Ethyl Acetate → HCID 57084567, compound

HRID 915703Notes

Reaction equation

HRID 915703 reaction equation
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[CH2:19]([O:26][C:27]1[C:49]([O:50][CH3:51])=[CH:48][C:30]([C:31]([N:33]2[CH2:37][C:36](=[CH2:38])[CH2:35][C@H:34]2[CH2:39][O:40][Si](C(C)(C)C)(C)C)=[O:32])=[C:29]([N+:52]([O-:54])=[O:53])[CH:28]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.CCOC(C)=O.[NH4+].[Cl-]>C1COCC1.CCOCC>[CH2:19]([O:26][C:27]1[C:49]([O:50][CH3:51])=[CH:48][C:30]([C:31]([N:33]2[CH2:37][C:36](=[CH2:38])[CH2:35][C@H:34]2[CH2:39][OH:40])=[O:32])=[C:29]([N+:52]([O-:54])=[O:53])[CH:28]=1)[C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 2724141Tetrabutylammonium FluorideHCID 69461525HCID 69461525, compound

Product 1

HCID 57084567HCID 57084567, compoundYield 96%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of TBAF (2.10 mL of a 1M solution in THF, 2.10 mmol) was added to the silyl-ether 16 (0.86 g, 1.68 mmol) in THF (20 mL) at 0° C. (ice/acetone). The reaction mixture was allowed to warm to room temperature following a colour change (yellow→dark red). After a further 40 minutes TLC (50% EtOAc/Pet-Ether 40°-60°) revealed the complete disappearance of starting material. Saturated NH4Cl (100 mL) was added and the reaction mixture extracted with EtOAc (3×40 mL), washed with brine (30 mL), dried (MgSO4), filtered and evaporated in vacuo to give a dark orange oil which was purified by flash chromatography (60% EtOAc/Petroleum Ether) to provide the pure alcohol 17 as a white solid (0.64 g, 96%): [α]19D=−22.9° (c=0.20, MeOH); 1H NMR (270 MHz, CDCl3) (Rotamers) δ 7.78 and 7.76 (s×2, 1Harom), 7.49-7.33 (m, 5Harom), 6.91 and 6.82 (s×2, 1Harom), 5.22 (s, 2H, PhCH2O), 5.10 (m,1H, OH), 5.03-5.01 (m, 1H, NCH2C═CH2), 4.90-4.85 (m,1H, NCH2C═CH2), 4.65-4.55 (m, 1H, NCHCH2OH), 3.99 and 3.95 (s×2, 3H, OCH3), 3.90-3.72 (m, 4H, NCHCH2OH and NCH2C═CH2), 2.90-2.87 (m,1H, NCH2C═CH2CH2), 2.53-2.47 (m, 1H, NCH2C═CH2CH2); 13C NMR (67.8 MHz, CDCl3) (Rotamers) δ 177.4 (NC═O), 155.1 (Cquat), 148.3 (Cquat), 142.6 (Cquat), 137.0 (Cquat), 135.2 (Cquat), 128.9,128.6 and 127.6 (BnC—Harom), 109.1 (C—Harom), 108.5 (C—Harom), 108.3 (NCH2C═CH2), 71.4 (PhCH2O), 65.2 and 63.7 (NCHCH2OH), 60.4 (NCHCH2OH), 56.8 and 56.7 (OCH3), 53.0 and 50.1 (NCH2C═CH2), 35.1 and 34.4 (NCH2C═CH2CH2); MS (EI), m/z (relative intensity) 398 (M+, 2), 380 (3), 368 (4), 354 (1), 286 (M-NCH2C═CH2CH2CHCH2OH, 54), 270 (2), 256 (1), 164 (2), 136 (4), 135 (3), 121 (4), 112 (NCH2C═CH2CH2CHCH2OH, 3), 91 (PhCH2, 100), 82 (3), 69 (4), 65 (6); IR (NUJOL7) 3600-3200 (br, OH), 2923, 2853, 1718, 1663, 1611 (NC═O), 1577, 1517, 1460, 1376, 1332, 1275, 1224, 1176, 1052, 990, 925, 886, 862, 796, 759, 723, 702 615 cm−1; exact mass calcd for C21H22N2O6 m/e 398.1478, obsd m/e 398.1490.

Workup

  1. extractionthe reaction mixture extracted with EtOAc (3×40 mL)
  2. washwashed with brine (30 mL)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. customevaporated in vacuo
  6. customto give a dark orange oil which
  7. customwas purified by flash chromatography (60% EtOAc/Petroleum Ether)

Sources & evidence

ORD record
ord-2afd74f99db4473c8fb26b7126a20b9f
Source dataset
uspto-grants-2007_09
Patent number
US07265105B2

Reaction notes

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