Hydrochloric Acid → ethyl 6-nonafluorobutyl-2,2-bis(fluoromethyl)-2H-1-benzopyran-4-carboxylate

HRID 264863Notes

Reaction equation

HRID 264863 reaction equation
[F:1][CH2:2][C:3]1([CH2:19][F:20])[CH:8]=[C:7]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:6]2[CH:14]=[C:15](I)[CH:16]=[CH:17][C:5]=2[O:4]1.[F:21][C:22]([F:34])([C:30]([F:33])([F:32])[F:31])[C:23]([F:29])([F:28])[C:24](I)([F:26])[F:25].CN(C)P(=O)(N(C)C)N(C)C.Cl>[Cu].C(OCC)(=O)C>[F:21][C:22]([F:34])([C:30]([F:31])([F:32])[F:33])[C:23]([F:28])([F:29])[C:24]([F:25])([F:26])[C:15]1[CH:16]=[CH:17][C:5]2[O:4][C:3]([CH2:19][F:20])([CH2:2][F:1])[CH:8]=[C:7]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:6]=2[CH:14]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 12679HexamethylphosphoramideHCID 67917Perfluorobutyl iodide2×HCID 19037016ethyl 2,2-bisfluoromethyl-6-iodo-2H-1-benzopyran-4-carboxylate

Product 1

HCID 19037030ethyl 6-nonafluorobutyl-2,2-bis(fluoromethyl)-2H-1-benzopyran-4-carboxylateYield 51.3%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 0.30 g of ethyl 2,2-bis(fluoromethyl)-6-iodo-2H-1-benzopyran-4-carboxylate, 3.50 g of nonafluoro-butyl iodide, 0.30 g of copper powder, 0.32 g of cuprous iodide and 3 ml of hexamethylphosphoric triamide was stirred with heating at 70° C. for 22 hours, added another 1.75 g of nonafluorobutyl iodide, and stirred with heating at 150° C. for 5 hours. A mixture of 2N HCl and ethyl acetate was added to the reaction mixture, and insoluble materials were separated off using a celite. An organic layer was taken up, and an aqueous layer was extracted with ethyl acetate. The organic layers were combined, washed with saturated sodium chloride solution, dried over sodium sulfate, and concentrated in vacuo. The resultant residue was purified with silica gel column chromatography (developing solution, methylene chloride:hexane=5:1) to obtain 0.19 g of ethyl 6-nonafluorobutyl-2,2-bis(fluoromethyl)-2H-1-benzopyran-4-carboxylate as an oil.

Workup

  1. stirringstirred
  2. temperaturewith heating at 150° C. for 5 hours
  3. additionwas added to the reaction mixture, and insoluble materials
  4. customwere separated off
  5. extractionan aqueous layer was extracted with ethyl acetate
  6. washwashed with saturated sodium chloride solution
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe resultant residue was purified with silica gel column chromatography (developing solution, methylene chloride:hexane=5:1)

Sources & evidence

ORD record
ord-e2d450789e04499281cfc8bf3b4811bb
Source dataset
uspto-grants-1997_07
Patent number
US05646308

Reaction notes

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