Ethanol → (5-bromo-1-trityl-1H-pyrazolo[3,4-b]pyridin-3-yl)methanol

HRID 334468ノート

反応式

HRID 334468 の反応式
[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([C:11](OC)=[O:12])=[N:9][N:8]([C:15]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[C:5]2=[N:6][CH:7]=1.CCO.[Li+].[BH4-]>C1COCC1>[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([CH2:11][OH:12])=[N:9][N:8]([C:15]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)([C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:5]2=[N:6][CH:7]=1

参加物

5

反応物 3

HCID 702EthanolHCID 4148881Lithium borohydrideHCID 86701062methyl 5-bromo-1-trityl-1H-pyrazolo[3,4-b]pyridine-3-carboxylate

生成物 1

HCID 86701061(5-bromo-1-trityl-1H-pyrazolo[3,4-b]pyridin-3-yl)methanol収率 100%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of methyl 5-bromo-1-trityl-1H-pyrazolo[3,4-b]pyridine-3-carboxylate (XXII) (4.16 Kg, 8.3 mol) in anhydrous THF (62 L) cooled to 10° C. was added anhydrous EtOH (0.97 L, 16.6 mol) and LiBH4 (271 g, 12.5 mol). The reaction was warmed to room temperature and stirred for 24 hours. The solution was concentrated under vacuum to a volume of 4 L then taken up in DCM (80 L). The pH was then adjusted to 8.0 by dropwise addition of aqueous 0.4N HCl (˜280 L). The organic layer was separated and washed with aqueous 25% NaCl (28 L) and then concentrated under vacuum to a volume of 4 L to produce (5-bromo-1-trityl-1H-pyrazolo[3,4-b]pyridin-3-yl)methanol (XXIII) (3.9 Kg, 8.3 mol, 82.3% purity, 100% assay yield). 1H NMR (DMSO-d6, 400 MHz) δ ppm 4.70 (d, J=6 Hz, 2H), 5.49 (t, J=6 Hz, 1H), 7.19 (d, J=7.2 Hz, 5H), 7.20-7.35 (m, 10H), 8.31 (d, J=2.4 Hz, 1H), 8.51 (d, J=2.4 Hz, 1H); ESIMS found C26H20BrN3O m/z 492.0 (M+Na).

後処理

  1. concentrationThe solution was concentrated under vacuum to a volume of 4 L
  2. additionThe pH was then adjusted to 8.0 by dropwise addition of aqueous 0.4N HCl (˜280 L)
  3. customThe organic layer was separated
  4. washwashed with aqueous 25% NaCl (28 L)
  5. concentrationconcentrated under vacuum to a volume of 4 L

出典と根拠

ORDレコード
ord-1434d5d35e674be0b64c48a960c87683
出典データセット
uspto-grants-2014_11
特許番号
US08883822B2

反応ノート

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