Triphenylphosphine → 4-(4-Chlorobenzyl)thiophene-2-carbaldehyde

HRID 1363249

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HRID 1363249 반응식
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.P(O[CH2:29][C:30]1[CH:35]=[CH:34][C:33]([Cl:36])=[CH:32][CH:31]=1)(OCC)(OCC)=O.[CH:37]([C:39]1[S:43][CH:42]=[C:41](B(O)O)[CH:40]=1)=[O:38].[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C(#N)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:36][C:33]1[CH:32]=[CH:31][C:30]([CH2:29][C:41]2[CH:40]=[C:39]([CH:37]=[O:38])[S:43][CH:42]=2)=[CH:35][CH:34]=1

참가 물질

7

반응물 4

HCID 11776TriphenylphosphineHCID 62657Potassium Phosphate, TribasicHCID 110841152-Formylthiophene-4-boronic acidHCID 112774384-Chlorobenzyl diethyl phosphate

생성물 1

HCID 596485254-(4-Chlorobenzyl)thiophene-2-carbaldehyde수율 28%

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 6342Acetonitrile용매

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온도
90 °C

실험 절차

A solution mixture of Pd(OAc)2 (144 mg, 0.64 mmol) and triphenylphosphine (TPP) (136 mg, 0.52 mmol) were weighed into a vial, dissolved in acetonitrile and transferred into a 40 mL Wheaton vial containing diethyl 4-chlorobenzyl phosphate (Org. Lett. 2005, 7, 4875-4878; 3.08 g, 11.6 mmol), 5-formylthiophen-3-ylboronic acid (2.0 g, 12.8 mmol), K3PO4 (2.72 g, 12.8 mmol) and a stir-bar. Nitrogen gas was bubbled through the mixture. The vial was closed tightly and heated to 90° C. and vigorously stirred for 16 h. The reaction was diluted with water and extracted with dichloromethane (DCM) (3×100 mL). The combined extracts were washed with brine, dried over Na2SO4, filtered and concentrated. Purification by flash chromatography (Isco CombiFlash) (0-20% heptane/EtOAc) yielded 4-(4-chlorobenzyl)thiophene-2-carbaldehyde: 835 mg, 28% yield. 1H NMR (400 MHz, CDCl3) δ ppm: 10.10 (d, 1H), 7.80 (d, 1H), 7.63 (m, 1H), 7.55 (m, 2H), 7.40 (m, 2H), 4.23 (s, 2H).

후처리

  1. customNitrogen gas was bubbled through the mixture
  2. customThe vial was closed tightly
  3. additionThe reaction was diluted with water
  4. extractionextracted with dichloromethane (DCM) (3×100 mL)
  5. washThe combined extracts were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by flash chromatography (Isco CombiFlash) (0-20% heptane/EtOAc)

출처 및 근거

ORD 기록
ord-b2a23646235e488e853b624b000ddd59
출처 데이터셋
uspto-grants-2011_02
특허 번호
US07884124B2

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