Tributyltin Chloride → HCID 15288193, Verbindung

HRID 1288950Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1288950
[CH3:1][C:2]1([CH3:12])[CH2:6][O:5][C:4]([C:7]2[S:8][CH:9]=[CH:10][CH:11]=2)=[N:3]1.C([Li])CCC.C([Sn](Cl)(CCCC)CCCC)CCC.[N+:32]([C:35]1[CH:42]=[CH:41][CH:40]=[CH:39][C:36]=1[CH2:37]Br)([O-:34])=[O:33]>CCOCC.C1(C)C=CC=CC=1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][C:2]1([CH3:12])[CH2:6][O:5][C:4]([C:7]2[S:8][CH:9]=[CH:10][C:11]=2[CH2:37][C:36]2[CH:39]=[CH:40][CH:41]=[CH:42][C:35]=2[N+:32]([O-:34])=[O:33])=[N:3]1

Komponenten

8

Edukt 4

HCID 15096Tributyltin ChlorideHCID 77569alpha-Bromo-2-nitrotolueneHCID 50082824,5-dihydro-4,4-dimethyl-2-(2-thienyl)-oxazoleHCID 178418339Butyllithium

Produkt 1

HCID 15288193HCID 15288193, VerbindungAusbeute 72,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 1140TolueneLösungsmittelHCID 3283Diethyl EtherLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a solution of 4,5-dihydro-4,4-dimethyl-2-(2-thienyl)-oxazole (4.5 gms 25 mmol) in anhydrous ether at -70° C., n-butyl-lithium (2.5 molar solution in hexane, 11 ml) is added drop by drop under N2 atmosphere. The reaction mixture is stirred at -78° C. for 45 minutes and tri-n-butyltin chloride (8.3 gms 25 mmol) in dry ether is added drop by drop. The reaction mixture is stirred at room temperature for 1 hour and quenched with water. The reaction mixture is extracted with ether, washed well with water, dried and concentrated. The product obtain is pure enough for further transformation. The oil product, 4,5-dihydro-4,4-dimethyl-2-[(3-(tributylstannyl)-2-thienyl]-oxazole is mixed with 2-nitrobenzyl bromide (5.5 g 25 mmol) in toluene and refluxed in the presence of tetrakis (triphenylphosphine)-palladium (0) (200 mg) for 16 hours. At the end, reaction mixture is cooled to room temperature and filtered. Toluene is removed under reduced pressure and the product is isolated as brown oil by silica gel column chromatography by eluting it with 30% ethyl acetate:hexane to give 5.7 g of the desired product. Mass spectrum; M+ 316.

Aufarbeitung

  1. stirringThe reaction mixture is stirred at room temperature for 1 hour
  2. customquenched with water
  3. extractionThe reaction mixture is extracted with ether
  4. washwashed well with water
  5. customdried
  6. concentrationconcentrated
  7. customThe product obtain
  8. customAt the end, reaction mixture
  9. temperatureis cooled to room temperature
  10. filtrationfiltered
  11. customToluene is removed under reduced pressure
  12. customthe product is isolated as brown oil by silica gel column chromatography
  13. washby eluting it with 30% ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-24056343a0364aa2a0882e2a2ac7f7e7
Quelldatensatz
uspto-grants-1998_05
Patentnummer
US05747487

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