Dichloroacetic Acid → HCID 59289330、化合物

HRID 2191034ノート

反応式

HRID 2191034 の反応式
O[CH2:2][C@@H:3]1[C@H:7]2[O:8][C:9]([CH3:12])([CH3:11])[O:10][C@H:6]2[C@H:5]([N:13]2[C:17]3=[N:18][CH:19]=[N:20][C:21]([NH:22][C:23](=[O:30])[C:24]4[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=4)=[C:16]3[CH:15]=[N:14]2)[O:4]1.ClC(Cl)C(O)=O.C1CCC(N=C=NC2CCCCC2)CC1.[CH2:52]([O:54][P:55]([CH:60]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:57][CH2:58][CH3:59])=[O:56])[CH3:53]>CS(C)=O.O.CO>[C:23]([NH:22][C:21]1[N:20]=[CH:19][N:18]=[C:17]2[N:13]([C@H:5]3[C@@H:6]4[O:10][C:9]([CH3:12])([CH3:11])[O:8][C@@H:7]4[C@@H:3](/[CH:2]=[CH:60]/[P:55](=[O:56])([O:57][CH2:58][CH3:59])[O:54][CH2:52][CH3:53])[O:4]3)[N:14]=[CH:15][C:16]=12)(=[O:30])[C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

参加物

8

反応物 4

HCID 6597Dichloroacetic AcidHCID 10868DicyclohexylcarbodiimideHCID 10573715Diethyl(triphenylphosphoranylidene)methylphosphonateHCID 59289350HCID 59289350、化合物

生成物 1

HCID 59289330HCID 59289330、化合物収率 27%

試薬・触媒・溶媒 3

HCID 679Dimethyl Sulfoxide溶媒HCID 887Methanol溶媒HCID 962Water溶媒

実験手順

Compound 22.3 (2.03 g, 4.93 mmol) in anhydrous dimethyl sulfoxide (25 mL, 0.2 M) was treated with dichloroacetic acid (400 μL, 4.93 mmol) and DCC (2.04 g, 9.67 mmol). The solution was stirred at room temperature for 2 h. [(Diethoxyphosphinyl)methylidene]triphenylphosphorane (2.0 g, 4.93 mmol, J. Org. Chem. 1996, 61, 7697-7701) was added and the mixture was stirred overnight. MeOH (25 mL) and H2O (25 mL) were added and the mixture was filtered over a plug of SiO2 and washed with MeOH (3×25 mL). The solvent was removed in vacuo and residue was suspended in CH2Cl2 and filtered over a plug of SiO2, and the solvent removed in vacuo. The residue was subjected to a column chromatography eluting with 0-100% EtOAc-hexanes, followed by 0-20% MeOH—CH2Cl2 to afford compound 22.4 (734 mg, 27% yield, E/Z ratio not determined) as a white solid (data for major isomer): 1H NMR (CDCl3, 300 MHz) 9.73 (br s, 1H), 8.71 (s, 2H), 7.91 (d, J=7.8 Hz, 2H), 7.50 (m, 1H), 7.35 (t, J=7.5 Hz, 2H), 6.89 (m, 1H), 6.15 (br s, 1H), 5.95 (m, 1H), 4.78 (m, 1H), 4.62 (m, 1H), 4.36 (m, 1H), 4.01 (m, 4H), 1.23 (m, 12H); 31P NMR (DMSO-d6, 121.4 MHz) 15.9; MS (ESI) m/z 544 [M+H+].

後処理

  1. additionwas added
  2. filtrationthe mixture was filtered over a plug of SiO2
  3. washwashed with MeOH (3×25 mL)
  4. customThe solvent was removed in vacuo and residue
  5. filtrationfiltered over a plug of SiO2
  6. customthe solvent removed in vacuo
  7. washeluting with 0-100% EtOAc-hexanes

出典と根拠

ORDレコード
ord-333793ed727c42829d876d7693e85eee
出典データセット
uspto-grants-2012_12
特許番号
US08324179B2

反応ノート

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