Lithium Chloride → 2-Methoxy-3'-carboethoxy-[1,1'-biphenyl]-6-carboxaldehyde

HRID 275170Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 275170
[C:1]([C:6]1[CH:7]=[C:8]([Sn](CCCC)(CCCC)CCCC)[CH:9]=[CH:10][CH:11]=1)([O:3][CH2:4][CH3:5])=[O:2].FC(F)(F)S(O[C:31]1[C:38]([O:39][CH3:40])=[CH:37][CH:36]=[CH:35][C:32]=1[CH:33]=[O:34])(=O)=O.[Li+].[Cl-].[F-].[K+]>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(Cl)Cl.CCCCCC.CCOCC>[CH3:40][O:39][C:38]1[CH:37]=[CH:36][CH:35]=[C:32]([CH:33]=[O:34])[C:31]=1[C:8]1[CH:9]=[CH:10][CH:11]=[C:6]([C:1]([O:3][CH2:4][CH3:5])=[O:2])[CH:7]=1

Komponenten

9

Edukt 4

HCID 433294Lithium Chloride2×HCID 522689Potassium FluorideHCID 10517141Methanesulfonic acid, trifluoro-, 2-formyl-6-methoxyphenyl esterHCID 109502313-Carboethoxyphenyltributyl-stannane2×

Produkt 1

HCID 152329312-Methoxy-3'-carboethoxy-[1,1'-biphenyl]-6-carboxaldehydeAusbeute 94,1 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418476HCID 178418476, VerbindungKatalysator2×HCID 3283Diethyl EtherLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 21226440Methylenechloride HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
150 °C

Versuchsvorschrift

Stannane 3a (4.25 g., 9.68 mmol, 1.5 equiv.) and triflate 2 (1.80 g., 6.44 mmol, 1 equiv.) are suspended in 17 mL of DMF. Bis(triphenylphosphine)palladium dichloride (0.68 g., 0.969 mmol, 0.15 equiv.) and LiCl (0.82 g., 19.3 mmol, 3 equiv.) are added and the mixture is heated to 150° C. After 45 min., more bis(triphenylphospine)palladium dichloride (0.2 g., 0.285 mmol, 0.04 equiv.), more LiCl (0.4 g., 9.42 mmol, 1.46 equiv.), and more stannane 3a (0.8 g., 1.82 mmol, 0.28 equiv.) is added, and heating is continued for 2 hours. (The reaction generally turns from yellow-brown to black when complete.) The mixture is allowed to cool to room temperature, and 15 mL of aqueous saturated KF and 10 mL of ether are added. The mixture is stirred for 30 min., and then filtered through celite to remove the tin salts. The filter cake is washed with EtOAc and ether, and the combined filtrates are washed with water, followed by 3% aqueous ammonia solution and then brine. The organic phase is dried (MgSO4) and then concentrated in vacuo. Chromatography on silica gel using 25%, 50% then 75% methylene chloride/hexane affords 2-methoxy-3'-carboethoxy-[1,1'-biphenyl]-6-carboxaldehyde (4a) (1.72 g., 6.06 mmol, 94%) as a slightly yellow oil which crystallizes on standing: mp=67°-69° C.; UVmax (CHCl3) 242 nm (ε=15819), 324 nm (ε=3953); 1H NMR (300 MHz, CDCl3) δ9.70 (s, 1H, CHO), 8.09 (ddd, J=2, 2, 7 Hz, 1H, ArH), 7.99 (s, 1H, ArH), 7.62 (dd, J=2, 8 Hz, 1H, ArH), 7.49 (m, 3H, ArH), 7.19 (dd, J=2, 8 Hz, 1H, ArH), 4.37 (q, J=7 Hz, 2H, CO2CH2), 3.76 (s, 3H, OCH3), 1.34 (t, J=7 Hz, 3H, CO2CH2CH3); 13C NMR (75 MHz, CDCl3 ) δ191.93 (C=O), 166.31 (C=O), 156.98, 135.27, 133.73, 133.57, 131.92, 130.42, 129.17, 129.09, 128.09,119.30, 115.95, 61.14, 56.06, 14.32; IR (film) 2980, 2940, 2838, 1718, 1694, 1468, 1294, 1260, 1234, 1110, 794 cm- 1 ; MS (DCI) m/e 285 (MH+), 239 (M--C2H5O). Anal. Calcd for C17H16O4.0.25 H2O: C, 70.69; H, 5.76. Found: C, 70.64; H, 5.59.

Aufarbeitung

  1. temperatureheating
  2. waitis continued for 2 hours
  3. custom(The reaction
  4. temperatureto cool to room temperature
  5. filtrationfiltered through celite
  6. customto remove the tin salts
  7. washThe filter cake is washed with EtOAc and ether
  8. washthe combined filtrates are washed with water
  9. dry with materialThe organic phase is dried (MgSO4)
  10. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-c2e752b5ee014ae985c9bbcb09b3c2ba
Quelldatensatz
uspto-grants-1995_02
Patentnummer
US05391817

Notizen zur Reaktion

Wird geladen…