Hydrochloric Acid → HCID 11774917, compound

HRID 1357382Notes

Reaction equation

HRID 1357382 reaction equation
[CH3:1][O:2][C:3](=[O:22])[C:4]1[C:5](=[C:10]([O:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[NH2:21])[CH:11]=[CH:12][CH:13]=1)C(OC)=O.[N+:23]([C:26]1[CH:27]=[C:28]([CH:31]=[CH:32][CH:33]=1)[CH:29]=O)([O-:25])=[O:24].C([BH3-])#N.[Na+].Cl>C1(C)C=CC=CC=1.CCOCC>[CH3:1][O:2][C:3](=[O:22])[C:13]1[C:4](=[CH:5][C:10]([O:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[NH:21][CH2:29][C:28]2[CH:31]=[CH:32][CH:33]=[C:26]([N+:23]([O-:25])=[O:24])[CH:27]=2)=[CH:11][CH:12]=1)[C:3]([O:2][CH3:1])=[O:22]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 74493-NitrobenzaldehydeHCID 5003444Sodium cyanoborohydrideHCID 69997156HCID 69997156, compound

Product 1

HCID 11774917HCID 11774917, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

A solution of 3-(2-aminophenoxy)phthalic acid dimethyl ester (200 mg, 0.54 mmol) and 3-nitrobenzaldehyde (90 mg, 0.60 mmol) in toluen (20 ml) was refluxed for 30 hours with a Dean-Stark trap. The reaction mixture is cooled to room temperature and evaporated to dryness in vacuo. The residue was dissolved in methanol (5ml), sodium cyanoborohydride (100 mg, 1.58 mmol) was added, and pH adjusted to 4.5 by means of hydrogen chloride in ether. The mixture was stirred at room temperature for 20 hours, evaporated in dryness in vacuo, and partioned between methylene chloride (5 ml) and water (5 ml). The organic phase was isolated, dried over magnesium sulphate, and evaporated to dryness in vacuo. The crude compound was purified on silica gel (eluent: methylene chloride:ethyl acetate (95:5)) to give 4-[2-(3-nitrobenzylamino)phenoxy]phthalic acid dimethyl ester as a yellow oil (yield: 130 mg (55%). 1H—NMR (CDCl3) in ppm: δ 8.05-8.18 (2H,m); 7.84 (1H,d); 7.63 (1H,d); 7.50 (1H,t); 7.20 (1H,d); 6.9-7.1 (3H,m); 6.73 (1H,d.t.); 6.6 (1H,d.d.); 4.56 (1H,broad, s): 4.48 (2H,broad s); 3.9 (3H,s); 3.87 (3H,s). LC-MS: m/e 459 (M+Na), 437 (MH+).

Workup

  1. customevaporated to dryness in vacuo
  2. dissolutionThe residue was dissolved in methanol (5ml)
  3. customevaporated in dryness in vacuo
  4. customThe organic phase was isolated
  5. dry with materialdried over magnesium sulphate
  6. customevaporated to dryness in vacuo
  7. customThe crude compound was purified on silica gel (eluent: methylene chloride:ethyl acetate (95:5))

Sources & evidence

ORD record
ord-f323ac65a7e740148def6270ae7021c4
Source dataset
uspto-grants-2003_07
Patent number
US06590118B1

Reaction notes

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