Sulfuric Acid → [6-(Hydroxymethyl)pyridin-3-yl]methanol

HRID 370435

반응식

HRID 370435 반응식
[N:1]1[CH:6]=[C:5]([C:7](OCC)=[O:8])[CH:4]=[CH:3][C:2]=1[C:12](OCC)=[O:13].[BH4-].[Na+].[Cl-].[Cl-].[Ca+2].OS(O)(=O)=O>CCO>[N:1]1[CH:6]=[C:5]([CH2:7][OH:8])[CH:4]=[CH:3][C:2]=1[CH2:12][OH:13]

참가 물질

6

반응물 4

HCID 1118Sulfuric AcidHCID 254728Diethyl 2,5-pyridinedicarboxylateHCID 4311764Sodium borohydrideHCID 5284359Calcium Chloride

생성물 1

HCID 820251[6-(Hydroxymethyl)pyridin-3-yl]methanol수율 51%

시약·촉매·용매 1

HCID 702Ethanol용매2회

실험 절차

To a solution of 33.5 g (0.15 mol) of diethyl pyridine-2,5-dicarboxylate in 300 mL of absolute EtOH was added 11.4 g (0.3 mol) of NaBH4 in several portions over a 30-min period. Then a solution of 33.3 g (0.3 mol) of anhydrous CaCl2 in 200 ml of EtOH was added dropwise over a 1-h period. The mixture was stirred at room temperature for 16 h, and then it was neutralized with 12 to 13 mL of concentrated H2SO4. The CaSO4, which precipitated, was removed by centrifugation (two EtOH washings). The combined supernatant was concentrated, dissolved in about 10 mL of H2O, and applied to a 4.5×18-cm column of Dowex 50W-X8 cation exchange resin (H+ form). The column was eluted with H2O until the eluate was no longer acidic, and then it was eluted with dilute NH4OH, which removed the 2,5-pyridinedimethanol from the column. Evaporation afforded 10.6 g (51% yield) of 2,5-pyridinedimethanol as a light brown hygroscopic solid: 1H NMR (Me2SO-d6) δ4.55 and 4.59 (2 s, 4, CH2OH), 5.23 (broad s, 2, CH2OH), 7.42 (d, J=8 Hz, 1, 3'--H), 7.72 (dd, J=2 Hz, J=8 Hz, 1, 4--H), 8.42 (d, J=2 Hz, 1, 6'--H).

후처리

  1. customThe CaSO4, which precipitated
  2. customwas removed by centrifugation (two EtOH washings)
  3. concentrationThe combined supernatant was concentrated
  4. dissolutiondissolved in about 10 mL of H2O
  5. washThe column was eluted with H2O until the eluate
  6. washit was eluted with dilute NH4OH, which
  7. customremoved the 2,5-pyridinedimethanol from the column
  8. customEvaporation

출처 및 근거

ORD 기록
ord-ed760393c94e4fd9b01c9a8a64d4c7c2
출처 데이터셋
uspto-grants-1985_07
특허 번호
US04526787

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