Potassium Hydroxide → HCID 86622039, compound

HRID 2252508Notes

Reaction equation

HRID 2252508 reaction equation
[OH-].[K+].C[O:4][C:5](=[O:70])/[CH:6]=[CH:7]\[CH:8]=[CH:9]\[C@H:10]([CH3:69])[C@@H:11]([O:61][Si:62]([C:65]([CH3:68])([CH3:67])[CH3:66])([CH3:64])[CH3:63])[CH2:12][C@H:13]([O:53][Si:54]([C:57]([CH3:60])([CH3:59])[CH3:58])([CH3:56])[CH3:55])/[CH:14]=[CH:15]\[C@H:16]([CH3:52])[C@H:17]([O:44][Si:45]([C:48]([CH3:51])([CH3:50])[CH3:49])([CH3:47])[CH3:46])[C@H:18]([CH3:43])[CH2:19][C@@H:20]([CH3:42])[CH2:21][CH2:22][C@@H:23]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[C@H:24]([CH3:33])[C@@H:25]([OH:32])[C@@H:26]([CH3:31])/[CH:27]=[CH:28]\[CH:29]=[CH2:30]>CCO.C1COCC1>[Si:62]([O:61][C@@H:11]([CH2:12][C@H:13]([O:53][Si:54]([C:57]([CH3:60])([CH3:59])[CH3:58])([CH3:55])[CH3:56])/[CH:14]=[CH:15]\[C@H:16]([CH3:52])[C@H:17]([O:44][Si:45]([C:48]([CH3:51])([CH3:50])[CH3:49])([CH3:46])[CH3:47])[C@H:18]([CH3:43])[CH2:19][C@@H:20]([CH3:42])[CH2:21][CH2:22][C@@H:23]([O:34][Si:35]([C:38]([CH3:39])([CH3:40])[CH3:41])([CH3:37])[CH3:36])[C@H:24]([CH3:33])[C@@H:25]([OH:32])[C@@H:26]([CH3:31])/[CH:27]=[CH:28]\[CH:29]=[CH2:30])[C@@H:10]([CH3:69])/[CH:9]=[CH:8]/[CH:7]=[CH:6]\[C:5]([OH:70])=[O:4])([C:65]([CH3:66])([CH3:67])[CH3:68])([CH3:64])[CH3:63]

Participants

5

Reactant 2

HCID 14797Potassium HydroxideHCID 86602911HCID 86602911, compound

Product 1

HCID 86622039HCID 86622039, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

1N aqueous KOH solution (1.2 mL) was added to a stirred solution of the above 97 (0.12 g, 0.12 μmol) in EtOH (12 mL), THF (1 mL) and the mixture was refluxed gently until the ester disappeared (about 5 h) as determined by TLC analysis. The ethanolic solution was concentrated and then diluted with ether (4 mL). After the solution was acidified to pH3 with 1N HCl solution, organic phase was separated and aqueous phase was extracted with Et2O (2×5 mL). The combined organic phases were dried with MgSO4, concentrated and used without further purification: IR (CHCl3) 2957, 2929, 2857, 1692, 1471, 1462, 1254, 1089, 836, 773 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.34 (dd, J=15.1, 11.4 Hz, 1H), 6.64 (ddd, J=16.0, 10.8, 10.5 Hz, 1H), 6.61 (t, J=11.2 Hz, 1H), 6.22 (dd, J=15.4, 6.0 Hz, 1H), 6.09 (t, J=11.0 Hz, 1H), 5.58 (d, J=11.3 Hz, 1H), 5.49-5.39 (m, 2H), 5.34-5.28 (m, 1H), 5.20 (d, J=16.7 Hz, 1H), 5.11 (d, J=10.2 Hz, 1H), 4.55 (m, 1H), 3.95 (m, 1H), 3.76 (m, 1H), 3.50 (m, 1H), 3.27 (m, 1H), 2.81 (m, 1H), 2.58 (m, 2H), 1.71 (m, 1H), 1.57-1.50 (m, 3H), 1.44-1.31 (m, 3H), 1.25 (d, J=7.3 Hz, 3H), 1.21 (d, J=6.1 Hz, 3H), 1.04 (d, J=6.9 Hz, 3H), 0.99 (d, J=7.0 Hz, 3H), 0.96-0.89 (m, 40H), 0.81 (d, J=6.2 Hz, 3H), 0.79 (d, J=5.9 Hz, 3H), 0.11-0.05 (m, 24H); 13C NMR (75 MHz, CDCl3) δ 171.1, 148.1, 147.3, 135.2, 132.8, 132.3, 131.6, 129.9, 126.6, 117.6, 115.0, 81.3, 77.6, 72.7, 66.4, 58.3, 43.0, 42.6, 40.1, 37.9, 36.0, 35.4, 35.2, 33.8, 32.2, 30.6, 26.3, 26.0, 25.9, 25.2, 19.6, 19.0, 18.4, 18.09, 18.05, 17.7, 16.6, 14.5, 7.0, −2.8, −3.45, −3.54, −3.7, −4.1, −4.2, −4.4; LRMS (ESI) 1029.7 [M+Na]+, 915.7, 897.7; HRMS (ESI) calcd for C56H110O7Si4Na 1029.7226 [M+Na]+, found 1029.7257; [α]20D−41.7 (c 1.4, CHCl3).

Workup

  1. custom(about 5 h)
  2. concentrationThe ethanolic solution was concentrated
  3. additiondiluted with ether (4 mL)
  4. customwas separated
  5. extractionaqueous phase was extracted with Et2O (2×5 mL)
  6. dry with materialThe combined organic phases were dried with MgSO4
  7. concentrationconcentrated
  8. customused without further purification

Sources & evidence

ORD record
ord-90dbaa9e4bac43e9ae53b50c7ce8d42e
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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