Sodium Iodide → HCID 1393419, compound

HRID 981348Notes

Reaction equation

HRID 981348 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[I-].[Na+].Cl[C:23]1[CH:24]=[C:25]([C:29]([F:32])([F:31])[F:30])[CH:26]=[CH:27][CH:28]=1.Cl[C:34]1[CH:43]=[CH:42][C:37]([C:38]([O:40][CH3:41])=[O:39])=[CH:36][CH:35]=1>[Zn].[Ni](Cl)Cl.C(Cl)(Cl)Cl.CN(C)C=O>[F:30][C:29]([F:32])([F:31])[C:25]1[CH:24]=[C:23]([C:34]2[CH:43]=[CH:42][C:37]([C:38]([O:40][CH3:41])=[O:39])=[CH:36][CH:35]=2)[CH:28]=[CH:27][CH:26]=1

Participants

9

Reactant 4

HCID 5238Sodium IodideHCID 73743-ChlorobenzotrifluorideHCID 11776TriphenylphosphineHCID 14307Methyl 4-chlorobenzoate

Product 1

HCID 1393419HCID 1393419, compound

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 24385Nickel DichlorideCatalystHCID 6212ChloroformSolventHCID 6228DimethylformamideSolvent2×

Procedure

33 g of zinc powder, 33 g of triphenylphosphine, 5 of sodium iodide, 2.2 g of nickel(II) chloride and 200 ml of dimethylformamide were mixed under a nitrogen atmosphere and the mixture was initially introduced into the reaction vessel. The mixture was kept at 50° to 60° C. for half an hour, after which a suspension coloured deep red-brown was present. A solution containing 20.2 g (0.11 mol) of 3-chloro-benzotrifluoride, 38.2 g (0.22 mol) of methyl 4-chloro-benzoate and 100 ml of dimethylformamide was added dropwise to this suspension in the course of half an hour. After 6 hours at 80° C., the reaction mixture was introduced into 500 ml of chloroform and filtered. The residue on the filter was boiled up in 400 ml of toluene and filtered off hot. After cooling, 15 g of dimethyl biphenyl-4,4'-dicarboxylate (50.5% of theory--based on the methyl 4-chloro-benzoate employed) of melting point 213° to 214° C. were obtained. The filtrate was extracted by shaking with dilute aqueous hydrochloric acid and with water and the organic phase was dried over sodium sulphate and concentrated. The resulting residue was distilled. 6.4 g of 3,3'-bis-(trifluoromethyl)-biphenyl (20% of theory--based on the 3-chloro-benzotrifluoride employed) and a total of 16 g of methyl 4-(3-trifluoromethylphenyl)-benzoate (52% of theory--based on the 3-chloro-benzotrifluoride employed) of boiling point 125° C. to 130° C. under 0.1 to 0.3 mbar were obtained in this manner.

Workup

  1. additionthe mixture was initially introduced into the reaction vessel
  2. waitThe mixture was kept at 50° to 60° C. for half an hour
  3. additionwas added dropwise to this suspension in the course of half an hour
  4. filtrationfiltered
  5. filtrationfiltered off hot
  6. temperatureAfter cooling
  7. customwere obtained
  8. extractionThe filtrate was extracted
  9. dry with materialthe organic phase was dried over sodium sulphate
  10. concentrationconcentrated
  11. distillationThe resulting residue was distilled
  12. customwere obtained in this manner

Sources & evidence

ORD record
ord-9dbdb115738f446f8e9139ddc50959c3
Source dataset
uspto-grants-1991_02
Patent number
US04990647

Reaction notes

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