2-(2,4-dinitrophenyl)ethyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)-phenoxy]methyl}phenyl)prop-2-enoate → 2-(2,4-diaminophenyl)ethyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]methyl}phenyl)prop-2-enoate

HRID 511724Notes

Reaction equation

HRID 511724 reaction equation
[F:1][C:2]([F:43])([O:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH2:36][CH2:37][CH2:38][C:39]([F:42])([F:41])[F:40])=[CH:31][CH:30]=1)[C:3]1[CH:8]=[CH:7][C:6](/[CH:9]=[CH:10]/[C:11]([O:13][CH2:14][CH2:15][C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-])=O)=[CH:18][C:17]=2[N+:25]([O-])=O)=[O:12])=[CH:5][CH:4]=1>CN(C)C=O.O.[Zn]>[F:1][C:2]([F:43])([O:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH2:36][CH2:37][CH2:38][C:39]([F:42])([F:41])[F:40])=[CH:31][CH:30]=1)[C:3]1[CH:4]=[CH:5][C:6](/[CH:9]=[CH:10]/[C:11]([O:13][CH2:14][CH2:15][C:16]2[CH:21]=[CH:20][C:19]([NH2:22])=[CH:18][C:17]=2[NH2:25])=[O:12])=[CH:7][CH:8]=1

Participants

5

Reactant 1

HCID 866765602-(2,4-dinitrophenyl)ethyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)-phenoxy]methyl}phenyl)prop-2-enoate

Product 1

HCID 866765612-(2,4-diaminophenyl)ethyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]methyl}phenyl)prop-2-enoateYield 71.5%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

5.11 g (8.38 mmol) of 2-(2,4-dinitrophenyl)ethyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)-phenoxy]methyl}phenyl)prop-2-enoate are dissolved in a mixture of 54 mL of N,N-di-methyl-formamide and 6 mL water. 13.9 g (51.4 mmol) ferric chloride hexahydrate are added. 5.60 g (85.7 mmol) zinc powder is added portion wise within 60 minutes. The mixture is allowed to react for 2 hours. The reaction mixture is partitioned between ethyl acetate and water and filtrated. The organic phase is washed repeatedly with water, dried over sodium sulfate, filtrated and concentrated under reduced pressure. Filtration of the residue on 200 g silica gel using toluene:ethyl acetate 1:3 as eluent and crystallization from ethyl acetate:hexane mixture yields 3.30 g of 2-(2,4-diaminophenyl)ethyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenoxy]methyl}phenyl)prop-2-enoate as yellow crystals.

Workup

  1. customto react for 2 hours
  2. customThe reaction mixture is partitioned between ethyl acetate and water
  3. filtrationfiltrated
  4. washThe organic phase is washed repeatedly with water
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltrated
  7. concentrationconcentrated under reduced pressure
  8. filtrationFiltration of the residue on 200 g silica gel
  9. customcrystallization from ethyl acetate

Sources & evidence

ORD record
ord-e5cda977ce7846b197856dbd3ba320ac
Source dataset
uspto-grants-2015_08
Patent number
US09097938B2

Reaction notes

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