Ethanol → HCID 59516141、化合物

HRID 1799429ノート

反応式

HRID 1799429 の反応式
[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH:2]1[NH:11][C:12]([C:14]1[CH:15]=[N:16][N:17]([C:23]3[CH:28]=[CH:27][C:26](Cl)=[CH:25][C:24]=3[CH3:30])[C:18]=1[C:19]([CH3:22])([CH3:21])[CH3:20])=[O:13])[CH2:8]2.C(N(C(C)C)C(C)C)C.F[B-](F)(F)F.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.O1C[CH2:62][O:61][CH2:60][CH2:59]1.C([OH:66])C>CN(C)C1C=CN=CC=1.[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Mo].CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC(O)=O.CC(O)=O.[Pd].[Pd]>[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH:2]1[NH:11][C:12]([C:14]1[CH:15]=[N:16][N:17]([C:23]3[CH:28]=[CH:27][C:26]([C:62]([O:61][CH2:60][CH3:59])=[O:66])=[CH:25][C:24]=3[CH3:30])[C:18]=1[C:19]([CH3:22])([CH3:21])[CH3:20])=[O:13])[CH2:8]2

参加物

9

反応物 5

HCID 702EthanolHCID 312751,4-DioxaneHCID 81531DiisopropylethylamineHCID 44558591Tri-t-butylphosphine fluoroborateHCID 59516130N-(2-adamantyl)-1-(4-chloro-2-methyl-phenyl)-5-tert-butyl-pyrazole-4-carboxamide2 回

生成物 1

HCID 59516141HCID 59516141、化合物収率 50%

試薬・触媒・溶媒 3

HCID 142844-(Dimethylamino)pyridine触媒HCID 98885Molybdenum carbonyl (Mo(CO)6)触媒HCID 11104995trans-Bis(acetato)bis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium(II)触媒

反応条件

温度
150 °C

実験手順

N-(2-adamantyl)-1-(4-chloro-2-methyl-phenyl)-5-tert-butyl-pyrazole-4-carboxamide (Intermediate #114) (647 mg, 1.52 mmol), Molybdenum hexacarbonyl (0.102 mL, 0.76 mmol), 4-Dimethylaminopyridine (371 mg, 3.04 mmol), N-Ethyldiisopropylamine (0.529 mL, 3.04 mmol), trans-Di-mu-acetatobis[2-(di-o-tolylphosphino)benzyl]dipalladium(II) (71.4 mg, 0.08 mmol) and Tri-tert-butylphosphine tetrafluoroborate (88 mg, 0.30 mmol) were suspended in ethanol (6 mL) and dioxane (6.00 mL) and sealed into a microwave tube. The reaction was heated to 150° C. for 1 hour in the microwave reactor and cooled to RT. The reaction mixture was evaporated to dryness and redissolved in EtOAc (100 mL), and washed with water (10 mL), filtered, then washed with 2M HCl (10 mL), and saturated brine (10 mL). The organic layer was dried over MgSO4, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution gradient 0 to 2.5% EtOAc in isohexane. Pure fractions were evaporated to dryness to afford ethyl 4-[4-(2-adamantylcarbamoyl)-5-tert-butyl-pyrazol-1-yl]-3-methyl-benzoate (352 mg, 50.0%) as a colourless oil.

後処理

  1. temperaturecooled to RT
  2. customThe reaction mixture was evaporated to dryness
  3. dissolutionredissolved in EtOAc (100 mL)
  4. washwashed with water (10 mL)
  5. filtrationfiltered
  6. washwashed with 2M HCl (10 mL), and saturated brine (10 mL)
  7. dry with materialThe organic layer was dried over MgSO4
  8. filtrationfiltered
  9. customevaporated
  10. customto afford crude product
  11. customThe crude product was purified by flash silica chromatography, elution gradient 0 to 2.5% EtOAc in isohexane
  12. customPure fractions were evaporated to dryness

出典と根拠

ORDレコード
ord-d889c6674c8e44618fdef2111b17b10c
出典データセット
uspto-grants-2013_01
特許番号
US08344016B2

反応ノート

読み込み中…