4-Chlorobenzothiazole → 4-(4-(1,1,1,3,3,3-Hexafluoropropane-2-yl)phenyl)benzo[d]thiazole

HRID 547964Notes

Reaction equation

HRID 547964 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:13]([F:16])([F:15])[F:14])[C:9]([F:12])([F:11])[F:10])=[CH:4][CH:3]=1.Cl[C:18]1[C:23]2[N:24]=[CH:25][S:26][C:22]=2[CH:21]=[CH:20][CH:19]=1>C1COCC1.[Cl-].[Zn+2].[Cl-].[Pd].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:10][C:9]([F:12])([F:11])[CH:8]([C:5]1[CH:6]=[CH:7][C:2]([C:18]2[C:23]3[N:24]=[CH:25][S:26][C:22]=3[CH:21]=[CH:20][CH:19]=2)=[CH:3][CH:4]=1)[C:13]([F:16])([F:15])[F:14]

Participants

7

Reactant 2

HCID 108210264-ChlorobenzothiazoleHCID 58592758HCID 58592758, compound

Product 1

HCID 580035814-(4-(1,1,1,3,3,3-Hexafluoropropane-2-yl)phenyl)benzo[d]thiazoleYield 91%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

a 500 mL 2-neck round-bottomed flask was equipped with a reflux condenser and replaced by nitrogen. 70 mL of THF that was dried with 0.11 mol of Mg metal was added to the above flask and then, 0.10 mol of 1-bromo-4-(1,1,1,3,3,3-hexafluoropropane-2-yl)benzene was added in a dropwise fashion. The reaction was significantly exodermic and thus a cooling bath was equipped to reduce the temperature inside the reactor less than 50° C. It was agitated for 2 hours at room temperature, 0.11 mol of zinc chloride was added with 100 mL of THF, and further agitated for 2 hours to obtain a slurry-phase reaction mixture. Another flask was replaced by nitrogen and then 0.10 mol of 4-chlorobenzothiazole derivative, 0.10 mol of Pd, and 3 mol % of Pd(PPh3)4 were dissolved in 100 mL of THF. The prepared solution was added to the reaction mixture and then agitated 60° C. for 24 hours. After the reaction is complete, the resulting product was placed on a silica gel column to remove an inorganic slurry, and then a THF solution was concentrated under vacuum to obtain 4-(4-(1,1,1,3,3,3-hexafluoropropane-2-yl)phenyl)benzo[d]thiazole using column chromatography at a yield of 91%.

Workup

  1. customa 500 mL 2-neck round-bottomed flask was equipped with a reflux condenser
  2. additionwas added to the above flask
  3. customthus a cooling bath was equipped
  4. custominside the reactor less than 50° C
  5. stirringfurther agitated for 2 hours
  6. customto obtain
  7. customa slurry-phase reaction mixture
  8. customAnother flask was replaced by nitrogen
  9. additionThe prepared solution was added to the reaction mixture
  10. stirringagitated 60° C. for 24 hours
  11. customto remove an inorganic slurry
  12. concentrationa THF solution was concentrated under vacuum

Sources & evidence

ORD record
ord-4de58ad61f74459baca93a9a82308148
Source dataset
uspto-grants-2011_05
Patent number
US07939669B2

Reaction notes

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