m-Chloroperbenzoic acid → HCID 86747540, compound

HRID 260395Notes

Reaction equation

HRID 260395 reaction equation
[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[C:29][Si:30]([CH3:33])([CH3:32])[CH3:31])[C:22]3[CH2:21][CH2:20][CH2:19][CH:18]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[C:17]=3[C:16]3[CH:15]=[CH:14][C:13]([O:42][C:43](=[O:48])[C:44]([CH3:47])([CH3:46])[CH3:45])=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C1C=C(Cl)C=C(C(OO)=[O:57])C=1>C(Cl)Cl>[C:1]1([O:7][C:8]([N:10]2[CH:23]([C:24]#[C:25]/[CH:26]=[CH:27]\[C:28]#[C:29][Si:30]([CH3:31])([CH3:33])[CH3:32])[C:22]34[O:57][C:17]3([CH:18]([O:34][Si:35]([C:38]([CH3:41])([CH3:39])[CH3:40])([CH3:36])[CH3:37])[CH2:19][CH2:20][CH2:21]4)[C:16]3[CH:15]=[CH:14][C:13]([O:42][C:43](=[O:48])[C:44]([CH3:47])([CH3:46])[CH3:45])=[CH:12][C:11]2=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 88413590HCID 88413590, compound

Product 1

HCID 86747540HCID 86747540, compoundYield 71.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
25 °C

Procedure

To a solution of Compound 209 (mixture of diastereomers, 13.0 g, 19.06 mmol) in CH2Cl2 (100 mL) cooled at zero degrees C was added mCPBA (50 percent, 7.9 g, 22.98 mmol) followed by stirring at 25° C. for one hour. The reaction mixture was diluted with CH2Cl2 (500 mL), washed with saturated aqueous NaHCO3, dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was purified by flash column chromatography (silica gel, 10 percent ethyl ether in petroleum ether) to afford Compound 210 (9.5 g, 71 percent) as a mixture of diastereomers. Major isomer: Rf =0.38 (silica, 10 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 2958, 2933, 1730 (shoulder), 1721, 1382, 1307, 1118, 846 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 7.28 (d, J=8.6 Hz, 1 H, H1), 7.40-7.10 (m, 6 H, H4 and aromatic), 6.95 (dd, J=8.6, 1.9 Hz, 1 H, H2), 5.84-5.62 (m, 3 H, H6 and olefinic), 4.76 (dd, J=9.6, 5.7 Hz, 1 H, H10), 2.45 (dd, J=14.5, 4.6 Hz, 1 H, H7), 1.97- 1.57 (m, 5 H, H7, H8 and H9), 1.31 (br s, 9 H, COC(CH3)3), 0.87 (s, 9 H, SiC(CH3)3), 0.19 (s, 12 H, Si(CH3)3 and SiCH3), 0.06 (s, 3 H, SiCH3); MS (FAB+) m/e (rel intensity) 830 (M+Cs, 100), 681 (6), 624 (9), 534 (11); HRMS for C40H51NO6Si2Cs (M+Cs), calcd 830.2309, found 830.2361. Minor isomer: Rf =0.22 (silica, 10 percent ethyl ether in petroleum ether); IR (CHCl3) νmax 2958, 2933, 1747 (shoulder), 1721, 1494, 1381, 1306, 1256, 1181, 1118, 909, 844 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 7.58 (d, J=8.7 Hz, 1 H, H1), 7.40-7.10 (m, 6 H, H4 and aromatic), 6.95 (dd, J=8.7, 2.5 Hz, 1 H, H2), 5.80-5.60 (m, 3 H, H6 and olefinic), 4.89 (d, J=2.4 HZ, 1 H, H10), 2.66-2.50 (m, 1 H, H7), 2.18-1.63 (m, 5 H, H7, H8 and H9), 1.31 (br s, 9 H, COC(CH3)3), 0.94 and 0.79 (s, 9 H, SiC(CH3)3), 0.23, 0.21 and 0.19 (s, 9 H, Si(CH3)3), 0.14 (s, 3 H, SiCH3), 0.06 (s, 3 H, SiCH3); MS (FAB+) m/e (rel intensity) 830 (M+Cs, 100), 708 (8), 640 (13), 534 (7); HRMS for C40H51NO6Si2Cs (M+Cs), calcd 830.2309, found 830.2296.

Workup

  1. washwashed with saturated aqueous NaHCO3
  2. dry with materialdried over anhydrous Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified by flash column chromatography (silica gel, 10 percent ethyl ether in petroleum ether)

Sources & evidence

ORD record
ord-de325a6e741a4d398f58a80174fb2bb8
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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