Hydrochloric Acid → HCID 22420405, compound

HRID 1720161Notes

Reaction equation

HRID 1720161 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][CH:11]=1)[C:6]([OH:8])=O)#[N:2].[CH2:12]([O:16][C:17]1[CH:22]=[CH:21][CH:20]=[C:19]([O:23]C)[CH:18]=1)[CH2:13][CH2:14][CH3:15].Cl>S(Cl)(Cl)=O>[CH2:12]([O:16][C:17]1[CH:22]=[CH:21][C:20]([C:6]([C:5]2[CH:4]=[C:3]([CH:11]=[CH:10][CH:9]=2)[C:1]#[N:2])=[O:8])=[C:19]([OH:23])[CH:18]=1)[CH2:13][CH2:14][CH3:15]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 158753-Cyanobenzoic acidHCID 98775381-Butoxy-3-methoxybenzene

Product 1

HCID 22420405HCID 22420405, compoundYield 5.5%

Reagents, catalysts & solvents 1

HCID 24386Thionyl ChlorideSolvent

Procedure

First, 3-cyanobenzoic acid (20 grams) is heated under reflux for 1.5 hours in thionyl chloride (100 ml). The excess thionyl chloride is removed by distillation. The crude acid chloride which remains is diluted with nitrobenzene (200 ml). Anhydrous aluminum chloride (21.75 g) is added and the mixture cooled in an ice bath. Then, 1-butoxy-3-methoxybenzene (20 g, 0.11 mole) is added in one portion. The reaction mixture is stirred at room temperature overnight and then heated to 105° C. for 2 hours. The resulting mixture is cooled and poured into a mixture of ice water (1000 ml) and concentrated hydrochloric acid (100 ml). The product is extracted with ether (3×300 mls). The extract was dried over MgSO4, filtered and evaporated to dryness. The residual dark oil is chromatographed on silica gel (hexane:ether at 80:20) to yield 3-(4-butoxy-2-hydroxybenzoyl)benzonitrile (1.8 g) followed by 3-(2-hydroxy-4-methoxybenzoyl)benzonitrile (2.75 g). The 3-(4-butoxy-2-hydroxybenzoyl)benzonitrile thereby obtained, is heated under reflux in a mixture of acetic acid (18 g) and concentrated hydrochloric acid (18 g) for a hours. The resulting mixture is diluted with water (100 ml) and extracted with methylene chloride (3×50 ml). The extract is dried over magnesium sulfate, filtered, and evaporated to dryness. The residue is recrystallized from heptane/ethanol to yield 3-(4-butoxy-2-hydroxybenzoyl)benzoic acid (1.13 g), m.p. 175° C.

Workup

  1. customThe excess thionyl chloride is removed by distillation
  2. additionThe crude acid chloride which remains is diluted with nitrobenzene (200 ml)
  3. additionAnhydrous aluminum chloride (21.75 g) is added
  4. temperaturethe mixture cooled in an ice bath
  5. temperatureheated to 105° C. for 2 hours
  6. temperatureThe resulting mixture is cooled
  7. extractionThe product is extracted with ether (3×300 mls)
  8. dry with materialThe extract was dried over MgSO4
  9. filtrationfiltered
  10. customevaporated to dryness
  11. customThe residual dark oil is chromatographed on silica gel (hexane:ether at 80:20)

Sources & evidence

ORD record
ord-33f9f0e04d454e6c986e63ef0dcc821b
Source dataset
uspto-grants-1996_04
Patent number
US05504244

Reaction notes

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