HCID 86676555, compound → HCID 86676554, compound

HRID 511716Notes

Reaction equation

HRID 511716 reaction equation
[F:1][C:2]([F:81])([C:67]1[CH:72]=[CH:71][C:70]([O:73][CH2:74][CH2:75][CH2:76][C:77]([F:80])([F:79])[F:78])=[CH:69][CH:68]=1)[O:3][C:4]1[CH:9]=[CH:8][C:7](/[CH:10]=[CH:11]/[C:12]([O:14][CH2:15][C:16]([CH2:57][C:58]2[CH:63]=[CH:62][C:61]([N+:64]([O-])=O)=[CH:60][CH:59]=2)([CH2:47][C:48]2[CH:53]=[CH:52][C:51]([N+:54]([O-])=O)=[CH:50][CH:49]=2)[CH2:17][O:18][C:19](=[O:46])/[CH:20]=[CH:21]/[C:22]2[CH:27]=[CH:26][C:25]([O:28][C:29]([F:45])([F:44])[C:30]3[CH:35]=[CH:34][C:33]([O:36][CH2:37][CH2:38][CH2:39][C:40]([F:43])([F:42])[F:41])=[CH:32][CH:31]=3)=[CH:24][CH:23]=2)=[O:13])=[CH:6][CH:5]=1>CN(C)C=O.O.[Zn]>[F:1][C:2]([F:81])([C:67]1[CH:72]=[CH:71][C:70]([O:73][CH2:74][CH2:75][CH2:76][C:77]([F:80])([F:79])[F:78])=[CH:69][CH:68]=1)[O:3][C:4]1[CH:9]=[CH:8][C:7](/[CH:10]=[CH:11]/[C:12]([O:14][CH2:15][C:16]([CH2:47][C:48]2[CH:49]=[CH:50][C:51]([NH2:54])=[CH:52][CH:53]=2)([CH2:57][C:58]2[CH:63]=[CH:62][C:61]([NH2:64])=[CH:60][CH:59]=2)[CH2:17][O:18][C:19](=[O:46])/[CH:20]=[CH:21]/[C:22]2[CH:23]=[CH:24][C:25]([O:28][C:29]([F:44])([F:45])[C:30]3[CH:31]=[CH:32][C:33]([O:36][CH2:37][CH2:38][CH2:39][C:40]([F:41])([F:42])[F:43])=[CH:34][CH:35]=3)=[CH:26][CH:27]=2)=[O:13])=[CH:6][CH:5]=1

Participants

5

Reactant 1

HCID 86676555HCID 86676555, compound

Product 1

HCID 86676554HCID 86676554, compoundYield 87.4%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

9.57 g (8.38 mmol) of 2,2-bis(4-nitrobenzyl)-3-{[(2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenyl]methoxy}phenyl)prop-2-enoyl]oxy}propyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenyl]methoxy}phenyl)prop-2-enoate are dissolved in a mixture of 54 mL of N,N-dimethylformamide 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 400 g silica gel using toluene:ethyl acetate 1:3 as eluent and crystallization from ethyl acetate:hexane mixture yielded 7.93 g of 2,2-bis(4-aminobenzyl)-3-{[(2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenyl]methoxy}phenyl)prop-2-enoyl]oxy}propyl (2E)-3-(4-{difluoro[4-(4,4,4-trifluorobutoxy)phenyl]methoxy}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 400 g silica gel
  9. customcrystallization from ethyl acetate

Sources & evidence

ORD record
ord-74a75ca3470b48309c7b2227e9e957f0
Source dataset
uspto-grants-2015_08
Patent number
US09097938B2

Reaction notes

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