Stannous Chloride → HCID 59609198, 화합물

HRID 405039

반응식

HRID 405039 반응식
[CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[CH:13]([Mg]Cl)([CH3:15])[CH3:14].[S:18]1[CH:22]=[CH:21][C:20]2[C:23](=O)[C:24]3[S:25][CH:26]=[CH:27][C:28]=3[C:29](=O)[C:19]1=2.Cl[Sn]Cl>C1COCC1.Cl.[Cl-].[Na+].O>[C:1]([C:23]1[C:24]2[S:25][CH:26]=[CH:27][C:28]=2[C:29]([C:14]#[C:13][CH2:15][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])=[C:19]2[S:18][CH:22]=[CH:21][C:20]=12)#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

참가 물질

8

반응물 4

HCID 24479Stannous ChlorideHCID 698211-DodecyneHCID 288478(Benzo(1,2-b:4,5-b)dithiophene-4,8-dione)HCID 178418918HCID 178418918, 화합물

생성물 1

HCID 59609198HCID 59609198, 화합물수율 57%

시약·촉매·용매 3

HCID 313Hydrochloric Acid용매HCID 8028Tetrahydrofuran용매2회HCID 57417360Sodium chloride; water용매

반응 조건

온도
50 °C

실험 절차

To a solution of dodecyne (17.5 mL, 81.7 mmol) in THF (20 mL) in a 250 mL flask equipped with a condenser under an argon atmosphere was added dropwise 36 mL (72 mmol) of a 2 M solution of isopropylmagnesium chloride in THF at room temperature. After addition, the reaction mixture was heated at 50° C. for 95 min and cooled to room temperature. 4,8-Dihydrobenzo[1,2-b:4,5-b′]dithiophene-4,8-dione (3 g, 13.6 mmol) was added, and the mixture was heated at 50° C. for 1 hour before cooling down to room temperature. Subsequently, a solution of 20 g of SnCl2 in 50 mL 10% aqueous HCl solution was added in a dropwise fashion followed by further heating at 60° C. for 1 hour. After the reaction, brine (30 mL) was added. The organic phase was separated and evaporated under vacuum. The residue was diluted with MeOH (100 mL) and filtered. The solid was washed with MeOH several times. The brown solid was purified by column chromatography with CHCl3:hexane 5:6 as eluent. Recrystallization of the crude product collected from flash chromatography from hexane gave 4.03 g (57% yield) of a pale yellow crystal after drying in vacuo. 1H NMR (CDCl3, 500 MHz), δ=7.59 (d, J=5.5 Hz, 2H), 7.51 (d, J=6.0 Hz, 2H), 2.65 (t, J=6.5 Hz, 4H), 1.70-1.80 (m, 4H), 1.56-1.65 (m, 4H), 1.22-1.47 (m, 24H), 0.90 (t, J=6.5 Hz, 6H).

후처리

  1. additionAfter addition
  2. temperaturecooled to room temperature
  3. temperaturethe mixture was heated at 50° C. for 1 hour
  4. temperaturebefore cooling down to room temperature
  5. temperatureby further heating at 60° C. for 1 hour
  6. additionwas added
  7. customThe organic phase was separated
  8. customevaporated under vacuum
  9. additionThe residue was diluted with MeOH (100 mL)
  10. filtrationfiltered
  11. washThe solid was washed with MeOH several times
  12. customThe brown solid was purified by column chromatography with CHCl3:hexane 5:6 as eluent
  13. customRecrystallization of the crude product
  14. customcollected from flash chromatography from hexane

출처 및 근거

ORD 기록
ord-dcbce6d826744041abdb4d2490cf7f51
출처 데이터셋
uspto-grants-2014_06
특허 번호
US08748739B2

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