Formic Acid → 4,4'-((5-(4-(5-(Bis(4-hydroxy-3-methylphenyl)methyl)bicyclo[2.2.1]heptan-2-yl)phenyl) bicyclo[2.2.1]heptan-2-yl)methylene)bis(2-methylphenol)

HRID 40442

反応式

HRID 40442 の反応式
I[C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[CH:9]12[CH2:15][CH:12]([CH:13]=[CH:14]1)[CH2:11][CH:10]2[CH:16]([C:25]1[CH:30]=[CH:29][C:28]([OH:31])=[C:27]([CH3:32])[CH:26]=1)[C:17]1[CH:22]=[CH:21][C:20]([OH:23])=[C:19]([CH3:24])[CH:18]=1.C(N([CH2:38][CH3:39])CC)C.[CH:40]([OH:42])=O.C([O:46][CH2:47][CH3:48])(=O)C>[Pd].CN(C=O)C>[OH:31][C:28]1[CH:29]=[CH:30][C:25]([CH:16]([C:17]2[CH:22]=[CH:21][C:20]([OH:23])=[C:19]([CH3:24])[CH:18]=2)[CH:10]2[CH2:11][CH:12]3[CH2:15][CH:9]2[CH2:14][CH:13]3[C:2]2[CH:7]=[CH:6][C:5]([CH:13]3[CH2:14][CH:9]4[CH2:15][CH:12]3[CH2:11][CH:10]4[CH:16]([C:25]3[CH:26]=[CH:27][C:40]([OH:42])=[C:38]([CH3:39])[CH:30]=3)[C:17]3[CH:22]=[CH:48][C:47]([OH:46])=[C:19]([CH3:20])[CH:18]=3)=[CH:4][CH:3]=2)=[CH:26][C:27]=1[CH3:32]

参加物

8

反応物 5

HCID 284Formic AcidHCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 12208p-DiiodobenzeneHCID 676064534,4'(Bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2-methylphenol)

生成物 1

HCID 668370994,4'-((5-(4-(5-(Bis(4-hydroxy-3-methylphenyl)methyl)bicyclo[2.2.1]heptan-2-yl)phenyl) bicyclo[2.2.1]heptan-2-yl)methylene)bis(2-methylphenol)収率 60%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
75 °C

実験手順

1,4-Diiodobenzene (7.51 g; 22.8 mmol), (tris-o-tolylphosphine)2PdCl2 (0.713 g, 0.907 mmol), 4,4′-(bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2-methylphenol) (21.8 g; 68.0 mmol) and DMF (100 mL) were weighed and charged to an appropriately sized reaction vessel equipped with stirring and a reflux condenser and placed under a nitrogen atmosphere. Triethylamine (19.0 mL, 136 mmol) and formic acid (4.40 mL, 117 mmol) were then added with stirring to this mixture. The mixture was heated to 75° C. using an oil bath. During the course of heating the mixture changed from yellow to orange and became clear. The temperature of the reaction mixture rose to 119° C. due to the exotherm of the reaction and the solution became darker, with gas evolution. The reaction mixture was allowed to stir overnight (16 hours) at 75° C. in the oil bath. The reaction mixture obtained was a clear yellow solution with black palladium particles present. The reaction mixture was diluted with ethyl acetate (100 ml) and filtered through a silica gel plug. The filtrate was washed with water and the organic layer obtained was dried over anhydrous MgSO4. The crude mixture was purified with medium pressure column chromatography and the eluting solution was gradually changed from 100% hexanes to 100% ethyl acetate. This separation resulted in the isolation of 9.5 g of the PP719 (60% yield; 95% purity). The identity of the product was confirmed by as PP719 by LC-MS (ES1) and proton NMR.

後処理

  1. additioncharged to an appropriately sized reaction vessel
  2. customequipped
  3. customa reflux condenser and placed under a nitrogen atmosphere
  4. stirringwith stirring to this mixture
  5. temperatureDuring the course of heating the mixture
  6. customThe temperature of the reaction mixture rose to 119° C. due to the exotherm of the reaction
  7. stirringto stir overnight (16 hours) at 75° C. in the oil bath
  8. customThe reaction mixture obtained
  9. filtrationfiltered through a silica gel plug
  10. washThe filtrate was washed with water
  11. customthe organic layer obtained
  12. dry with materialwas dried over anhydrous MgSO4
  13. customThe crude mixture was purified with medium pressure column chromatography
  14. customThis separation
  15. customresulted in the isolation of 9.5 g of the PP719 (60% yield; 95% purity)

出典と根拠

ORDレコード
ord-a1e632ef3fbe4725be9e693d3580f997
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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