Water → HCID 58104896, compound

HRID 2278478Notes

Reaction equation

HRID 2278478 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[O:15][C:14]([C:16]3[CH:17]=[C:18]([C:22]4[O:26][C:25]([C:27]5[CH:28]=[C:29]([OH:33])[CH:30]=[CH:31][CH:32]=5)=[N:24][N:23]=4)[CH:19]=[CH:20][CH:21]=3)=[N:13][N:12]=2)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].CC1C=CC(S(O[CH2:45][CH:46]2[CH2:51][CH:50]3[CH2:52][CH:47]2[CH:48]=[CH:49]3)(=O)=O)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].O>CN(C=O)C.ClCCl.CO>[CH:47]12[CH2:52][CH:50]([CH:49]=[CH:48]1)[CH2:51][CH:46]2[CH2:45][O:33][C:29]1[CH:28]=[C:27]([C:25]2[O:26][C:22]([C:18]3[CH:19]=[CH:20][CH:21]=[C:16]([C:14]4[O:15][C:11]([C:8]5[CH:9]=[CH:10][C:5]([C:1]([CH3:4])([CH3:2])[CH3:3])=[CH:6][CH:7]=5)=[N:12][N:13]=4)[CH:17]=3)=[N:23][N:24]=2)[CH:32]=[CH:31][CH:30]=1

Participants

7

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 13695169HCID 13695169, compoundHCID 58104887HCID 58104887, compound

Product 1

HCID 58104896HCID 58104896, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

To a solution of 3-(5-(3-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)phenyl)-1,3,4-oxadiazol-2-yl)phenol (0.92 g, 2.10 mmol) and bicyclo[2,2,1]hept-5-en-2-ylmethyl 4-methylbenzenesulfonate (1.6 g, 5.75 mmol) in DMF (45.0 ml), was added Cs2CO3 (4.5 g, 13.81 mmol) at room temperature under nitrogen. The reaction was carried out at 100° C. for 2 hours. After cooling down to room temperature, water (100.0 ml) was added into the reaction mixture. A brown solid precipitate was collected by filtration and washed with methanol and then dried under vacuum. The crude product was purified by a silica gel column using dichloromethane/ethyl acetate, ratio (9.3:0.7), as the eluent. After removal of the solvents, a pure white solid product was obtained in 0.97 g (85.1%) yield by recrystallization from dichloromethane/methanol. 1H NMR (400 MHz, CDCl3) δ: 8.86 (m, 1H), 8.34 (dd, 2H, J1=8.0 Hz, J2=1.6 Hz), 8.11 (d, 2H, J=8.4 Hz), 7.73 (m, 2H), 7.67 (m, 1H), 7.58 (d, 2H, J=8.4 Hz), 7.45 (m, 1H), 7.12 (m, 1H), 6.22-5.99 (m, 2H, C═C—H, endo and exo), 4.17-3.64 (m, 2H, OCH2, endo and exo), 3.09 (s, br), 2.91 (m, br), 2.61 (m, br), 1.95 (m), 1.52 (m), 1.39 (s, 9H, 3×CH3), 1.40-1.23 (m), 0.68 (m) ppm. 13C NMR (100 MHz, CDCl3) δ: 165.14, 163.65, 163.38, 159.57, 155.67, 137.68, 136.90, 136.38, 132.29, 130.26, 129.99, 129.77, 129.71, 126.92, 126.13, 125.13, 124.98, 124.94, 124.61, 120.73, 119.31, 119.22, 118.90, 112.29, 72.57, 71.78, 49.42, 45.06, 43.87, 43.69, 42.23, 41.60, 38.54, 38.32, 35.12, 31.10, 29.62, 28.99 ppm. MS (m/z): [M+1]+ calcd for C34H32N4O3 545.3. found 545.2. Anal. Calcd for C34H32N4O3: C, 74.98; H, 5.92; N, 10.29. Found: C, 74.77; H, 6.02; N, 10.27.

Workup

  1. filtrationA brown solid precipitate was collected by filtration
  2. washwashed with methanol
  3. customdried under vacuum
  4. customThe crude product was purified by a silica gel column
  5. customAfter removal of the solvents
  6. customa pure white solid product was obtained in 0.97 g (85.1%)

Sources & evidence

ORD record
ord-e83dd87c375a4eb7931f4d6670a09525
Source dataset
uspto-grants-2015_09
Patent number
US09133177B2

Reaction notes

Loading…