Benzoic acid, 2-iodo-, methyl ester → HCID 10709347, compound

HRID 1977922Notes

Reaction equation

HRID 1977922 reaction equation
[CH2:1]([C:5]1[C:10]([O:11][CH3:12])=[CH:9][CH:8]=[CH:7][C:6]=1[O:13]C)[CH2:2][CH2:3][CH3:4].CC(C)([O-])C.[K+].I[C:22]1[CH:31]=[CH:30][CH:29]=C[C:23]=1[C:24]([O:26][CH3:27])=[O:25]>N1C=CC=CC=1.O.[Cu]I>[CH3:27][O:26][C:24](=[O:25])[C:23]1[CH:22]=[CH:31][CH:30]=[CH:29][C:12]=1[O:11][C:10]1[CH:9]=[CH:8][CH:7]=[C:6]([OH:13])[C:5]=1[CH2:1][CH2:2][CH2:3][CH3:4]

Participants

7

Reactant 3

HCID 69132Benzoic acid, 2-iodo-, methyl esterHCID 5248402-Butyl-1,3-dimethoxybenzeneHCID 23665647Potassium tert-butoxide

Product 1

HCID 10709347HCID 10709347, compoundYield 13%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 1049PyridineSolvent2×

Procedure

2-Butyl-1,3-dimethoxybenzene (14.98 g, 77.6 mmol) was de-methylated as described above for the preparation of Example 10(B) to provide 19 g crude product as a brown oil. A solution of 15 g of this material and potassium tert-butoxide (9.70 g, 86.5 mmol) in pyridine (150 mL) was added to a second solution of methyl 2-iodobenzoate (11.9 g, 180 mmol) and copper(I) iodide (17.3 g, 91.0 mmol) in pyridine (150 mL). The resulting mixture was refluxed for 36 hours. The mixture was cooled to room temperature, diluted with water, and extracted three times with diethyl ether. The combined ether fractions were filtered through a mat of Celite®, washed once with 5N aqueous hydrochloric acid, once with 2N aqueous sodium hydroxide, and filtered again through a mat of Celite®. The resulting solution was dried over magnesium sulfate, filtered, and evaporated in vacuo. Silica gel chromatography (ethyl acetate/hexane) provided 3.02 g (11%) of the title intermediate product as an orange oil: NMR (CDCl3) 7.91 (d, J=8 Hz, 1H), 7.41 (t, J=8 Hz, 1H), 7.14 (t, J=8 Hz, 1H), 6.97 (t, J=9 Hz, 1H), 6.83 (d, J=8 Hz, 1H), 6.59 (d, J=8 Hz, 1H), 6.39 (d, J=8 Hz, 1H), 5.04 (bs, 1H, —OH), 3.83 (s, 3H), 2.66 (t, J=9 Hz, 2H), 1.54 (quintet, J=5 Hz, 2H), 1.35 (hextet, J=5 Hz, 2H), 0.91 (t, J=8 Hz, 3H); MS-EI m/e 300 (p, 34), 225 (100), 213 (42), 197 (53), 107 (38); IR (mull, cm−1) 3410, 2926, 1709, 1600, 1463, 1234, 1107, 1090, 992.

Workup

  1. customas described above for the preparation of Example 10(B)
  2. customto provide 19 g crude product as a brown oil
  3. temperatureThe resulting mixture was refluxed for 36 hours
  4. extractionextracted three times with diethyl ether
  5. filtrationThe combined ether fractions were filtered through a mat of Celite®
  6. washwashed once with 5N aqueous hydrochloric acid, once with 2N aqueous sodium hydroxide
  7. filtrationfiltered again through a mat of Celite®
  8. dry with materialThe resulting solution was dried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated in vacuo

Sources & evidence

ORD record
ord-3f065de2147a4868bdc7d6665de3742c
Source dataset
uspto-grants-2001_05
Patent number
US06235785B1

Reaction notes

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