Dimethyl(methylene)ammounium iodide → HCID 57611912, compound

HRID 1919916Notes

Reaction equation

HRID 1919916 reaction equation
[CH3:1][O:2][C:3](=[O:18])[CH2:4][C:5]1[CH:17]=[CH:16][C:8]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[CH:7][CH:6]=1.C[Si](C)(C)[N-][Si](C)(C)C.[Li+].[CH3:29][N+:30]([CH3:32])=[CH2:31].[I-]>C1COCC1.O>[CH3:29][N:30]([CH2:32][CH:4]([C:5]1[CH:17]=[CH:16][C:8]([C:9]([O:11][C:12]([CH3:14])([CH3:15])[CH3:13])=[O:10])=[CH:7][CH:6]=1)[C:3]([O:2][CH3:1])=[O:18])[CH3:31]

Participants

6

Reactant 3

HCID 2724133Dimethyl(methylene)ammounium iodideHCID 2733832Lithium HexamethyldisilazideHCID 57611856Tert-butyl 4-((methoxycarbonyl)methyl)benzoate

Product 1

HCID 57611912HCID 57611912, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of tert-butyl 4-(2-methoxy-2-oxoethyl)benzoate (800 mg, 3.20 mmol) in THF (15 mL) was cooled to −78° C. before adding lithium hexamethyldisilazide (1M in THF, 4.16 mL, 4.16 mmol) dropwise. After 15 minutes, Eschenmoser's salt (1.18 g, 6.40 mmol) was added in one portion. The reaction was stirred at −78° C. for 5 minutes, warmed to room temperature, and stirred an additional 1 h. The mixture was diluted with water and extracted with EtOAc. The organic layer was then extracted with 1N HCl. The acidic aqueous layer was neutralized with sat. NaHCO3 and extracted with EtOAc. The new organic extracts were dried over MgSO4 and evaporated to yield tert-butyl 4-{1-[(dimethylamino)methyl]-2-methoxy-2-oxoethyl}benzoate as a white solid. 1H NMR (CDCl3) δ 7.91 (d, J=8.5 Hz, 2H), 7.35 (d, J=8.2 Hz, 2H), 3.84 (dd, J=9.7, 5.6 Hz, 1H), 3.65 (s, 3H), 3.10 (dd, J=12.3, 9.7 Hz, 1H), 2.47 (dd, J=12.3, 5.6 Hz, 1H), 2.24 (s, 6H), 1.55 (s, 9H). MS (ESI) calcd [M+H]+ 308.1, found 308.1.

Workup

  1. temperaturewarmed to room temperature
  2. stirringstirred an additional 1 h
  3. extractionextracted with EtOAc
  4. extractionThe organic layer was then extracted with 1N HCl
  5. extractionextracted with EtOAc
  6. dry with materialThe new organic extracts were dried over MgSO4
  7. customevaporated

Sources & evidence

ORD record
ord-c50bbcf1c4fb418da05f73dfe947fc9b
Source dataset
uspto-grants-2012_05
Patent number
US08168658B2

Reaction notes

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