Allyl Alcohol → 3-(2-(Methylthio)benzo[d]thiazol-6-yl)propanal

HRID 1848111노트

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HRID 1848111 반응식
I[C:2]1[CH:12]=[CH:11][C:5]2[N:6]=[C:7]([S:9][CH3:10])[S:8][C:4]=2[CH:3]=1.[CH2:13]([OH:16])[CH:14]=[CH2:15].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C([O-])(O)=O.[Na+]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].O>[CH3:10][S:9][C:7]1[S:8][C:4]2[CH:3]=[C:2]([CH2:15][CH2:14][CH:13]=[O:16])[CH:12]=[CH:11][C:5]=2[N:6]=1

참가 물질

8

반응물 4

HCID 7858Allyl AlcoholHCID 80271Tri-o-tolylphosphineHCID 516892Sodium BicarbonateHCID 669058856-Iodo-2-(methylthio)benzo[d]thiazole

생성물 1

HCID 866810863-(2-(Methylthio)benzo[d]thiazol-6-yl)propanal수율 52%

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 962Water용매HCID 6228Dimethylformamide용매

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온도
100 °C

실험 절차

A mixture of 6-iodo-2-(methylthio)benzo[d]thiazole (5.0 g, 16.3 mmol), allyl alcohol (2.2 mL, 32.6 mmol), Pd(OAc)2 (0.36 g, 1.63 mmol), tris(o-tolyl) phosphine (1.0 g, 3.3 mmol) and NaHCO3 (2.8 g, 32.6 mmol) in DMF (75 mL) was stirred at 100° C. under nitrogen atmosphere for 4 h. Then the mixture was cooled to rt and water (300 mL) was added. The mixture was extracted with EtOAc (200 mL×3). The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography eluting with 10:1 to 5:1 petroleum ether/EtOAc to afford 3-(2-(methylthio)benzo[d]thiazol-6-yl)propanal as a dark yellow oil (2.0 g, 52%). 1H NMR (300 MHz, CDCl3) δ 9.83 (t, J=1.2 Hz, 1H), 7.78 (d, J=8.4 Hz, 1H), 7.58 (d, J=1.2 Hz, 1H), 7.23 (dd, J=1.8, 8.4 Hz, 1H), 3.05 (t, J=7.5 Hz, 2H), 2.85 (t, J=7.5 Hz, 2H), 2.78 (s, 3H). LCMS (ESI) m/z 238 (M+H)+.

후처리

  1. temperatureThen the mixture was cooled to rt
  2. extractionThe mixture was extracted with EtOAc (200 mL×3)
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel chromatography
  8. washeluting with 10:1 to 5:1 petroleum ether/EtOAc

출처 및 근거

ORD 기록
ord-c61fd1d879854da586453d4f1bcd62c3
출처 데이터셋
uspto-grants-2015_02
특허 번호
US08952058B2

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