2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 68904099, compound

HRID 2110357Notes

Reaction equation

HRID 2110357 reaction equation
[CH3:1][C:2]1([CH3:14])[O:6][C@@H:5]([C@H:7]([C:9]2[S:10][CH:11]=[CH:12][CH:13]=2)O)[CH2:4][O:3]1.CC1(C)O[C@@H]([C@@H](C2SC=CC=2)O)CO1.[C-]#[C-].[Na+].[Na+].C1(C)C=CC(S(Cl)(=O)=O)=CC=1.[NH:44]1[C:52]2[C:47](=[CH:48][CH:49]=[CH:50][CH:51]=2)[CH2:46][CH2:45]1.N1C(C)=CC=CC=1C.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCCC1.O1CCOCC1.C(OCC)(=O)C>[CH3:1][C:2]1([CH3:14])[O:6][C@@H:5]([C@H:7]([C:9]2[S:10][CH:11]=[CH:12][CH:13]=2)[N:44]2[C:52]3[C:47](=[CH:48][CH:49]=[CH:50][CH:51]=3)[CH:46]=[CH:45]2)[CH2:4][O:3]1

Participants

11

Reactant 7

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 73974-Toluenesulfonyl chlorideHCID 79372,6-LutidineHCID 10328IndolineHCID 68902962HCID 68902962, compoundHCID 68907768HCID 68907768, compoundHCID 178463197HCID 178463197, compound

Product 1

HCID 68904099HCID 68904099, compound

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of (R)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl](2-thienyl)methanol and (S)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl](2-thienyl)methanol (1.5 g, 7.0 mmol) was dissolved in tetrahydrofuran (28 mL) and sodium acetylide (2.1 g, 7.7 mmol; 18 wt % slurry in xylenes/light mineral oil) and the mixture was stirred for 2 hours. para-Toluenesulfonyl chloride (1.46 g, 7.7 mmol) was added, and stirring was continued for 2 hours, then indoline (2.5 g, 21 mmol) was added followed by 2,6-lutidine (0.81 mL, 7.0 mmol). After 72 hours the mixture was quenched with a saturated aqueous solution of ammonium chloride, diluted with ethyl acetate, washed with water, and saturated brine. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The crude product was purified via Isco chromatography (Redisep, silica, gradient 1-10% ethyl acetate in hexane) to afford 590 mg that was immediately dissolved in dioxane (10 mL) and treated with dichlorodicyanobenzoquinone (552 mg, 2.4 mmol) and stirred for 30 minutes. The mixture was diluted with ethyl acetate and washed with a saturated aqueous solution of sodium bicarbonate, water, and saturated brine. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. The crude product was purified via Isco chromatography (Redisep, silica, gradient 1-20% ethyl acetate in hexane) to afford 160 mg of 1-[(R)-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl](2-thienyl)methyl]-1H-indole. HRMS: calcd for C18H19NO2S+H+, 314.12092; found (ESI-FTMS, [M+H]1+), 314.12089.

Workup

  1. customAfter 72 hours the mixture was quenched with a saturated aqueous solution of ammonium chloride
  2. additiondiluted with ethyl acetate
  3. washwashed with water, and saturated brine
  4. customThe organic layer was separated
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified via Isco chromatography (Redisep, silica, gradient 1-10% ethyl acetate in hexane)
  9. customto afford 590 mg that
  10. stirringstirred for 30 minutes
  11. washwashed with a saturated aqueous solution of sodium bicarbonate, water, and saturated brine
  12. customThe organic layer was separated
  13. dry with materialdried over anhydrous magnesium sulfate
  14. filtrationfiltered
  15. concentrationconcentrated in vacuo
  16. customThe crude product was purified via Isco chromatography (Redisep, silica, gradient 1-20% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-2b9c65a4cd684b6f83933fbf702133de
Source dataset
uspto-grants-2009_04
Patent number
US07517899B2

Reaction notes

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