Hydrochloric Acid → HCID 58970492、化合物

HRID 606373ノート

反応式

HRID 606373 の反応式
[Li]CCCC.C(NC(C)C)(C)C.[Cl:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[CH:20]([O:22][C:23]1[CH:27]=[CH:26][S:25][C:24]=1[C:28]([O:30][CH3:31])=[O:29])[CH3:21].C(O[B:36]1[O:40][C:39]([CH3:42])([CH3:41])[C:38]([CH3:44])([CH3:43])[O:37]1)(C)C.Cl>C1COCC1>[Cl:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[CH:20]([O:22][C:23]1[CH:27]=[C:26]([B:36]2[O:40][C:39]([CH3:42])([CH3:41])[C:38]([CH3:44])([CH3:43])[O:37]2)[S:25][C:24]=1[C:28]([O:30][CH3:31])=[O:29])[CH3:21]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 58525266Methyl 3-(1-(2-chlorophenyl)ethoxy)thiophene-2-carboxylateHCID 178418339Butyllithium

生成物 1

HCID 58970492HCID 58970492、化合物収率 51.6%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

2.5 M n-BuLi in hexanes (2.3 mL, 5.77 mmol, 1.5 Eq.) was added dropwise to a stirred solution of diisopropylamine (815 μL, 5.77 mmol, 1.5 Eq.) in anhydrous THF (20 mL) at −78° C. under nitrogen. The reaction was stirred at this temperature for 15 minutes then warmed to 0° C. for 30 minutes. The reaction was cooled to −78° C. and a solution of methyl 3-(1-(2-chlorophenyl)ethoxy)thiophene-2-carboxylate (1.14 g, 3.84 mmol, 1.0 Eq.) in anhydrous THF (10 mL) was added dropwise. After stirring at this temperature for 10 minutes, a solution of 2-isopropoxy-4,4,5,5-tetramethyl[1,3,2]-dioxaborolane (1.78 mL, 5.77 mmol, 1.0 Eq.) in anhydrous THF (10 mL) was added dropwise and stirred at −78° C. for 15 minutes then warmed to ambient temperature for 45 minutes. 1M HCl (30 mL) was added and the mixture extracted with EtOAc (3×40 mL). The combined organic extracts were washed with brine (30 mL), dried (MgSO4) and the solvent removed in vacuo. The residue was recrystalised from cyclohexane to give the sub-title compound as a white solid (837 mg, 1.98 mmol, 51%); 1H NMR (400 MHz, CDCl3) δ 1.38 (12H, s), 1.67 (3H, d), 3.90 (3H, s), 5.80 (1H, quint), 7.18 (1H, s), 7.21-7.7.34 (2H, m), 7.38 (1H, dd), 7.77 (1H, dd).

後処理

  1. temperatureThe reaction was cooled to −78° C.
  2. stirringAfter stirring at this temperature for 10 minutes
  3. stirringstirred at −78° C. for 15 minutes
  4. temperaturethen warmed to ambient temperature for 45 minutes
  5. extractionthe mixture extracted with EtOAc (3×40 mL)
  6. washThe combined organic extracts were washed with brine (30 mL)
  7. dry with materialdried (MgSO4)
  8. customthe solvent removed in vacuo
  9. customThe residue was recrystalised from cyclohexane

出典と根拠

ORDレコード
ord-b9bc73b52faa4d7a8cccfd98974cc584
出典データセット
uspto-grants-2011_03
特許番号
US07915305B2

反応ノート

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