Hydrochloric Acid → HCID 68597147, compound

HRID 2385085Notes

Reaction equation

HRID 2385085 reaction equation
[CH3:1][N:2]1[C:10]2[CH:9]=[C:8]3[O:11][CH2:12][CH2:13][O:14][C:7]3=[CH:6][C:5]=2[CH:4]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[N+:21]([O-:23])=[O:22])[C:3]1=[O:24].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].C([C:37]([O:39][CH3:40])=[O:38])#N.Cl>O1CCCC1>[CH3:1][N:2]1[C:10]2[CH:9]=[C:8]3[O:11][CH2:12][CH2:13][O:14][C:7]3=[CH:6][C:5]=2[C:4]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[N+:21]([O-:23])=[O:22])([C:37]([O:39][CH3:40])=[O:38])[C:3]1=[O:24]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 28660Carbonocyanidic acid, methyl esterHCID 2733832Lithium HexamethyldisilazideHCID 68598885HCID 68598885, compound

Product 1

HCID 68597147HCID 68597147, compoundYield 45.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 6-methyl-8-(2-nitrophenyl)-2,3,6,8-tetrahydro-7H-[1,4]dioxino[2,3-f]indol-7-one (0.40 g, 1.2 mmol) in tetrahydrofuran (10 mL) was added lithium bis(trimethylsilyl)amide (1.0 M solution in tetrahydrofuran, 1.5 mL, 1.5 mmol) at 0° C. The reaction mixture was stirred at 0° C. for 10 min, methyl cyanoformate (0.12 mL, 1.5 mmol) was added and the mixture was stirred at ambient temperature for 18 h. 10% w/v hydrochloric acid (5 mL) was added at 0° C. and the mixture was extracted with ethyl acetate (3×50 mL). The combined organic extracts were washed with water and brine, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo. The residue was purified by column chromatography and eluted with ethyl acetate/hexanes (1/2) to afford methyl 6-methyl-8-(2-nitrophenyl)-7-oxo-2,3,7,8-tetrahydro-6H-[1,4]dioxino[2,3-f]indole-8-carboxylate (0.21 g, 44%): 1H NMR (300 MHz, CDCl3) δ 7.92-7.89 (m, 1H), 7.48-7.37 (m, 2H), 7.20-7.19 (m, 1H), 6.97 (s, 1H), 6.41 (s, 1H), 4.21-4.14 (m, 4H), 3.65 (s, 3H), 3.12 (s, 3H).

Workup

  1. stirringthe mixture was stirred at ambient temperature for 18 h
  2. additionwas added at 0° C.
  3. extractionthe mixture was extracted with ethyl acetate (3×50 mL)
  4. washThe combined organic extracts were washed with water and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated in vacuo
  8. customThe residue was purified by column chromatography
  9. washeluted with ethyl acetate/hexanes (1/2)

Sources & evidence

ORD record
ord-459cc010279d435ca39b2cc120cf383c
Source dataset
uspto-grants-2012_09
Patent number
US08263606B2

Reaction notes

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