Ammonium Chloride → (+/-)-2-Azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enol

HRID 1523439ノート

反応式

HRID 1523439 の反応式
[CH3:1][CH:2]1[CH2:7][C:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][C:9]=2[N+:14]([O-:16])=[O:15])=[CH:5][CH:4]=[CH:3]1.C1C=C(Cl)C=C(C(OO)=[O:25])C=1.[N-:28]=[N+:29]=[N-:30].[Na+].[Cl-].[NH4+]>C(Cl)Cl.C(O)C.O>[N:28]([CH:4]1[CH:5]=[C:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][C:9]=2[N+:14]([O-:16])=[O:15])[CH2:7][CH:2]([CH3:1])[CH:3]1[OH:25])=[N+:29]=[N-:30]

参加物

8

反応物 4

HCID 25517Ammonium ChlorideHCID 33557Sodium AzideHCID 70297m-Chloroperbenzoic acidHCID 59226560HCID 59226560、化合物

生成物 1

HCID 72238239(+/-)-2-Azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enol収率 49%

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

To a solution of (+/−)-4-(5-methylcyclohexa-1,3-dienyl)-3-nitropyridine (1.0 equiv.) in DCM (0.1M) at 0° C. was added m-CPBA (1.1 equiv.) and the reaction was allowed to warm to room temperature. After 3 hours, the mixture was quenched with saturated NaHCO3, extracted with DCM, and the organic phase was dried with sodium sulfate, filtered, and concentrated to give a yellow oil. The crude was dissolved in ethanol and water (3:1, 0.1 M), and sodium azide (2.0 equiv.) and ammonium chloride (2.0 equiv.) were added. The reaction was stirred for 4 hours, then concentrated in vacuo. To the crude was added ethyl acetate and water, the organic phase was washed with brine, dried with sodium sulfate, filtered, and concentrated. The crude material was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (1:1) to afford (+/−)-2-azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enol as an oil in 49% yield. LC/MS=276.1 (M+H), Rt=0.71 min.

後処理

  1. customthe mixture was quenched with saturated NaHCO3
  2. extractionextracted with DCM
  3. dry with materialthe organic phase was dried with sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a yellow oil
  7. concentrationconcentrated in vacuo
  8. additionTo the crude was added ethyl acetate and water
  9. washthe organic phase was washed with brine
  10. dry with materialdried with sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe crude material was purified via silica gel column chromatography
  14. washeluting with ethyl acetate and hexanes (1:1)

出典と根拠

ORDレコード
ord-9342b1d62a344d9a9168346d77fd88da
出典データセット
uspto-grants-2015_07
特許番号
US09079889B2

反応ノート

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