Citric Acid → HCID 131730353, compound

HRID 1950756Notes

Reaction equation

HRID 1950756 reaction equation
C(OC([NH:8][CH2:9][CH2:10][O:11][C:12]1[CH:17]=[C:16]([C:18]([CH3:26])([CH3:25])[O:19][SiH2:20][C:21]([CH3:24])([CH3:23])[CH3:22])[CH:15]=[C:14]([C:27]([CH3:35])([CH3:34])[O:28][SiH2:29][C:30]([CH3:33])([CH3:32])[CH3:31])[CH:13]=1)=O)(C)(C)C.I[CH3:37].[H-].[Na+].C(O)(=O)[CH2:41][C:42]([CH2:47]C(O)=O)([C:44](O)=O)[OH:43].[O:53]1CCC[CH2:54]1>O>[C:42]([O:43][C:54]([CH:9]([NH:8][CH3:37])[CH2:10][O:11][C:12]1[CH:17]=[C:16]([C:18]([CH3:26])([CH3:25])[O:19][SiH2:20][C:21]([CH3:22])([CH3:24])[CH3:23])[CH:15]=[C:14]([C:27]([CH3:35])([CH3:34])[O:28][SiH2:29][C:30]([CH3:32])([CH3:31])[CH3:33])[CH:13]=1)=[O:53])([CH3:41])([CH3:44])[CH3:47]

Participants

7

Reactant 5

HCID 311Citric AcidHCID 6328Methyl iodideHCID 8028Tetrahydrofuran2×HCID 24758Sodium hydrideHCID 131730354HCID 131730354, compound

Product 1

HCID 131730353HCID 131730353, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 1-(2-tert-butoxycarbonylamino-ethoxy)-3,5-bis-(tert-butyl-dimethyl-silyloxymethyl)-benzene (270 mg) in tetrahydrofurane (5 mL) was added iodomethane (70 μL) and the reaction mixture was cooled (0° C.). To the cooled solution, sodium hydride was added (68 mg). After 1 hour, the temperature was allowed to warm up to room temperature. After 16 hours, a mixture of THF and water 1:1 (2 mL) was slightly added, then citric acid until pH=2. The aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate and concentrated in vacuo to a residue. The residue was purified by silica gel chromatography (Merck SuperVarioFlash 25 g column, Si60 15-40 μm), using gradient elution with a mixture of heptane (A)/ethyl acetate (B), (gradient: 100% A down to 85% A: 15% B) to give 1-(2-(tert-butoxycarbonyl)-methylamino-ethoxy)-3,5-bis-(tert-butyl-dimethyl-silyloxy methyl)-benzene (220 mg): LC/MS (Method A2): ES: m/z 562 (M+Na)+; m/z 308 (M+H−C5H8O2−OSiC6H16)+; RT=1.50 min

Workup

  1. temperatureto warm up to room temperature
  2. waitAfter 16 hours
  3. additionwas slightly added
  4. extractionThe aqueous phase was extracted three times with ethyl acetate
  5. washThe combined organic layers were washed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated in vacuo to a residue
  8. customThe residue was purified by silica gel chromatography (Merck SuperVarioFlash 25 g column, Si60 15-40 μm)
  9. washelution
  10. additionwith a mixture of heptane (A)/ethyl acetate (B)

Sources & evidence

ORD record
ord-340a78df95314310b714eb0e4332cbb0
Source dataset
uspto-grants-2013_03
Patent number
US08404678B2

Reaction notes

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