Sulfuric Acid → HCID 178447922, compound

HRID 1492105Notes

Reaction equation

HRID 1492105 reaction equation
[CH2:1]([C@H:4]1[CH2:9][CH2:8][C@H:7]([C:10]2[CH:15]=[C:14]([F:16])[C:13](I)=[C:12]([F:18])[CH:11]=2)[CH2:6][CH2:5]1)[CH2:2][CH3:3].[CH3:19][C:20](O)(C#C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:45]1[CH:50]=[CH:49][C:48]([F:51])=[C:47]([F:52])[CH:46]=1.[OH-].[K+].S(=O)(=O)(O)O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.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.O1CCCC1.C(N(CC)CC)C>[CH2:1]([C@H:4]1[CH2:9][CH2:8][C@H:7]([C:10]2[CH:15]=[C:14]([F:16])[C:13]([C:19]#[C:20][C:45]3[CH:50]=[CH:49][C:48]([F:51])=[C:47]([F:52])[CH:46]=3)=[C:12]([F:18])[CH:11]=2)[CH2:6][CH2:5]1)[CH2:2][CH3:3]

Participants

11

Reactant 6

HCID 1118Sulfuric AcidHCID 82582-Methyl-3-butyn-2-olHCID 11776TriphenylphosphineHCID 14797Potassium HydroxideHCID 676754-Bromo-1,2-difluorobenzeneHCID 178447924HCID 178447924, compound

Product 1

HCID 178447922HCID 178447922, compound

Reagents, catalysts & solvents 4

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of 1 g of 1-(trans-4-propylcyclohexyl)-3,5-difluoro-4-iodobenzene, 0.294 g of 2-methyl-3-butyn-2-ol, 0.077 g of bis(triphenylphosphine)palladium dichloride, 0.842 g of triethylamine, 0.084 g of triphenylphosphine and 10 ml of tetrahydrofuran was held under reflux for 48 hrs. Then, 0.326 ml of 1-bromo-3,4-difluorobenzene, 0.493 g of powdered potassium hydroxide and 0.205 g of tetrabutylammonium hydrogen sulphate were added in this sequence and the mixture was left to react under reflux for 16 hrs. Thereupon, the reaction mixture was cooled, poured into 25 ml of 1N sulphuric acid and extracted with ether. The ether phase was washed several times with sat. sodium chloride solution, dried over magnesium sulphate and evaporated on a rotary evaporator. Chromatography of the residue on 170 g of silica gel with hexane and subsequent crystallization from methanol gave 0.53 g of 4-(trans-4-propylcyclohexyl)-2,6,3',4'-tetrafluorotolane. M.p. (C/N) 71.3° C., cl.p. (N/I) 126° C.

Workup

  1. temperatureunder reflux for 48 hrs
  2. waitthe mixture was left
  3. customto react
  4. temperatureunder reflux for 16 hrs
  5. temperatureThereupon, the reaction mixture was cooled
  6. extractionextracted with ether
  7. washThe ether phase was washed several times with sat. sodium chloride solution
  8. dry with materialdried over magnesium sulphate
  9. customevaporated on a rotary evaporator
  10. customChromatography of the residue on 170 g of silica gel with hexane and subsequent crystallization from methanol

Sources & evidence

ORD record
ord-e132b03ff0d34fc68ab1378496608e66
Source dataset
uspto-grants-1994_12
Patent number
US05372746

Reaction notes

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