Ammonium Chloride → HCID 58497067, compound

HRID 910046Notes

Reaction equation

HRID 910046 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].C([Li])CCC.[CH2:12]([O:14][C:15](=[O:27])[CH2:16][O:17][C:18]1[CH:23]=[CH:22][C:21]([Br:24])=[CH:20][C:19]=1[CH:25]=[O:26])[CH3:13].[NH4+].[Cl-]>C1COCC1.CCOCC>[CH2:12]([O:14][C:15](=[O:27])[CH2:16][O:17][C:18]1[CH:23]=[CH:22][C:21]([Br:24])=[CH:20][C:19]=1[CH:25]([OH:26])[C:6]#[C:5][Si:2]([CH3:4])([CH3:3])[CH3:1])[CH3:13]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 66111TrimethylsilylacetyleneHCID 880259ethyl (4-bromo-2-formylphenoxy)acetateHCID 178418339Butyllithium

Product 1

HCID 58497067HCID 58497067, compoundYield 54.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a cooled (−78° C.) solution of (trimethylsilyl)acetylene (3.93 g, 40.0 mmol) in dry THF (40 mL) was slowly added a 2.5 M solution of butyllithium in hexanes (14.54 mL, 36.36 mmol). After stirring for 30 minutes at −78° C., the mixture was transferred to a cooled (−78° C.) solution of (4-bromo-2-formylphenoxy)acetic acid ethyl ester (10.44 g, 36.36 mmol) in dry THF (120 mL). Upon completion, the reaction mixture was stirred at −78° C. for 45 minutes. Saturated aq. NH4Cl (40 mL) was slowly added to the reaction mixture followed by Et2O (40 mL). The quenched reaction mixture was allowed to warm up to room temperature. The phases were separated and the aqueous phase was extracted with Et2O (2×). The combined organic phases were washed with brine, dried (MgSO4) and concentrated in vacuo. The crude oil was purified by column chromatography (SiO2), then was stirred for 90 min with polystyrene-supported trisamine (PS-Trisamine, 4.17 mmol/g, 8 g) in CH2Cl2 (160 mL). The resin was filtered off and the filtrate was concentrated in vacuo to give the title compound as pale yellow oil (7.6 g, 19.7 mmol, 54%). LC/MS (an10p8) Rt 4.30 min, m/z 408 [M+Na]+; 1H NMR (CDCl3): δ 0.24 (s, 9H), 1.31 (t, 3H), 4.27 (q, 2H), 4.71 (s, 2H), 5.79 (s, 1H), 6.74 (d, 1H), 7.39 (dd, 1H), 7.79 (d, 1H).

Workup

  1. stirringUpon completion, the reaction mixture was stirred at −78° C. for 45 minutes
  2. customThe quenched reaction mixture
  3. temperatureto warm up to room temperature
  4. customThe phases were separated
  5. extractionthe aqueous phase was extracted with Et2O (2×)
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customThe crude oil was purified by column chromatography (SiO2)
  10. stirringwas stirred for 90 min with polystyrene-
  11. filtrationThe resin was filtered off
  12. concentrationthe filtrate was concentrated in vacuo

Sources & evidence

ORD record
ord-4c92aefa8db4423d9c63364548c6381b
Source dataset
uspto-grants-2011_09
Patent number
US08022063B2

Reaction notes

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