Dimethyl Sulfide → HCID 15678071, compound

HRID 260402Notes

Reaction equation

HRID 260402 reaction equation
[CH3:1][O:2][C:3]1[CH:16]=[CH:15][C:14]2[C:5](=[C:6]3[C:11](=[CH:12][N:13]=2)[CH2:10][CH2:9][CH2:8][CH2:7]3)[CH:4]=1.C1C=C(Cl)C=C(C(OO)=[O:25])C=1.CSC.C(=O)(O)[O-].[Na+]>ClCCl>[CH3:1][O:2][C:3]1[CH:16]=[CH:15][C:14]2[N+:13]([O-:25])=[CH:12][C:11]3[CH2:10][CH2:9][CH2:8][CH2:7][C:6]=3[C:5]=2[CH:4]=1

Participants

6

Reactant 4

HCID 1068Dimethyl SulfideHCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 10856826HCID 10856826, compound

Product 1

HCID 15678071HCID 15678071, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
25 °C

Procedure

To a solution of Compound 273 (91.80 g, 430 mmol) in dichloromethane (500 mL) cooled at zero degrees C. was added a solution of mCPBA (55 percent, 161.7 g, 516 mmol) in dichloromethane (900 mL), and the resulting mixture was stirred at 25° C. for 1 hour. Dimethyl sulfide (6.95 mL, 94.6 mmol) was added and stirring was continued for 15 minutes followed by addition of saturated aqueous sodium bicarbonate solution (1000 mL). The organic layer was separated and the aqueous layer was extracted with dichloromethane (500 mL). The combined organic layers were dried (MgSO4), filtered through a 3 cm×3 cm plug of silica, and evaporated in vacuo. The residue was purified recrystallization from benzene-cyclohexane to give a total of 88.34 g (90 percent) of the N-oxide Compound 280a: off-white crystalline solid; mp 167-169° C; R f =0.31 (silica, 20 percent methanol in ethyl acetate); IR (CHCl 3) νmax 2943, 1617, 1512, 1459, 1428, 1379, 1108 cm- ; 1H NMR (500 MHz, CDCl3) δ 8.65 (d, J=9.5 Hz, 1 H, H4), 8.18 (s, 1 H, H 6), 7.30 (dd, J=9.5, 2.6 Hz, 1 H, H3), 7.10 (d, J=2.6 Hz, 1 H, Hi), 2.95 (t, J=6.2 Hz, 2 H, H10), 2.77 (t, J=6.2 Hz, 2 H, H7), 1.99-1.94 and 1.89-1.85 (m, 2 H each, H and H9); NMR (125 MHz, CDCl3) δ 159.1, 134.8, 134.3, 131.4, 130.8, 121.7, 120.3, 101.8, 55.5, 27.0, 24.7, 22.1, 21.8; MS (FAB+) m/e (rel intensity) 230 (M +H, 100), 213 (10); HRMS for C14H 1 6 NO 2 (M +H), calcd 230.1181, found 230. 1194.

Workup

  1. stirringstirring
  2. waitwas continued for 15 minutes
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted with dichloromethane (500 mL)
  5. dry with materialThe combined organic layers were dried (MgSO4)
  6. filtrationfiltered through a 3 cm×3 cm plug of silica
  7. customevaporated in vacuo
  8. customThe residue was purified
  9. customrecrystallization from benzene-cyclohexane

Sources & evidence

ORD record
ord-0a7bbb2cd74f497485c918d4228f9ba4
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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