Acetic Acid → 3-(4-n-Hexyloxy-2-methylbenzoyl)benzoic acid

HRID 1720166Notes

Reaction equation

HRID 1720166 reaction equation
[CH3:1][C:2]1[CH:17]=[C:16]([O:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH:15]=[CH:14][C:3]=1[C:4]([C:6]1[CH:7]=C([CH:11]=[CH:12][CH:13]=1)C#N)=[O:5].S(=O)(=O)(O)O.[C:30]([OH:33])(=[O:32])[CH3:31]>>[CH2:19]([O:18][C:16]1[CH:15]=[CH:14][C:3]([C:4]([C:6]2[CH:7]=[C:31]([CH:11]=[CH:12][CH:13]=2)[C:30]([OH:33])=[O:32])=[O:5])=[C:2]([CH3:1])[CH:17]=1)[CH2:20][CH2:21][CH2:22][CH2:23][CH3:24]

Participants

4

Reactant 3

HCID 176Acetic AcidHCID 1118Sulfuric AcidHCID 224203923-(2-Methyl-4-n-hexyloxybenzoyl)benzonitrile

Product 1

HCID 224203873-(4-n-Hexyloxy-2-methylbenzoyl)benzoic acid

Procedure

Anhydrous aluminium chloride (38.35 g) is added to a solution of the acid chloride prepared from 3-cyanobenzoic acid (36.3 g) as described in Example 26 and nitrobenzene (200 ml). A solution of 3-n-hexyloxytoluene (39.5 g) in nitrobenzene (50 ml) is added and the resulting mixture heated to 110°-120° C. for 3 hours. The reaction mixture is cooled and poured into a mixture of ice water (1,000 ml) and concentrated hydrochloric acid (100 ml). The mixture is extracted with ether (3×300 ml) and the combined extracts concentrated and the nitrobenzene removed by steam distillation. The resulting residue is dissolved in ether, dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue is chromatographed on silica gel (hexanes:ether; 70:30) to yield 3-(2-methyl-4-n-hexyloxybenzoyl)benzonitrile (21.1 g) as a dark brown oil and 3-(2-hydroxy-4-methylbenzoyl)benzonitrile, which is recrystallized from ethanol to give 5.78 g as a yellow solid (m.p. 126°-128°C.). The 3-(2-methyl-4-n-hexyloxybenzoyl)benzonitrile thereby obtained is heated under reflux in a mixture of acetic acid (160 g) and a solution of 75% sulfuric acid (160 g) for 1 hour. The cooled mixture is then poured into ice water (500 ml) and extracted with ether (3×200 ml). The extract is dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue is chromatographed on silica gel (hexanes:ether:acetic acid; 50:50:1). The main fraction is collected and concentrated in vacuo. The residual yellow solid is crystallized from heptane to yield 3-(4-n-hexyloxy-2-methylbenzoyl)benzoic acid (9.62 g) as yellow needles m.p. 136°-138° C.

Workup

  1. temperatureis heated
  2. extractionextracted with ether (3×200 ml)
  3. dry with materialThe extract is dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue is chromatographed on silica gel (hexanes:ether:acetic acid; 50:50:1)
  7. customThe main fraction is collected
  8. concentrationconcentrated in vacuo
  9. customThe residual yellow solid is crystallized from heptane

Sources & evidence

ORD record
ord-3f59d114a14c4cc4b385ee4a91e1edcf
Source dataset
uspto-grants-1996_04
Patent number
US05504244

Reaction notes

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