Sodium Hydroxide → HCID 69516187、化合物

HRID 1297213ノート

反応式

HRID 1297213 の反応式
[C:1]([N:20]1[N:24]=[N:23][C:22]([CH2:25][C:26]#[N:27])=[N:21]1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C=O)CCCCC1.[OH-].[Na+].[I-].C[S+](C)(C)=O.[H-].[Na+].[CH:46]1([CH:52]=[C:53](C2N=NN(C(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)N=2)C#N)[CH2:51][CH2:50][CH2:49][CH2:48][CH2:47]1>C1C=CC=CC=1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C.CCOC(C)=O>[CH:46]1([CH:52]2[CH2:53][C:25]2([C:22]2[N:23]=[N:24][N:20]([C:1]([C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)([C:8]3[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=3)[C:14]3[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=3)[N:21]=2)[C:26]#[N:27])[CH2:51][CH2:50][CH2:49][CH2:48][CH2:47]1

参加物

11

反応物 6

HCID 14798Sodium HydroxideHCID 16275CyclohexanecarboxaldehydeHCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 58914637HCID 58914637、化合物HCID 69516184HCID 69516184、化合物

生成物 1

HCID 69516187HCID 69516187、化合物収率 89.4%

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide触媒HCID 241Benzene溶媒HCID 6228Dimethylformamide溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of (2-trityl-2H-tetrazol-5-yl)-acetonitrile (1.0 g, 2.85 mmol) in 15 mL benzene was added cyclohexanecarboxaldehyde (0.38 mL, 3.13 mmol), 10 mL 10% NaOH (aq), and tetrabutylammonium bromide (50 mg). The mixture was stirred for 1 h, then poured into EtOAc. The phases were separated, and the organic phase dried (MgSO4) and concentrated. Meanwhile, to trimethylsulfoxonium iodide (0.75 g, 3.42 mmol) in 7.0 mL DMF was added sodium hydride (60% dispersion in mineral oil, 0.14 g, 3.42 mmol). The mixture was stirred for 30 min at which time a solution of crude 3-cyclohexyl-2-(2-trityl-2H-tetrazol-5-yl)-acrylonitrile 2 (ca. 2.8 mmol) in 5.0 mL DMF was added quickly dropwise. The orange solution was stirred overnight, partitioned between EtOAc and H2O, and the phases separated. The organic phase was washed with brine, dried (MgSO4) and concentrated. Flash chromatography of the residue (15→20% EtOAc/hexanes) provided 1.15 g (88%, two steps) of 2-cyclohexyl-1-(2-trityl-2H-tetrazol-5-yl)-cyclopropanecarbonitrile as a colorless foam. 1H NMR (CDCl3) δ 7.33 (m, 9H), 7.07 (m, 6H), 1.88 (dd, J=4.9, 8.8 Hz, 1H, cyclopropyl —CHH), 1.66-1.84 (m, 4H), 1.57 (dd, J=4.9, 7.7 Hz, 1H, cyclopropyl —CHH), 1.25 (m, 8H).

後処理

  1. customThe phases were separated
  2. dry with materialthe organic phase dried (MgSO4)
  3. concentrationconcentrated
  4. additionwas added quickly dropwise
  5. stirringThe orange solution was stirred overnight
  6. custompartitioned between EtOAc and H2O
  7. customthe phases separated
  8. washThe organic phase was washed with brine
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated

出典と根拠

ORDレコード
ord-f213cf0fa26f4df28c2bcb771a2f51ee
出典データセット
uspto-grants-2007_07
特許番号
US07250433B2

反応ノート

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