Formic Acid → HCID 66835690、化合物

HRID 40443

反応式

HRID 40443 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([CH3:9])[CH:3]=1.[CH:10]12[CH2:16][CH:13]([CH:14]=[CH:15]1)[CH2:12][CH:11]2[CH:17]([C:26]1[CH:31]=[CH:30][C:29]([OH:32])=[C:28]([CH3:33])[CH:27]=1)[C:18]1[CH:23]=[CH:22][C:21]([OH:24])=[C:20]([CH3:25])[CH:19]=1.C(N(CC)CC)C.C(O)=O>C(OCC)(=O)C.CN(C=O)C>[OH:8][C:5]1[CH:6]=[CH:7][C:2]([CH:14]2[CH2:15][CH:10]3[CH2:16][CH:13]2[CH2:12][CH:11]3[CH:17]([C:18]2[CH:23]=[CH:22][C:21]([OH:24])=[C:20]([CH3:25])[CH:19]=2)[C:26]2[CH:31]=[CH:30][C:29]([OH:32])=[C:28]([CH3:33])[CH:27]=2)=[CH:3][C:4]=1[CH3:9]

参加物

7

反応物 4

HCID 284Formic AcidHCID 8471TriethylamineHCID 168964-Bromo-2-methylphenolHCID 676064534,4'(Bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2-methylphenol)

生成物 1

HCID 66835690HCID 66835690、化合物収率 54%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
75 °C

実験手順

Under a nitrogen atmosphere, 4-Bromo-2-methylphenol (4.69 g, 25.1 mmol), (tris-o-tolylphosphine)2PdCl2 (0.377 g; 0.480 mmol), and 4,4′-(bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2-methylphenol) (5.14 g; 16.0 mmol) were charged to an appropriately sized and equipped reaction vessel. DMF (80 mL) was added to this reactant mixture to give a suspension. Triethylamine (11.0 mL, 78.9 mmol) and formic acid (2.30 mL, 60.9 mmol) were added to this suspension and then heated to 75° C. in an oil bath. The reaction mixture turned from its original orange suspension to pale yellow and became clear. During, the course of the reaction, the temperature of the reaction mixture rose to 82° C. and turned darker, and a gas evolved very slowly. After the initial exothermic reaction ceased, the reaction mixture was stirred overnight at 75° C. After this time, the reaction mixture was a clear, pale yellow solution with black particles. The cooled reaction mixture was diluted with ethyl acetate (80 mL) and washed with water (160 mL) to remove DMF. The organic layer was dried over anhydrous MgSO4. The crude mixture was purified by preparative TLC using a hexanes/ethyl acetate mixture (50:50) as developer to afford 3.7 g of 4,4′-((5-(4-hydroxy-3-methylphenyl)bicyclo[2.2.1]heptan-2-yl)methylene)-bis(2-methylphenol) (54% yield). The identity of the product as PP429 was confirmed by LC-MS (ESI) and proton NMR.

後処理

  1. customequipped
  2. customreaction vessel
  3. customto give a suspension
  4. customDuring, the course of the reaction
  5. customrose to 82° C.
  6. customAfter the initial exothermic reaction
  7. customThe cooled reaction mixture
  8. washwashed with water (160 mL)
  9. customto remove DMF
  10. dry with materialThe organic layer was dried over anhydrous MgSO4
  11. customThe crude mixture was purified by preparative TLC

出典と根拠

ORDレコード
ord-c9d62b0ed0ea42c28630c89a99825095
出典データセット
uspto-grants-2013_09
特許番号
US08530133B2

関連ノート

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