Hydrochloric Acid → HCID 22676743, compound

HRID 1006278Notes

Reaction equation

HRID 1006278 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-])=O)[C:3]=1/[CH:11]=[CH:12]/[C:13]([O:15][CH2:16][CH3:17])=[O:14].[Si:18](Cl)([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19].N1C=CN=C1.Cl.P(OCC)(OCC)OCC>C(OCC)(=O)C.CN(C)C=O>[CH3:19][Si:18]([CH3:20])([O:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]2[C:3]=1[CH:11]=[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[NH:8]2)[C:21]([CH3:24])([CH3:23])[CH3:22]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 795ImidazoleHCID 28928tert-Butyldimethylsilyl chlorideHCID 31215Triethyl phosphiteHCID 86587877HCID 86587877, compound

Product 1

HCID 22676743HCID 22676743, compoundYield 64%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
170 °C

Procedure

To a round-bottomed flask at rt was charged with ethyl (2E)-3-(2-hydroxy-6-nitrophenyl)prop-2-enoate (Example 206, 260 mg, 1.10 mmol), N,N-dimethylformamide (2 mL), t-butyldimethylsilyl chloride (198 mg, 1.32 mmol), and imidazole (150 mg, 2.20 mmol). The resulting mixture was left stirring at rt for 2 hours before hydrochloric acid was added and the mixture was extracted with diethyl ether (2×20 mL). The combined organic layer was washed with water, brine, and dried over anhydrous sodium sulfate. The concentrated residue was used without further purification. It was mixed with triethyl phosphite (920 mg, 5.50 mmol) and heated to 170° C. for 3 hours before it was cooled to rt and diluted with ethyl acetate. The mixture was washed with water, brine and dried over anhydrous sodium sulfate. The concentrated residue was purified with silica gel flash chromatography by using hexane/ethyl acetate (3/1) as the eluant to give ethyl 4-(1,1,2,2-tetramethyl-1-silapropoxy)indole-2-carboxylate as a white solid (224 mg, 64%): Rf0.57 (3/1 hexane/ethyl acetate); %): MS (MH+) calcd for C17H26NO3Si 320.2, found 320.2; 1H NMR (DMSO-d6) δ 11.87 (br s, 1H), 6.99-7.15 (m, 3H), 6.47 (dd, J=7.3, 0.6 Hz, 1H), 4.33 (q, J=7.0 Hz, 2H), 1.33 (t, J=7.0 Hz, 3H), 1.01 (s, 9H), 0.22 (s, 6H).

Workup

  1. waitThe resulting mixture was left
  2. additionwas added
  3. extractionthe mixture was extracted with diethyl ether (2×20 mL)
  4. washThe combined organic layer was washed with water, brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customThe concentrated residue was used without further purification
  7. temperaturewas cooled to rt
  8. washThe mixture was washed with water, brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. customThe concentrated residue was purified with silica gel flash chromatography

Sources & evidence

ORD record
ord-aabffe30b25140beb69b156cbd309421
Source dataset
uspto-grants-2004_09
Patent number
US06787651B2

Reaction notes

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