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Benzyl Alcohol → Benzyl 2-(5-(2,3-dichlorophenyl)pyridin-3-yl)cyclopropylcarbamate

HRID 2407461
ノート
印刷プレビュー

反応式

HRID 2407461 の反応式
[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C:9]1[CH:10]=[C:11]([CH:15]2[CH2:17][CH:16]2C(OC)=O)[CH:12]=[N:13][CH:14]=1.[OH-].[Na+].C1(OP(N=[N+]=[N-])([O:33][C:34]2C=CC=CC=2)=O)C=CC=CC=1.C([N:45](CC)CC)C.[CH2:50]([OH:57])[C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1.C([O-])(O)=O.[Na+]>CO>[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][CH:5]=[CH:4][C:3]=1[C:9]1[CH:10]=[C:11]([CH:15]2[CH2:17][CH:16]2[NH:45][C:34](=[O:33])[O:57][CH2:50][C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)[CH:12]=[N:13][CH:14]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

8

反応物 6

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 123414Diphenylphosphoryl azideHCID 516892Sodium BicarbonateHCID 59578384Methyl 2-(5-(2,3-dichlorophenyl)pyridin-3-yl)cyclopropanecarboxylate

生成物 1

HCID 59578428
Benzyl 2-(5-(2,3-dichlorophenyl)pyridin-3-yl)cyclopropylcarbamate
収率 27.2%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

To a solution of methyl 2-(5-(2,3-dichlorophenyl)pyridin-3-yl)cyclopropanecarboxylate (270 mg, 0.838 mmol) in MeOH (3 ml) was added NaOH (5 M in water, 0.503 ml, 2.51 mmol) at room temperature. The resulting mixture was stirred at room temperature for 30 min. The reaction was quenched by the addition of HCl (5 M in water), and the mixture was extracted with AcOEt/trifluoroethanol (10:1). The extract was washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo. The resulting crude was dissolved in toluene (7 ml). Diphenylphosphonoazide (0.272 ml, 1.257 mmol), triethylamine (0.175 ml, 1.257 mmol) were added to the solution, which was stirred for 12 h at 100° C. Benzyl alcohol (0.523 ml, 5.03 mmol) was added to the reaction mixture and this mixture was stirred for additional 4 h. A saturated NaHCO3 solution was added at room temperature and the mixture was extracted with AcOEt. The extract was washed with water and brine, dried over Na2SO4, filtered and concentrated in vacuo. Purification by flash column (EtOAc/Heptane=0-50%, v/v) gave benzyl 2-(5-(2,3-dichlorophenyl)pyridin-3-yl)cyclopropylcarbamate (94.1 mg, 0.228 mmol, 27% yield) ESI-MS m/z: 413[M+1]+. 1H NMR (CDCl3, 400 MHz) ppm 1.27-1.33 (m, 2H), 2.15-2.28 (m, 1H), 2.81-2.87 (m, 1H), 5.13 (s, 2H), 7.21 (bs, 1H), 7.29 (t, J=8.0 Hz, 1H), 7.35 (s, 5H), 7.52 (dd, J=8.0, 0.6 Hz, 2H), 8.48 (s, 2H)

後処理

  1. customThe reaction was quenched by the addition of HCl (5 M in water)
  2. extractionthe mixture was extracted with AcOEt/trifluoroethanol (10:1)
  3. washThe extract was washed with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. dissolutionThe resulting crude was dissolved in toluene (7 ml)
  8. stirringwas stirred for 12 h at 100° C
  9. stirringthis mixture was stirred for additional 4 h
  10. extractionthe mixture was extracted with AcOEt
  11. washThe extract was washed with water and brine
  12. dry with materialdried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo
  15. customPurification by flash column (EtOAc/Heptane=0-50%, v/v)

出典と根拠

ORDレコード
ord-4de66618ff6b42ed8cd55b49b7b3c9cb
出典データセット
uspto-grants-2014_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08809545B2

反応ノート

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