Acetic Acid → HCID 70099401, compound

HRID 278830Notes

Reaction equation

HRID 278830 reaction equation
[CH3:1]C(C)([O-])C.[K+].[O:7]([CH2:15][CH2:16][N:17]([C:28]1[CH:35]=[CH:34][C:31]([CH:32]=O)=[CH:30][CH:29]=1)[CH2:18][CH2:19][O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22])[Si:8]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:10])[CH3:9].C[CH:37]([C:42]1[C:43]([CH2:45][C:46]([CH3:51])([CH3:50])[CH2:47][C:48]=1[CH3:49])=[O:44])[CH2:38][CH2:39][CH2:40][CH3:41].C(O)(=O)C.C(=O)(O)[O-].[Na+]>COCCOCCOC>[O:7]([CH2:15][CH2:16][N:17]([C:28]1[CH:35]=[CH:34][C:31]([CH:32]=[CH:49][C:48]2[CH2:47][C:46]([CH3:50])([CH3:51])[CH2:45][C:43](=[O:44])[C:42]=2[CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:1])=[CH:30][CH:29]=1)[CH2:18][CH2:19][O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22])[Si:8]([C:11]([CH3:14])([CH3:13])[CH3:12])([CH3:10])[CH3:9]

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 516892Sodium BicarbonateHCID 11351100HCID 11351100, compoundHCID 23665647Potassium tert-butoxideHCID 86757791HCID 86757791, compound2×

Product 1

HCID 70099401HCID 70099401, compoundYield 22%

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Procedure

Potassium t-butoxide (30.32 g, 97%, 0.262 mol.) was added to a solution of p-N,N-Bis(2-t-butyldimethylsiloxyethyl)aminobenzaldehyde (, 53.4 g, 0.122 mol.) and 2-hexyl-isophorone (compound 10, 26.6 g, 0.118 mol.) in diglyme (200 mL, KOH dried) over 3 min. Ice bath was used to keep the temperature below 50° C. The reaction mixture was stirred at room temperature for 25 min. and then was poured to dilute acetic acid (0.28 mol HOAc in 200 mL of water). The extra acid was neutralized saturated aqueous sodium bicarbonate. The organic layer was separated, washed with water, dried with magnesium sulfate and rotovapped to dryness. The residue was purified by a silica gel column using ethyl acetate/hexane (1/20, v/v) to afford 8.33 g red thick oil: yield 22% based on reacted starting material. Only about starting materials reacted. 1H NMR (CDCl3): δ7.36 (d, 8.81 Hz, 2H), 7.14 (d, 16.06 Hz, 1H), 6.88 (d, 16.09 Hz, 1H), 6.69 (d, 8.91 Hz, 2H), 3.78 (t, 6.06 Hz, 4H), 3.56 (t, 5.89 Hz, 4H), 2.53 (br, 2H), 2.48 (s, 2H), 2.29 (s, 2H), 1.33 (m, 8H), 1.05 (s, 6H), 0.90 (s, 18H), 0.04 (s, 12H) ppm. 13C NMR (CDCl3): δ198.87, 148.41, 147.67, 134.47, 134.19, 128.52, 124.38, 121.71, 111.54, 60.21, 53.42, 51.37, 39.82, 32.27, 31.65, 29.90, 29.37, 28.39, 25.79, 24.30, 22.54 ppm.

Workup

  1. customIce bath was used
  2. customthe temperature below 50° C
  3. customThe organic layer was separated
  4. washwashed with water
  5. dry with materialdried with magnesium sulfate
  6. customThe residue was purified by a silica gel column

Sources & evidence

ORD record
ord-02ef59cb6c564cb095edfa0f9f734131
Source dataset
uspto-grants-2002_03
Patent number
US06361717B1

Reaction notes

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