반응 #171154

반응 방정식

hydrochloric acid

2-thiophenenitrile

diisopropyl succinate

potassium tert-butoxide

→

3,6-bis(thiophen-2-yl)-2H,5H-pyrrolo[3,4-c]pyrrole-1,4-dione

수율 82.7%

용매

water

methanol

methanol

tert-amyl alcohol

tert-amyl alcohol

반응 조건

후처리

1. 1
   기타equipped with a mechanical stirrer
2. 2
   workup.ADDITIONis added dropwise over a period of 3 h with rapid stirring
3. 3
   온도cooled to 50° C., at which point
4. 4
   workup.ADDITIONis added
5. 5
   온도The reaction mixture is heated
6. 6
   온도at reflux for 45 min
7. 7
   온도before cooling to room temperature
8. 8
   workup.STIRRINGthe mixture is stirred for 45 min
9. 9
   여과The mixture is filtered
10. 10
    세척the solid is washed with methanol (200 mL)
11. 11
    workup.STIRRINGstirred for 30 min
12. 12
    여과before being filtered again
13. 13
    workup.STIRRINGThis suspension in water, stirring
14. 14
    여과filtration
15. 15
    여과After filtering for the last time
16. 16
    기타dried at 80° C. for 16 h
17. 17
    기타dried under vacuum

실험 절차

As a specific example embodiment, potassium tert-butoxide (67.4 g, 0.60 mol) and tert-amyl alcohol (400 mL) are added to a nitrogen-protected oven-dried three-neck round-bottom flask equipped with a mechanical stirrer, a thermometer and a reflux condenser. The mixture is heated to 105° C. for 1.5 h and to this mixture is added 2-thiophenenitrile (55.2 g, 0.50 mol) and the stirring continued at 105° C. for 30 min. A mixture of diisopropyl succinate (40.4 g, 0.20 mol) in tert-amyl alcohol (60 mL) is added dropwise over a period of 3 h with rapid stirring. The mixture is then stirred at 105° C. for a further 2 h, then cooled to 50° C., at which point a mixture of methanol (300 mL) and water (80 mL) is added. The reaction mixture is heated at reflux for 45 min before cooling to room temperature. The mixture is poured over 500 g of ice, then concentrated hydrochloric acid (35% aq) (150 mL) and methanol (750 mL) are added and the mixture is stirred for 45 min. The mixture is filtered and the solid is washed with methanol (200 mL). The solid is then suspended in water (1 L) and stirred for 30 min before being filtered again. This suspension in water, stirring and filtration is repeated a further three times. After filtering for the last time, the solid is oven dried at 80° C. for 16 h, then dried under vacuum to give the product, 3,6-bis(thiophen-2-yl)-2H,5H-pyrrolo[3,4-c]pyrrole-1,4-dione, (49.7 g, 82% yield) as a red solid. This compound is used without further purification. 1HNMR (d6-DMSO, 300 MHz): δ 7.27 (2H, t, J=3.0), 7.89 (2H, dd, J1=6.0, J2=3.0), 8.23 (2H, d, J=3.0), 11.00 (2H, s); 13CNMR (d6-DMSO, 75 MHz): δ 113.6 (2C), 127.1 (2C), 128.3 (2C), 130.5 (2C), 136.6 (2C), 142.6 (2C), 168.2 (2C); m/z (EI+) 300.0 [M]+; Anal. Calc. for C14H8N2O2S2: C, 55.98; H, 2.68; N, 9.33; S, 21.35.

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