Cesium carbonate → HCID 86684833, compound

HRID 595143Notes

Reaction equation

HRID 595143 reaction equation
[NH:1]1[C:10]2[CH:9]=[C:8]3[O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][C:7]3=[CH:6][C:5]=2[C:4](=[O:21])[CH:3]=[CH:2]1.C(=O)([O-])[O-].[Cs+].[Cs+].F[C:29]1[CH:34]=[CH:33][C:32]([N+:35]([O-:37])=[O:36])=[CH:31][C:30]=1[F:38]>CN(C=O)C.CC#N>[F:38][C:30]1[CH:31]=[C:32]([N+:35]([O-:37])=[O:36])[CH:33]=[CH:34][C:29]=1[O:21][C:4]1[C:5]2[CH:6]=[C:7]3[O:20][CH2:19][CH2:18][O:17][CH2:16][CH2:15][O:14][CH2:13][CH2:12][O:11][C:8]3=[CH:9][C:10]=2[N:1]=[CH:2][CH:3]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 1230531,2-Difluoro-4-nitrobenzeneHCID 73977853HCID 73977853, compound

Product 1

HCID 86684833HCID 86684833, compoundYield 41%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 6342AcetonitrileSolvent2×

Procedure

To a round bottom flask equipped with a magnetic stir bar was added 7,8,10,11,13,14-Hexahydro-1H-6,9,12,15-tetraoxa-1-aza-cyclododeca[b]naphthalen-4-one (12.2 g, 43.3 mmol, 1.0 eq.), acetonitrile (150 ml), DMF (150 ml) and cesium carbonate (28.2 g, 86.5 mmol, 2.0 eq). The mixture was stirred at room temperature for 30 minutes at which time 1,2-difluoro-4-nitro-benzene (7.57 g, 47.6 mmoL, 1.1 eq) was added over a 10 minute period. After 2 hours the reaction was complete at which time 75% of the MeCN and DMF were removed and the resulting solution was poured over into ice water. The solid was filtered and dried and further columned with a biotage system. The eluent was 1:3 ethyl acetate/hexane. Removal of the solvent afforded 4-(2-Fluoro-4-nitro-phenoxy)-7,8,10,11,13,14-hexahydro-6,9,12,15-tetraoxa-1-aza-cyclodo-deca[b]naphthalene as a pale green solid (7.4 g, 41% yield). 1HNMR (400 MHz, DMSO): 8.58 (s, 1H), 7.80 (s, 1H), 7.50 (s, 1H), 7.04 (t, 1H), 6.88 (m, 1H), 6.50 (m, 2H), 4.35 (s, 4H), 3.87 (d, 4H), 3.62 (s, 4H). LC/MS Calcd for (M+H)+431.4. found 431.5.

Workup

  1. customTo a round bottom flask equipped with a magnetic stir bar
  2. additionwas added over a 10 minute period
  3. customwere removed
  4. additionthe resulting solution was poured over into ice water
  5. filtrationThe solid was filtered
  6. customdried
  7. customRemoval of the solvent

Sources & evidence

ORD record
ord-9fcdc2257ad94827bb464879441d3604
Source dataset
uspto-grants-2016_01
Patent number
US09242991B2

Reaction notes

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