrakis(triphenylphosphine)palladium(0) (45 mg, 0.04 mmol) in ethanol/dimethoxyethane (1:1, 2 mL), sodium carbonate(aq) (2 M, 4 mL, 4 mmol), copper(I)iodide (46 mg, 0.24 mmol) and the vial was once again purged with argon. The resultant solution was stirred at room temperature for 5 min when 3-bromopyridine (483 μL, 5 mmol) was added as a neat oil. The tube was purged with argon, capped, heated to 90° C. and stirred for 1 h. The solution was cooled to room temperature and poured into a flask containing anhydrous sodium sulfate (5 g). The solution was dried for 10 min, filtered and the solvent was removed in vacuo. The crude material was chromatographed on silica gel (CH3OH/CHCl3, 5/95, Rf=0.43) to afford the title compound 47 (295 mg, 97% yield) as a brown solid: mp=74-78° C.; 1H NMR (CDCl3) δ 8.63 (m, 1H), 8.51 (m, 1H), 7.67 (m, 1H), 7.22 (m, 1H), 5.05 (br s, 1H), 4.15 (m, 2H), 1.45 (s, 9H); LRMS (ESI) m/z calcd for C13H16N2O2 [M+H]+ 233. found 233; m/z calcd for C9H9N2O2 [M+H−CH2C(CH3)2]+ 177. found 177; m/z calcd for C8H9N2 [M+H−t-Boc]+ 133. found 133.

후처리

  1. additionTo a pressure tube containing a magnetic stir bar
  2. customthe vial was purged with argon
  3. customthe vial was once again purged with argon
  4. additionwas added as a neat oil
  5. customThe tube was purged with argon
  6. customcapped
  7. temperatureThe solution was cooled to room temperature
  8. additionpoured into a flask
  9. additioncontaining anhydrous sodium sulfate (5 g)
  10. customThe solution was dried for 10 min
  11. filtrationfiltered
  12. customthe solvent was removed in vacuo
  13. customThe crude material was chromatographed on silica gel (CH3OH/CHCl3, 5/95, Rf=0.43)

출처 및 근거

ORD 기록
ord-17df983c9d1b4643b8ff6daeb6bf115c
출처 데이터셋
uspto-grants-2013_12
특허 번호
US08609708B2

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