4'-Hydroxyacetophenone → HCID 19892555, compound

HRID 893432Notes

Reaction equation

HRID 893432 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.[CH2:11]([OH:16])[CH2:12][CH:13]([CH3:15])[CH3:14].N(O[CH2:20][CH2:21][CH:22]([CH3:24])[CH3:23])=O.C(OCC)(=[O:27])C>>[CH2:20]([O:10][C:8]([O:16][CH2:11][CH2:12][CH:13]([CH3:15])[CH3:14])([C:5]1[CH:6]=[CH:7][C:2]([OH:1])=[CH:3][CH:4]=1)[CH:9]=[O:27])[CH2:21][CH:22]([CH3:24])[CH3:23]

Participants

5

Reactant 4

HCID 74694'-HydroxyacetophenoneHCID 8053Isoamyl NitriteHCID 8857Ethyl AcetateHCID 31260Isoamyl Alcohol

Product 1

HCID 19892555HCID 19892555, compoundYield 62%

Conditions

Temperature
25 °C

Procedure

p-Hydroxyacetophenone (40g, 294 mmol) was charged into a reactor containing acidified isoamyl alcohol (200 mL, acidified with anhydrous HCl). Isoamyl nitrite (79 ml, 69g, 588 mmol) was added slowly to maintain a temperature of 25° C. Reaction was monitored by HPLC. At the end of the reaction, ethyl acetate (500 ml) was added and the reaction mixture was transferred to a separator funnel. The organic layer was washed with water (2 ×250 ml), saturated NaHCO3 (1×250 ml) and brine (1×250 ml). The organic solution was dried over MgSO4 and distilled under reduced pressure to remove solvents. Chromatography over silica gel with CH2Cl2 yielded, after removal of solvent, 56.5 g of product (183 mmol, 62% yield). The product was confirmed by mass spectroscopy and nmr. [1H-nmr(200 MHz, acetone-d6); δ 0.93 (m, 12 H, CH3), 1.4 (m, 4 H, C--CH2 -- C), 1.7 (m, 2H, --CH--), 3.5 and 3.8 (m, 4 h, --OCH2), 5.1 (s, lH, O--CH--O), 0), 6.9, 8.0 (dd, 2 H each, aromatic), and 9.3 (broad s, 1 H phenolic H); 13C-nmr (50 MHz, acetone -d6) δ22.7, 22.8 (CH3), 25.6, 39.4 (CH2 --CH--), 67.0 (CH2 -O), 105.1 (O--CH--O), 115.8, 126.9, 133.1, 163 (aromatic), 192.8 (C=O); MS (direct probe) m/z 308 (M+), 187, 121, 71 (100)].

Workup

  1. customReaction
  2. additionwas added
  3. customthe reaction mixture was transferred to a separator funnel
  4. washThe organic layer was washed with water (2 ×250 ml), saturated NaHCO3 (1×250 ml) and brine (1×250 ml)
  5. dry with materialThe organic solution was dried over MgSO4
  6. distillationdistilled under reduced pressure
  7. customto remove solvents
  8. customChromatography over silica gel with CH2Cl2 yielded

Sources & evidence

ORD record
ord-28e77563752e454d8f95009870d3ba6f
Source dataset
uspto-grants-1992_06
Patent number
US05124489

Reaction notes

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