Nitric Acid → HCID 12736684, compound

HRID 619365Notes

Reaction equation

HRID 619365 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]=[C:9]([O:13][CH3:14])[C:10]=1[O:11][CH3:12])C(O)=O.[N+:15]([O-])([OH:17])=[O:16]>C(O)(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([N+:15]([O-:17])=[O:16])[CH:8]=[C:9]([O:13][CH3:14])[C:10]=1[O:11][CH3:12]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 2400533-Chloro-4,5-dimethoxybenzoic acid

Product 1

HCID 12736684HCID 12736684, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

from 2-chloro-N-(3-methoxyphenyl)-4-pyrimidineamine (0.50 g, 2.13 mmol) [see Example 92] and 3-chloro-4,5-dimethoxyaniline (0.40 g, 2.13 mmol) to give the title compound (0.55 g) as a white soid m.p. 204-205°. δH (d6DMSO) 11.19 (1H, br s),10.85 (1H, brs), 8.00 (1H, d, J 7.1 Hz), 7.23 (4H, m), 7.12 (1H, d, J 4.4 Hz), 6.75 (1H, m), 6.59 (1H, d, J 7.1 Hz), 3.74 (3H, s), 3.69 (3H, s) and 3.65 (3H, s). MS m/z 387 (M+H)+. The aniline starting material was prepared in a similar manner to the analogous aniline of Example 113, from 1-chloro-2,3-dimethoxy-5-nitrobenzene (1.08 g, 5.82 mmol), to give the desired product (0.85 g) as a white solid m.p. 66-68°. MS m/z 188 (M+H)+. The 1-chloro-2,3-dimethoxy-5-nitrobenzene was prepared by heating a solution of 3-chloro-4,5-dimethoxybenzoic acid (3.50 g, 16.2 mmol) in glacial acetic acid (15 ml) and 70% nitric acid (15 ml) at 600 for 1 h. The reaction was poured onto ice-water and the white precipitate which formed was filtered off, washed with water and dried in vacuo and washed thoroughly with hexane. The hexane washings were evaporated and the residue subjected to column chromatography [silica 20% ethyl acetate-hexane] to give the desired product (1.03 g) as a white solid m.p. 104-105°. MS m/z 217 (M+H)+. The acid used as starting material was prepared according to the method of Y. Ohtani et al. Acta. Chem. Scand., Ser B. B36, 613 (1982).

Workup

  1. additionThe reaction was poured onto ice-water
  2. customthe white precipitate which formed
  3. filtrationwas filtered off
  4. washwashed with water
  5. customdried in vacuo
  6. washwashed thoroughly with hexane
  7. customThe hexane washings were evaporated

Sources & evidence

ORD record
ord-a470fbfbad5a41fa84aa3d0a257fa446
Source dataset
uspto-grants-1999_09
Patent number
US05958935

Reaction notes

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