Tributyltin Chloride → HCID 15288193, compound

HRID 1457634Notes

Reaction equation

HRID 1457634 reaction equation
[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.CC1(C)COC(C2SC=CC=2[Sn](CCCC)(CCCC)CCCC)=N1.[N+:57]([C:60]1[CH:67]=[CH:66][CH:65]=[CH:64][C:61]=1[CH2:62]Br)([O-:59])=[O:58]>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[CH2:62][C:61]2[CH:64]=[CH:65][CH:66]=[CH:67][C:60]=2[N+:57]([O-:59])=[O:58])=[N:3]1

Participants

9

Reactant 5

HCID 15096Tributyltin ChlorideHCID 77569alpha-Bromo-2-nitrotolueneHCID 50082824,5-dihydro-4,4-dimethyl-2-(2-thienyl)-oxazoleHCID 15288192HCID 15288192, compoundHCID 178418339Butyllithium

Product 1

HCID 15288193HCID 15288193, compoundYield 72.1%

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-78 °C

Procedure

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 obtained 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.

Workup

  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 obtained
  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

Sources & evidence

ORD record
ord-7b227120215d437f9b29cfaa2ee50b05
Source dataset
uspto-grants-1998_12
Patent number
US05849735

Reaction notes

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