Ammonia → 1-Naphthalenecarboxylic acid, 1,4-dihydro-2,7-dimethoxy-, methyl ester

HRID 328156Notes

Reaction equation

HRID 328156 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[CH:11][C:10]2[C:5](=[CH:6][C:7]([O:13][CH3:14])=[CH:8][CH:9]=2)[C:4]=1[C:15]([OH:17])=[O:16].N.[Li].[Cl-].[NH4+].[CH3:22]COCC>>[CH3:1][O:2][C:3]1[CH:4]([C:15]([O:17][CH3:22])=[O:16])[C:5]2[C:10]([CH2:11][CH:12]=1)=[CH:9][CH:8]=[C:7]([O:13][CH3:14])[CH:6]=2

Participants

6

Reactant 5

HCID 222Ammonia2×HCID 3283Diethyl EtherHCID 25517Ammonium ChlorideHCID 3028194LithiumHCID 122399171-Naphthalenecarboxylic acid, 2,7-dimethoxy-

Product 1

HCID 122399191-Naphthalenecarboxylic acid, 1,4-dihydro-2,7-dimethoxy-, methyl ester

Conditions

Temperature
-33 °C

Procedure

A solution of 2,7-dimethoxy-1-naphthoic acid (I) (0.1 mole) in 150 ml. ether and 600 ml. liquid ammonia was treated with 1.73 g. lithium wire in small portions with stirring under argon. This was allowed to reflux (-33° C.) for 11/2 hours. Ammonium chloride was added to quench the reaction and the ammonia was allowed to evaporate. The residue was taken up in water and washed with ether. The aqueos layer was acidified with 6 N hydrochloric acid and quickly extracted three times with ether. The ether extracts were washed with saturated sodium chloride; and then treated with an ethereal solution of excess diazomethane (prepared from 20.6 g. N-methyl-N-nitrosourea).1After 1/2 hr., acetic acid was added to destroy the excess diazomethane. The solution was washed with dilute sodium carbonate, dried (MgSO4), and concentrated. The residue was crystallized from methanol; mp 90°-91° C.

Workup

  1. customto quench
  2. customthe reaction
  3. customto evaporate
  4. washwashed with ether
  5. extractionquickly extracted three times with ether
  6. washThe ether extracts were washed with saturated sodium chloride
  7. additionand then treated with an ethereal solution of excess diazomethane (prepared from 20.6 g. N-methyl-N-nitrosourea).1After 1/2 hr
  8. addition, acetic acid was added
  9. customto destroy the excess diazomethane
  10. washThe solution was washed with dilute sodium carbonate
  11. dry with materialdried (MgSO4)
  12. concentrationconcentrated
  13. customThe residue was crystallized from methanol

Sources & evidence

ORD record
ord-32eb100e05214b4d83e666e2ff613bb7
Source dataset
uspto-grants-1977_04
Patent number
US04016167

Reaction notes

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