Phosphoric Acid → [3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid

HRID 564471ノート

反応式

HRID 564471 の反応式
Br[C:2]1[CH:3]=[C:4]([CH2:8][O:9][SiH:10]([CH3:12])[CH3:11])[CH:5]=[CH:6][CH:7]=1.C[C:14]([CH3:17])([CH3:16])[CH3:15].[Li]CCCC.[B:23](OCCCC)([O:29]CCCC)[O:24]CCCC.OP(O)(O)=O>C1COCC1>[CH3:15][C:14]([Si:10]([CH3:12])([CH3:11])[O:9][CH2:8][C:4]1[CH:3]=[C:2]([B:23]([OH:29])[OH:24])[CH:7]=[CH:6][CH:5]=1)([CH3:17])[CH3:16]

参加物

6

反応物 4

HCID 1004Phosphoric AcidHCID 12712Tributyl borateHCID 137331256{[(3-Bromophenyl)methyl]oxy}(dimethyl)silane 2,2-dimethylpropaneHCID 178418339Butyllithium

生成物 1

HCID 57813382[3-({[(1,1-Dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]boronic acid収率 74.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

To the solution of {[(3-bromophenyl)methyl]oxy}(dimethyl)silane-2,2-dimethylpropane (1:1) (100.0 g, 331.9 mmol) in THF (500 mL), which was cooled to −78° C., n-BuLi (132.7 mL, 331.9 mmol) was added dropwise. The mixture was stirred for 1 h at −78° C., then B(OBu)3 (107.5 mL, 398.2 mmol) was added one portion. The reaction mixture was warmed to room temperature, and stirred over night. After cooled to 0° C., 5% H3PO4 was added to pH=4-5, the mixture was stirred 0.5 h, then was filtered. After removing THF, the residue was extracted with Et2O (200 mL×2), and the organic layer was dried over Na2SO4. After removing the solvent, the residue was added to water, and white solid was precipitated which was dried in vacuo. 65.7 g of [3-({[(1,1-dimethylethyl)-(dimethyl)silyl]oxy}methyl)phenyl]boronic acid was obtained (Yield: 74.5%). 1H NMR (400 MHz, CDCl3): δ 0.14 (s, 6 H), 0.98 (s 9 H), 4.88 (s, 2 H), 7.49-7.59 (m, 2 H), 8.14 (d, J=7.6 Hz, 1 H), 8.19 (s, 1 H).

後処理

  1. temperatureThe reaction mixture was warmed to room temperature
  2. stirringstirred over night
  3. temperatureAfter cooled to 0° C.
  4. stirringthe mixture was stirred 0.5 h
  5. filtrationwas filtered
  6. customAfter removing THF
  7. extractionthe residue was extracted with Et2O (200 mL×2)
  8. dry with materialthe organic layer was dried over Na2SO4
  9. customAfter removing the solvent
  10. additionthe residue was added to water, and white solid
  11. customwas precipitated which
  12. customwas dried in vacuo

出典と根拠

ORDレコード
ord-4dadff922cfd494e8df0b7b32c1149dd
出典データセット
uspto-grants-2011_11
特許番号
US08067408B2

反応ノート

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