Toluene → 5,6-Dihydro-4H-thieno[2,3-b]thiopyran-4-one

HRID 258138ノート

反応式

HRID 258138 の反応式
C1(C)C=CC=CC=1.[S:8]1[CH:12]=[CH:11][CH:10]=[C:9]1[S:13][CH2:14][CH2:15][C:16]([OH:18])=O.FC(F)(F)C(OC(=O)C(F)(F)F)=O.[OH-].[Na+]>C(Cl)(Cl)Cl.C(OCC)(=O)C.CCCCCC.O>[S:8]1[C:9]2[S:13][CH2:14][CH2:15][C:16](=[O:18])[C:10]=2[CH:11]=[CH:12]1

参加物

9

反応物 4

HCID 1140TolueneHCID 9845Trifluoroacetic anhydrideHCID 14798Sodium HydroxideHCID 139116455-(2-Carboxyethylthio)thiophene2 回

生成物 1

HCID 110302745,6-Dihydro-4H-thieno[2,3-b]thiopyran-4-one

試薬・触媒・溶媒 4

HCID 962Water溶媒HCID 6212Chloroform溶媒HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

In a 2-L three-neck round-bottom flask fitted with an overhead mechanical stirrer, thermometer, addition funnel, reflux condenser, and nitrogen bubbler vented through an acid-vapor scrubber was placed the toluene solution of 11 (130.7 g, 695 mmol). The reaction mixture was brought to an initial temperature of 20° C. and trifluoroacetic anhydride (161 g, 765 mmol) was added over 5 minutes to the stirred solution of 11. The reaction was then heated to 35°-38° C. and stirred for about 1.5 hours. The reaction was then slowly added to water (500 mL) maintaining the temperature at <25° C. A pH probe was placed in the vessel and the mixture was titrated to pH 7.0 with 50% sodium hydroxide (123 g, 1.53 mole). The layers were separated and the aqueous phase was extracted once with toluene (200 mL). The combined organic extracts were then concentrated under vacuum (43 mBar) to a volume of 200 mL and then diluted to 1.2 L with ethyl acetate for the next step (oxidation). A small sample was chromatographed to obtain the following data: Rf =0.29 (85:15 hexane:ethyl acetate). m.p. 61°-62° C. IR (CHCl3): 3120 w, 3090 w, 3010 m, 2930 w, 1660 s (C=O), 1500 m, 1390 s, 1315 w, 1280 w, 1265 m, 1190 w, 1035 w, 890 w. 1H NMR: δ7.42 (d, J=5.4, H2); 6.98 (d, J=5.4, H3); 3.33 (m, C5H2); 2.82 (m, C6H2). 13C NMR: δ188.9 (C4), 150.9, 135.0 (C3a, C7a), 126.1, 121.8 (C2, C3), 38.1 (C6), 30.0 (C5).

後処理

  1. customIn a 2-L three-neck round-bottom flask fitted with an overhead mechanical stirrer
  2. additionthermometer, addition funnel
  3. temperaturereflux condenser
  4. temperatureThe reaction was then heated to 35°-38° C.
  5. temperaturemaintaining the temperature at <25° C
  6. customThe layers were separated
  7. extractionthe aqueous phase was extracted once with toluene (200 mL)
  8. concentrationThe combined organic extracts were then concentrated under vacuum (43 mBar) to a volume of 200 mL
  9. additiondiluted to 1.2 L with ethyl acetate for the next step (oxidation)
  10. customA small sample was chromatographed
  11. customto obtain the following data
  12. custom3120 w, 3090 w, 3010 m, 2930 w, 1660 s (C=O), 1500 m, 1390 s, 1315 w, 1280 w, 1265 m, 1190 w, 1035 w, 890 w

出典と根拠

ORDレコード
ord-3fd93351d3fc42b19253529b96b4edf3
出典データセット
uspto-grants-1993_11
特許番号
US05264585

反応ノート

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