Dimethylformamide → HCID 14154576, compound

HRID 1904089Notes

Reaction equation

HRID 1904089 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[C:10](Br)[C:11]([O:15][CH3:16])=[CH:12][CH:13]=2)[CH:8]=[CH:7][CH:6]=1)=[O:4].[NH4+].[OH-].[CH3:20][N:21](C)C=O>N1C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[C:10]([C:20]#[N:21])[C:11]([O:15][CH3:16])=[CH:12][CH:13]=2)[CH:8]=[CH:7][CH:6]=1)=[O:4]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 14923Ammonium HydroxideHCID 109352981-Naphthalenecarboxylic acid, 5-bromo-6-methoxy-, methyl ester

Product 1

HCID 14154576HCID 14154576, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineCatalyst

Conditions

Temperature
180 °C

Procedure

A solution of bromine (26.6 g, 0.167 mole) in glacial acetic acid (25 ml) was added dropwise to a cooled suspension of 6-methoxy-1-naphthalenecarboxylic acid methyl ester (30 g, 0.13 9 moles) in glacial acetic acid (2.75 ml). The precipitate was collected, washed with water and crystallized from ethanol to give 33.3 g of 5-bromo-6-methoxy-1-naphthalenecarboxylic acid methyl ester; mp 119° C.; NMR (CDCl3) δ3.97 (s, 3H), 4.03 (s, 3H), 7.35 (d, J=9.25 Hz, 1H), 7.4 (m, 1H), 8.05 (d, J=6.75 Hz, 1H), 8.45 (d, J=8.25 Hz, 1H), 8.9 (d, J=9.25, 1H). The latter ester (10.1 g, 34 mmoles) and Cu2 (CN)2.H2O (3.4 g, 17 mmoles) in distilled dimethylformamide (75 ml) containing 15 drops of pyridine was heated at 180° C. for 5 hr. The hot mixture was poured into a mixture of ice (50 g) and conc. NH4OH (50 ml). The resulting precipitate was collected, washed with water, dried and recrystallized from chloroform-ethyl acetate to afford 5.6 g of 5-cyano-6-methoxy-1-naphthalenecarboxylic acid methyl ester: mp 210°-211° C., NMR (CDCl3) δ3.95 (s, 3H), 4.15 (s, 3H). To a stirred solution of the latter ester (5.95 g, 24.66 mmoles) in 2-methoxyethanol (100 ml) at 20°-22° C., 4 N aqueous NaOH solution (12.3 ml) was added. The reaction mixture was stirred at 20°-22° C. for 60 hr, diluted with water, cooled to 0° C. and rendered acidic with 1 N aqueous HCl. The precipitate was collected and dried to yield 5.6 g of the title compound; mp>290° C.; NMR (DMSO-d6) δ4.1 (s, 3H), 8.1 (m, 5H).

Workup

  1. customThe resulting precipitate was collected
  2. washwashed with water
  3. customdried
  4. customrecrystallized from chloroform-ethyl acetate

Sources & evidence

ORD record
ord-aa9c6f131fbb43f6a7d984696797a884
Source dataset
uspto-grants-1984_03
Patent number
US04439617

Reaction notes

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