m-Chloroperbenzoic acid → HCID 16102691, compound

HRID 1640949Notes

Reaction equation

HRID 1640949 reaction equation
ClC1C=C(C=CC=1)C(OO)=[O:6].[Br:12][C:13]1[C:22]([O:23][CH3:24])=[C:21]2[C:16]([C:17](=[O:35])[C:18]([C:30]([O:32][CH2:33][CH3:34])=[O:31])=[C:19]([S:28][CH3:29])[N:20]2[CH:25]2[CH2:27][CH2:26]2)=[CH:15][CH:14]=1>C(Cl)Cl>[Br:12][C:13]1[C:22]([O:23][CH3:24])=[C:21]2[C:16]([C:17](=[O:35])[C:18]([C:30]([O:32][CH2:33][CH3:34])=[O:31])=[C:19]([S:28]([CH3:29])=[O:6])[N:20]2[CH:25]2[CH2:26][CH2:27]2)=[CH:15][CH:14]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 16102690HCID 16102690, compound

Product 1

HCID 16102691HCID 16102691, compoundYield 55.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

m-Chloroperoxybenzoic acid (≦77%, 273.5 mg, 1.22 mmol) is added in one portion to a solution of crude ethyl 15 (from above ˜1.22 mmol) in methylene chloride (5.0 mL) at room temperature. The reaction mixture is stirred for 1 h, diluted with methylene chloride (10 mL), and washed with a saturated aqueous solution of sodium bicarbonate (25 mL). The organic layer is dried over magnesium sulfate and evaporated under reduced pressure to give the crude product. This material is purified by flash column chromatography (eluting with ethyl acetate; Rf 0.37) to give 290.9 mg of pure ethyl 16 as a white solid. 1H NMR (CDCl3): δ 0.54 (m, 1H, c-Pr CH2 (A)), 0.93 (m, 1H, c-Pr CH2 (B)), 1.12 (m, 1H, c-Pr CH2 (A)), 1.28 (m, 1H, c-Pr CH2 (B)), 1.38 (t, J=7.0 Hz, 3H, CO2CH2CH3), 3.26 (s, 3H, S(O)CH3), 3.83 (s, 3H, OCH3), 3.92 (m, 1H, c-Pr CH), 4.40 (m, 2H, overlapping CO2CHHCH3), 7.58 (d, J=8.5 Hz, 1H, aromatic H-6), 7.87 (d, J=8.5 Hz, 1H, aromatic H-5). 13C{1H} NMR (CDCl3): δ 10.8 (br, c-Pr CH2 (A)), 13.9 (br, c-Pr CH2 (B)), 14.1 (CO2CH2CH3), 35.1 (c-Pr CH), 41.4 (S(O)—CH3), 61.1 (OCH3), 62.1 (CO2CH2CH3), 118.9 (C-3), 122.8 (CH, C-5), 123.9 (C—Br, C-7), 129.5 (C-4a), 130.0 (CH, C-6), 138.2 (C-8a), 148.3 (C—OCH3, C-8), 164.0 (CO2CH2CH3), 164.1 (br, C—S(O)—CH3, C-2), 174.6 (C═O, C-4). LCMS m/z calcd for C17H1879BrNO5S ([M]+) 427. Found 428 ([M+H]+). HRMS m/z calcd for C17H1879BrNNaO5S 449.9987 ([M+Na]+). Found 449.9977.

Workup

  1. washwashed with a saturated aqueous solution of sodium bicarbonate (25 mL)
  2. dry with materialThe organic layer is dried over magnesium sulfate
  3. customevaporated under reduced pressure
  4. customto give the crude product
  5. customThis material is purified by flash column chromatography (eluting with ethyl acetate; Rf 0.37)

Sources & evidence

ORD record
ord-b5c41da0333c4f9f827dde8cb3b11b12
Source dataset
uspto-grants-2012_02
Patent number
US08114888B2

Reaction notes

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