Sodium hydride → HCID 67727659、化合物

HRID 1736505ノート

反応式

HRID 1736505 の反応式
[H-].[Na+].[F:3][C:4]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[CH:8][C:5]=1[CH:6]=O.[Br-].[CH:15]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[CH2:16].[C:36]1(=[O:46])[NH:40][C:39](=[O:41])[C:38]2=[CH:42][CH:43]=[CH:44][CH:45]=[C:37]12.[K]>C1COCC1.C(O)C>[F:3][C:4]1[CH:11]=[CH:10][C:9]([O:12][CH3:13])=[CH:8][C:5]=1/[CH:6]=[CH:15]\[CH2:16][N:40]1[C:36](=[O:46])[C:37]2[C:38](=[CH:42][CH:43]=[CH:44][CH:45]=2)[C:39]1=[O:41]

参加物

7

反応物 4

HCID 24758Sodium hydrideHCID 2723893Triphenylvinylphosphonium bromideHCID 27348722-Fluoro-5-methoxybenzaldehydeHCID 24194345Phthalimide potassium salt

生成物 1

HCID 67727659HCID 67727659、化合物

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
45 °C

実験手順

A cold (0° C.) suspension of NaH (3.88 g, 97 mmol) and 2-fluoro-5-methoxy benzaldehyde (10.0 g, 65 mmol) in THF (400 mL) was treated with an admix of vinyltriphenylphosphonium bromide (31.2 g, 84.5 mmol) and potassium phthalimide (15.65 g, 84.5 mmol) under N2. The reaction was then slowly heated to 45° C. for 1 h, followed by standing at ambient temperature for 18 h. The dark solution was quenched with 5% citric acid (25mL), then diluted with H2O (800 mL). The suspension was extracted with EtOAc (3×), the organics were combined and washed with 5% citric acid (3×), H2O (1×), brine, and dried over K2CO3. The crude oil was flashed through a plug of silica gel (toluene-2%MeOH/toluene) to afford pure material as a cis / trans mix (60/40, based on NMR). The cis compound was isolated by recrystallization from hot ethanol to give the titled cis isomer, 2.08 g, as a white solid, 10%: 1H NMR (300 MHz, CDCl3) δ 3.82 (s, 3H), 4.48 (m, 2H), 5.76 (m, 1H), 6.56 (d, J=12.0 Hz, 1H), 6.70-7.05 (m, 3H), 7.68-7.86 (m, 4H; MS m/e 311; Analysis calc'd for C18H14NO3F 0.12(EtOH): C, 68.95; H, 4.78; N, 4.37; found: C, 69.23; H, 4.92; N, 4.37.

後処理

  1. customThe dark solution was quenched with 5% citric acid (25mL)
  2. additiondiluted with H2O (800 mL)
  3. extractionThe suspension was extracted with EtOAc (3×)
  4. washwashed with 5% citric acid (3×), H2O (1×), brine
  5. dry with materialdried over K2CO3
  6. customto afford pure material as a cis / trans
  7. additionmix (60/40, based on NMR)
  8. customto give the titled cis isomer, 2.08 g

出典と根拠

ORDレコード
ord-e5588e816fc94f7ca745624b43a57dd7
出典データセット
uspto-grants-1996_07
特許番号
US05541228

反応ノート

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