Sodium Carbonate → HCID 58691611、化合物

HRID 856010ノート

反応式

HRID 856010 の反応式
CC1(C)C(C)(C)OB([C:9]2[CH:10]=[C:11]([C:14]([O:16][CH3:17])=[O:15])[S:12][CH:13]=2)O1.CC1(C)C(C)(C)OB(B2OC(C)(C)C(C)(C)O2)O1.C([O-])(=O)C.[K+].Br[C:43]1[CH:44]=[N:45][C:46]2[N:47]([N:49]=[CH:50][C:51]=2[C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)[CH:48]=1.C(=O)([O-])[O-].[Na+].[Na+]>CN(C=O)C.O1CCOCC1.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].Cl[Pd]Cl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:52]1([C:51]2[CH:50]=[N:49][N:47]3[CH:48]=[C:43]([C:9]4[CH:10]=[C:11]([C:14]([O:16][CH3:17])=[O:15])[S:12][CH:13]=4)[CH:44]=[N:45][C:46]=23)[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=1

参加物

11

反応物 5

HCID 10340Sodium CarbonateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 52911233Methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxylateHCID 586916046-Bromo-3-phenylpyrazolo[1,5-a]pyrimidine

生成物 1

HCID 58691611HCID 58691611、化合物

試薬・触媒・溶媒 5

HCID 24290Palladium Chloride触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 178418397HCID 178418397、化合物触媒HCID 6228Dimethylformamide溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

A mixture of methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxylate (5-1, 3.00 g, 13.6 mmol, 1 equiv), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (3.80 g, 15.0 mmol, 1.10 equiv), potassium acetate (4.10 g, 41.8 mmol, 3.07 equiv), and 1,1′-bis(diphenylphophino)-ferrocene)dichloropalladium (360 mg, 0.44 mmol, 0.032 equiv) in DMF (50 mL) was heated at 80° C. for 4 hours. The reaction mixture was concentrated and the residue was partitioned between aqueous half-saturated sodium bicarbonate solution and ethyl acetate (150 mL). The organic layer was dried over sodium sulfate and concentrated. A solution of this residue, 6-bromo-3-phenylpyrazolo[1,5-a]pyrimidine (1-3, 1.90 g, 6.93 mmol, 0.510 equiv), and tetrakis(triphenylphosphine)palladium (400 mg, 0.350 mmol, 0.025 equiv) in a mixture of dioxane and aqueous sodium carbonate solution (2M, 7 mL, 14 mmol, 1.0 equiv) was heated at reflux for 20 hours. The reaction mixture was partitioned between aqueous saturated sodium bicarbonate solution and ethyl acetate. The organic layer was dried over sodium sulfate and concentrated. The residue was suspended in methanol and filtered to give methyl 4-(3-phenylpyrazolo[1,5-a]pyrimidin-6-yl)thiophene-2-carboxylate (5-2) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ 8.86 (d, 1H, J=2.4 Hz), 8.80 (d, 1H, J=2.2 Hz), 8.46 (s, 1H), 8.07 (d, 1H, J=1.6 Hz), 8.05 (br d, 2H, J=7.8 Hz), 7.75 (d, 1H, J=1.6 Hz), 7.47 (br t, 2H, J=7.7 Hz), 7.30 (t, 1H, J=7.5 Hz), 3.95 (s, 3H).

後処理

  1. concentrationThe reaction mixture was concentrated
  2. customthe residue was partitioned between aqueous half-saturated sodium bicarbonate solution and ethyl acetate (150 mL)
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. concentrationconcentrated
  5. temperaturewas heated
  6. temperatureat reflux for 20 hours
  7. customThe reaction mixture was partitioned between aqueous saturated sodium bicarbonate solution and ethyl acetate
  8. dry with materialThe organic layer was dried over sodium sulfate
  9. concentrationconcentrated
  10. filtrationfiltered

出典と根拠

ORDレコード
ord-4ae62f7073ee4ce290e48f5d6934b08f
出典データセット
uspto-grants-2007_08
特許番号
US07262199B2

反応ノート

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