Hydrochloric Acid → 1,2-Dihydro-10-hydroxy-8-(3-methyl-2-octyl)-5-oxo-4H,5H-thiopyrano[3,4-c][1]benzopyran

HRID 1282853ノート

反応式

HRID 1282853 の反応式
[OH:1][C:2]1[C:7]2[C:8]3[CH2:15][CH2:14][S:13][C:9]=3[C:10](=[O:12])[O:11][C:6]=2[CH:5]=[C:4]([CH:16]([CH:18]([CH3:24])[CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[CH3:17])[CH:3]=1.O=[C:26]1CCSCC1C(OCC)=O.Cl>C(O)C>[OH:1][C:2]1[C:7]2[C:8]3[CH2:15][CH2:14][S:13][CH2:26][C:9]=3[C:10](=[O:12])[O:11][C:6]=2[CH:5]=[C:4]([CH:16]([CH:18]([CH3:24])[CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[CH3:17])[CH:3]=1

参加物

5

反応物 3

HCID 313Hydrochloric AcidHCID 256936Ethyl 4-oxotetrahydro-2H-thiopyran-3-carboxylateHCID 214339001,2-Dihydro-9-hydroxy-7-(3-methyl-2-octyl)-4-oxo-4H-thieno[2,3-c][1]benzopyran

生成物 1

HCID 214339401,2-Dihydro-10-hydroxy-8-(3-methyl-2-octyl)-5-oxo-4H,5H-thiopyrano[3,4-c][1]benzopyran収率 68%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

A solution of 6.4 g. (0.027 mole) of 5-(3-methyl-2-octyl-resorcinol of Example 1 and 5.0 g. (0.0266 mole) of ethyl 4-oxo-2,3,5,6-tetrahydro-4H-thiopyran-3-carboxylate [prepared according to the method of Bennett and Scorah, J. Chem. Soc., 194 (1927)] in 35 ml. of absolute ethanol was cooled in an ice bath while it was saturated with hydrogen chloride. The resulting deep red solution was tightly stoppered and allowed to stand at room temperature for 120 hours. After one day yellow crystalline material had collected on the bottom of the flask. The reaction mixture was warmed gently on the steam bath for 15 minutes, cooled and poured onto a water-ice mixture. The gum-like material that precipitated was extracted with several portions of chloroform. The chloroform solution was washed with aqueous potassium bicarbonate and with water and dried over sodium sulfate. Evaporation of the solvent left 7.5 g. of a light-colored solid. This material was triturated several times with boiling petroleum ether to remove unreacted keto ester. The residue was recrystallized from an ethyl acetate-petroleum ether mixture to give 6.5 g. (68%) of the desired compound, m.p. 153°-155°C.

後処理

  1. customAfter one day yellow crystalline material had collected on the bottom of the flask
  2. temperatureThe reaction mixture was warmed gently on the steam bath for 15 minutes
  3. temperaturecooled
  4. additionpoured onto a water-ice mixture
  5. customThe gum-like material that precipitated
  6. extractionwas extracted with several portions of chloroform
  7. washThe chloroform solution was washed with aqueous potassium bicarbonate and with water
  8. dry with materialdried over sodium sulfate
  9. customEvaporation of the solvent
  10. waitleft 7.5 g
  11. customThis material was triturated several times with boiling petroleum ether
  12. customto remove unreacted keto ester
  13. customThe residue was recrystallized from an ethyl acetate-petroleum ether mixture
  14. customto give 6.5 g

出典と根拠

ORDレコード
ord-137af7e79a7643f4a973b09f7928d501
出典データセット
uspto-grants-1976_08
特許番号
US03972880

反応ノート

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