Dimethylformamide → HCID 19920598, compound

HRID 275180Notes

Reaction equation

HRID 275180 reaction equation
[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH:2]1C1C=CC(I)=CC=1OC)[CH2:8]2.[C:20]([Li])([CH3:23])([CH3:22])[CH3:21].CN(C)C=[O:28].[Cl-].[NH4+].[CH2:32]1[CH2:36][O:35][CH2:34][CH2:33]1>C(OCC)C>[C:7]12([C:33]3[CH:32]=[CH:23][C:20]([CH:22]=[O:28])=[CH:21][C:34]=3[O:35][CH3:36])[CH2:8][CH:1]3[CH2:2][CH:3]([CH2:4][CH:5]([CH2:10]3)[CH2:6]1)[CH2:9]2

Participants

7

Reactant 5

HCID 6228DimethylformamideHCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 19920648HCID 19920648, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 19920598HCID 19920598, compoundYield 43%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of 2-adamantyl-5-iodoanisole (1.29 g, 3.51 mmol) in anhydrous THF (50 mL) was cooled to -78° C. under argon and treated with t-butyllithium solution (4.34 mL, 1.7 M in pentane, 7.37 mmol). The reaction mixture was stirred at -78° C. for 20 min. and then treated with anhydrous N,N-dimethylformamide (0.28 g, 3.86 mmol). The reaction mixture was allowed to warm to room temperature, and was poured into a separatory funnel containing diethyl ether and saturated ammonium chloride solution. The layers were agitated and separated, and the organic layer was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude product was purified by column chromatography on silica gel (elution with 1:1 methylene chloride/hexanes) to afford 0.38 g (43% yield) of 4-(1-Adamantyl)-3-methoxybenzaldehyde as a white solid; 1H NMR (300 MHz, CDCl3) δ 9.92 (s, 1H, CHO), 7.37 (m, 3H, ArH), 3.88 (s, 3H, OCH3), 2.08 (s, 9H, adamantyl), and 1.76 (s, 6H, adamantyl); 13C NMR (75 MHz, CDCl3) δ 192.04 (C=O), 159.38, 146.00, 135.36, 127.06, 124.45, 109.54, 55.09 (OCH3), 40.15, 37.79, 36.95, and 28.90; IR (KBr) 2965, 2900, 2850, 1690 (C=O), 1250, 1160, 1135, 1035, and 1025 cm-1 ; MS (DCI) m/e 271 (MH+), 135 (C10H15+) . Anal. Calcd for C18H22O2.0.015 H2O: C, 79.88; H, 8.21. Found: C, 79.48; H, 8.34.

Workup

  1. temperatureto warm to room temperature
  2. additionwas poured into a separatory funnel
  3. stirringThe layers were agitated
  4. customseparated
  5. washthe organic layer was washed with saturated sodium chloride solution
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by column chromatography on silica gel (elution with 1:1 methylene chloride/hexanes)

Sources & evidence

ORD record
ord-8f2f5c3673ad4efa8cb9b7e67959ba04
Source dataset
uspto-grants-1995_02
Patent number
US05391817

Reaction notes

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