Dimethyl Disulfide → HCID 22988007, compound

HRID 1017671Notes

Reaction equation

HRID 1017671 reaction equation
CC1(C)CCCC(C)(C)N1.C([Li])CCC.[C:16]([O:20][C:21]([N:23]1[C:31]2[C:26](=[N:27][CH:28]=[CH:29][CH:30]=2)[C:25]([C:32]2[CH:37]=[CH:36][C:35]([F:38])=[CH:34][CH:33]=2)=[C:24]1[C:39]1[CH:44]=[CH:43][N:42]=[CH:41][CH:40]=1)=[O:22])([CH3:19])([CH3:18])[CH3:17].[CH3:45][S:46]SC>O1CCCC1>[C:16]([O:20][C:21]([N:23]1[C:31]2[C:26](=[N:27][CH:28]=[CH:29][C:30]=2[S:46][CH3:45])[C:25]([C:32]2[CH:37]=[CH:36][C:35]([F:38])=[CH:34][CH:33]=2)=[C:24]1[C:39]1[CH:44]=[CH:43][N:42]=[CH:41][CH:40]=1)=[O:22])([CH3:19])([CH3:17])[CH3:18]

Participants

6

Reactant 4

HCID 12232Dimethyl DisulfideHCID 130352,2,6,6-TetramethylpiperidineHCID 22987987HCID 22987987, compoundHCID 178418339Butyllithium

Product 1

HCID 22988007HCID 22988007, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

2,2,6,6-Tetramethylpiperidine (1.76 ml, 10.40 mmol) was dissolved in tetrahydrofuran (39 ml) and placed under an atmosphere of nitrogen. The solution was cooled to −78° C. and n-butyllithium (3.96 ml, 9.91 mmol, 2.5 M solution of in hexanes) was added at such a rate that the internal temperature did not exceed −70° C. The reaction mixture was warmed to −10° C. for 30 min., then re-cooled to −78° C. A solution of 1-tert-butoxycarbonyl-3-(4-fluorophenyl)-2-(pyridin-4-yl)-pyrrolo[3,2-b]pyridine (0.965 g, 2.47 mmol) in tetrahydrofuran (32 ml) was cooled to −78° C. and then added via cannula at such a rate that the internal temperature did not exceed −70° C. After 1 h, dimethyldisulfide (0.29 ml, 3.22 mmol) was added and the resulting solution was stirred for an additional 1 h at −78° C. The reaction mixture was quenched with saturated ammonium chloride solution and the product was extracted into ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The crude residue was purified by flash chromatography using 20% acetone/hexanes as the eluant to give 1-tert-butoxycarbonyl-3-(4-fluorophenyl)-7-methylthio-2-(pyridin-4-yl)-pyrrolo[3,2-b]pyridine. MS: 435 (M).

Workup

  1. customdid not exceed −70° C
  2. temperatureThe reaction mixture was warmed to −10° C. for 30 min.
  3. temperaturere-cooled to −78° C
  4. additionadded via cannula at such a rate that the internal temperature
  5. customdid not exceed −70° C
  6. customThe reaction mixture was quenched with saturated ammonium chloride solution
  7. extractionthe product was extracted into ethyl acetate
  8. washThe organic layer was washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated in vacuo
  11. customThe crude residue was purified by flash chromatography

Sources & evidence

ORD record
ord-278ab824254e4e859e312c44ed3784e2
Source dataset
uspto-grants-2002_11
Patent number
US06479507B2

Reaction notes

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