Ethyl Acetate → HCID 10022568, compound

HRID 1265233Notes

Reaction equation

HRID 1265233 reaction equation
C(OCC)(=O)C.C[O:8][C:9](=[O:35])[C:10]1[CH:15]=[CH:14][C:13]([C:16]([C:18]2[C:27]([CH2:28][CH2:29][CH3:30])=[CH:26][C:25]3[C:24]([CH3:32])([CH3:31])[CH2:23][CH2:22][C:21]([CH3:34])([CH3:33])[C:20]=3[CH:19]=2)=[O:17])=[CH:12][CH:11]=1>[OH-].[K+].CO>[CH2:28]([C:27]1[C:18]([C:16]([C:13]2[CH:12]=[CH:11][C:10]([C:9]([OH:35])=[O:8])=[CH:15][CH:14]=2)=[O:17])=[CH:19][C:20]2[C:21]([CH3:34])([CH3:33])[CH2:22][CH2:23][C:24]([CH3:31])([CH3:32])[C:25]=2[CH:26]=1)[CH2:29][CH3:30]

Participants

4

Reactant 2

HCID 8857Ethyl AcetateHCID 10318376HCID 10318376, compound

Product 1

HCID 10022568HCID 10022568, compound

Reagents, catalysts & solvents 1

HCID 23689386Potassium hydroxide methanolSolvent

Procedure

3-n-Propyl-5,6,7,8-tetrahydro-5,5,8,8-tetramethylnaphthalene (prepared from Friedel-Crafts alkylation/cyclization of n-propylbenzene with 2,5-dichloro-2,5-dimethylhexane) was combined with monomethylterephthalate acid chloride in dichloromethane and treated portionwise at ambient temperature with aluminum chloride until the spontaneous reflux had subsided and the solution become dark red/brown in color. After stirring at room temperature for 10-15 min, the reaction was poured into ice water and the layers were separated. The aqueous layer was extracted with EtOAc. The combined organic extracts were washed with water and brine, dried (MgSO4), filtered, and concentrated to give a yellow oil. The crude product was crystallized (CH2Cl2/hexanes) to give 4-[(3-n-propyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naphthyl)carbonyl]benzoic acid methyl ester as white crystals (95%): TLC (20% ethyl acetate: 80% hexanes) Rf 0.7; mp 112-114° C.; 1H-NMR (400 MHz, CDCl3) δ8.19 (½ABq, J=8.0 Hz, 2H, ArH); 7.89 (½ABq, J=8.0 Hz, 2H, ArH), 7.22 (s, 1H, ArH), 7.20 (s, 1H, ArH), 3.95 (s, 3H, OCH3), 2.64 (t, J=8.0 Hz, 2H, CH2), 1.69 (s, 4H, 2CH2), 1.55 (m, 2H, CH2), 1.31 (s, 6H, 2CH3), 1.20 (s, 6H, 2CH3), 0.89 (t, J=7.5 Hz, 3H, CH3), Anal. (C23H32O3) C, H. The ester was hydrolyzed in excess KOH/MeOH at ambient temperature for 24 h. The methanol was removed in vacuo. The residue was taken-up in water and the aqueous layer was adjusted to pH=4-5 with 1 M aqueous HCl. The aqueous solution was extracted 3 times with EtOAc; the organic layers were combined, and washed with water (2×) and brine. The organic solution was dried (Na2SO4), filtered, and concentrated to give 4-[(3-n-propyl-5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthyl)carbonyl]benzoic acid (101). Crystallization gave a white powder (93%): TLC (10% MeOH: 90% CHCl3) Rf 0.3; mp 252-254° C.; 1H-NMR (400 MHz, CDCl3) δ8.20 (½ABq, J=8.0 Hz, 2H, ArH), 7.90 (½Abq, J=8.0 Hz, 2H, ArH), 7.20 (s, 1H, ArH), 7.25 (s, 1H, ArH), 2.64 (t, J=8.0 Hz, 2H, CH2), 1.69 (s, 4H, 2CH2), 1.55 (m, 2H, CH2), 1.31 (s, 6H, 2CH3), 1.20 (s, 6H, 2CH3), 0.89 (t, J=7.5 Hz, 3H, CH3), Anal. (C25H30O3) C, H.

Workup

  1. customThe methanol was removed in vacuo
  2. extractionThe aqueous solution was extracted 3 times with EtOAc
  3. washwashed with water (2×) and brine
  4. dry with materialThe organic solution was dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-a925a1dd6b9b4fa1999756f382bdb02b
Source dataset
uspto-grants-2003_04
Patent number
US06545049B1

Reaction notes

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