Benzene, 1-bromo-4-(trifluoromethyl)- → HCID 18356786, compound

HRID 427239Notes

Reaction equation

HRID 427239 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([C:13]([F:16])([F:15])[F:14])=[CH:9][CH:8]=1.[Cl:17][C:18]1[CH:23]=[CH:22][N:21]=[C:20]([S:24][CH3:25])[N:19]=1>CCCCCC.C(OCC)C>[Cl:17][C:18]1[CH:23]=[C:22]([C:7]2[CH:12]=[CH:11][C:10]([C:13]([F:16])([F:15])[F:14])=[CH:9][CH:8]=2)[N:21]=[C:20]([S:24][CH3:25])[N:19]=1

Participants

6

Reactant 3

HCID 67872Benzene, 1-bromo-4-(trifluoromethyl)-HCID 971134-Chloro-2-methylthiopyrimidineHCID 178418339Butyllithium

Product 1

HCID 18356786HCID 18356786, compoundYield 67.9%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-30 °C

Procedure

31.3 ml 1.6M n-butyllithium in hexane are added at −70° C. to a solution of 11.25 g 4-bromo-benzotrifluorid in 50 ml diethylether. After stirring for 15 min. the solution is warmed to −30° C. and added to a −30° C. cold solution of 8.0 g 4-chloro-2-methylthio-pyrimidine in 50 ml ether. The mixture is stirred for 30 min. at −30° C. and another 30 min. at 0° C., then quenched with a mixture of 3.2 ml acetic acid, 0.5 ml water and 10 ml tetrahydrofuran (THF). Immediately after quenching, a solution of 11.8 g dichlorodicyanobenzoquinone (DDQ) in 50 ml THF is added and stirring is continued for 5 min. at room temperature. It is again cooled to 0° C. and 20 ml 10% aqueous sodium hydroxide are added. After stirring for 5 min. at 0° C. the organic layer is separated, dried and chromatographed to yield 10.3 g of the title compound (m.p. 93-96° C.).

Workup

  1. stirringThe mixture is stirred for 30 min. at −30° C. and another 30 min. at 0° C.
  2. customquenched with a mixture of 3.2 ml acetic acid, 0.5 ml water and 10 ml tetrahydrofuran (THF)
  3. customImmediately after quenching
  4. additiona solution of 11.8 g dichlorodicyanobenzoquinone (DDQ) in 50 ml THF is added
  5. stirringstirring
  6. waitis continued for 5 min. at room temperature
  7. temperatureIt is again cooled to 0° C.
  8. addition20 ml 10% aqueous sodium hydroxide are added
  9. stirringAfter stirring for 5 min. at 0° C. the organic layer
  10. customis separated
  11. customdried
  12. customchromatographed

Sources & evidence

ORD record
ord-f984a41c0ba64687a187e8e33703757f
Source dataset
uspto-grants-2001_11
Patent number
US06313072B1

Reaction notes

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