Methyl (1aRS,7bSR)-5-(2,2-dimethylpropionylamino)-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate → Methyl 5-amino-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate

HRID 927930ノート

反応式

HRID 927930 の反応式
CC(C)(C)C([NH:5][C:6]1[C:15]([C:16]([O:18][CH3:19])=[O:17])=[C:14]2[C:9]([CH:10]3[CH2:20][CH:11]3[CH2:12][O:13]2)=[CH:8][CH:7]=1)=O>CO.S(=O)(=O)(O)O>[NH2:5][C:6]1[C:15]([C:16]([O:18][CH3:19])=[O:17])=[C:14]2[C:9]([CH:10]3[CH2:20][CH:11]3[CH2:12][O:13]2)=[CH:8][CH:7]=1

参加物

4

反応物 1

HCID 77979731Methyl (1aRS,7bSR)-5-(2,2-dimethylpropionylamino)-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate2 回

生成物 1

HCID 86713293Methyl 5-amino-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate収率 53.6%

試薬・触媒・溶媒 2

HCID 1118Sulfuric Acid触媒2 回HCID 887Methanol溶媒

実験手順

Methyl (1aRS,7bSR)-5-(2,2-dimethylpropionylamino)-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate (Intermediate 43, 0.310 g) was suspended in methanol (7.5 mL) and concentrated sulphuric acid (4 drops) was added. The reaction mixture was heated to reflux, under an atmosphere of nitrogen, for 36 hours. A further 2 drops of concentrated sulphuric acid was added and heating was continued for a further 24 hours. After cooling, the mixture was concentrated in vacuo and the residue was partitioned between ethyl acetate and saturated aqueous potassium carbonate solution. The aqueous layer was extracted with ethyl acetate and the combined organic layers were dried (Na2SO4) and filtered. The filtrate was concentrated in vacuo and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane, with a gradient of 5-20% to give methyl (1aRS,7bSR)-5-amino-1,1a,2,7b-tetrahydrocyclopropa[c]chromene-4-carboxylate (0.120 g) as an off-white solid.

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux, under an atmosphere of nitrogen, for 36 hours
  3. temperatureheating
  4. temperatureAfter cooling
  5. concentrationthe mixture was concentrated in vacuo
  6. customthe residue was partitioned between ethyl acetate and saturated aqueous potassium carbonate solution
  7. extractionThe aqueous layer was extracted with ethyl acetate
  8. dry with materialthe combined organic layers were dried (Na2SO4)
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated in vacuo
  11. customthe residue was purified by chromatography on silica
  12. washeluting with a mixture of ethyl acetate and cyclohexane, with a gradient of 5-20%

出典と根拠

ORDレコード
ord-317f7cd9409745d68db0a8389e3bec33
出典データセット
uspto-grants-2016_03
特許番号
US09290472B2

反応ノート

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