Sodium Methoxide → HCID 87366641, compound

HRID 1670050Notes

Reaction equation

HRID 1670050 reaction equation
C[O-].[Na+].C([O:12][CH:13]([CH2:55][O:56][C@H:57]1[O:86][C@H:85]([CH2:87][O:88][CH2:89][C:90]2[CH:95]=[CH:94][CH:93]=[CH:92][CH:91]=2)[C@H:76]([O:77][CH2:78][C:79]2[CH:84]=[CH:83][CH:82]=[CH:81][CH:80]=2)[C@H:67]([O:68][CH2:69][C:70]2[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=2)[C@H:58]1[O:59][CH2:60][C:61]1[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=1)[CH2:14][O:15][C@H:16]1[O:45][C@H:44]([CH2:46][O:47][CH2:48][C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[C@H:35]([O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@H:26]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@H:17]1[O:18][CH2:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)(=O)C1C=CC=CC=1>CO.ClCCl>[CH2:19]([O:18][C@@H:17]1[C@@H:26]([O:27][CH2:28][C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[C@@H:35]([O:36][CH2:37][C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[C@@H:44]([CH2:46][O:47][CH2:48][C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)[O:45][C@@H:16]1[O:15][CH2:14][CH:13]([CH2:55][O:56][C@H:57]1[O:86][C@H:85]([CH2:87][O:88][CH2:89][C:90]2[CH:95]=[CH:94][CH:93]=[CH:92][CH:91]=2)[C@H:76]([O:77][CH2:78][C:79]2[CH:84]=[CH:83][CH:82]=[CH:81][CH:80]=2)[C@H:67]([O:68][CH2:69][C:70]2[CH:71]=[CH:72][CH:73]=[CH:74][CH:75]=2)[C@H:58]1[O:59][CH2:60][C:61]1[CH:62]=[CH:63][CH:64]=[CH:65][CH:66]=1)[OH:12])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

5

Reactant 2

HCID 10942334Sodium MethoxideHCID 87366546HCID 87366546, compound

Product 1

HCID 87366641HCID 87366641, compoundYield 79%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

Sodium methoxide (30%, ca 0.1 mL) was added dropwise to a stirred solution of benzoate 41 (209 mg, 0.168 mmol) in dry methanol (6 mL) and dichloromethane (2 mL) under argon. After 12 hrs the reaction mixture was partitioned between ether (50 mL) and 2M HCl (50 mL). The aqueous phase was re-extracted with ether (50 mL) and the combined ethereal extract washed with H2O (60 mL). After drying (MgSO4) and filtration the solvent was removed at reduced pressure to give the crude product that was purified by column chromatography on silica gel. Gradient elution with ethyl acetate/petroleum ether (30:70→50:50) afforded the title compound 42 (150 mg, 0.132 mmol, 79%) as a thin film; [α]D22 +61.3 (c 3.00, CH2Cl2); 1H NMR (300 MHz, CDCl3) δ 7.35-7.15 (m, 40H), 4.90-4.35 (m, 18H), 4.10-3.82 (m, 9H), 3.70-3.42 (m, 9H); 13C NMR (75 MHz, CDCl3) δ 139.2, 139.1, 139.0, 138.9, 138.4, 128.8, 128.7, 128.6, 128.5, 128.4, 128.2, 128.1, 128.0, 127.9, 99.4, 99.2, 79.5, 77.1, 77.0, 75.5, 75.2, 73.9, 73.8, 73.6, 73.5, 71.1, 71.0, 70.2, 69.7, 69.6, 69.5; HRMS-ESI (+ve) (Found: m/z 1154.5579 (MNH4+). C71H80NO14 requires m/z 1154.5624).

Workup

  1. customAfter 12 hrs the reaction mixture was partitioned between ether (50 mL) and 2M HCl (50 mL)
  2. extractionThe aqueous phase was re-extracted with ether (50 mL)
  3. extractionthe combined ethereal extract
  4. washwashed with H2O (60 mL)
  5. customAfter drying
  6. filtration(MgSO4) and filtration the solvent
  7. customwas removed at reduced pressure
  8. customto give the crude product that
  9. customwas purified by column chromatography on silica gel
  10. washGradient elution with ethyl acetate/petroleum ether (30:70→50:50)

Sources & evidence

ORD record
ord-e31250ff55e7423aa4a5b5217697d1e5
Source dataset
uspto-grants-2011_08
Patent number
US07989602B2

Reaction notes

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