Hexamethylenetetramine → Methyl 4-aminomethylsalicylate hydrochloride

HRID 128819Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 128819
C([O:4][C:5]1[CH:14]=[C:13]([CH2:15]Br)[CH:12]=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8])(=O)C.C1N2CN3CN(C2)C[N:18]1C3.C(Cl)(Cl)[Cl:28]>>[ClH:28].[NH2:18][CH2:15][C:13]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([OH:4])[CH:14]=1

Komponenten

4

Edukt 3

HCID 4101HexamethylenetetramineHCID 6212ChloroformHCID 21840999Methyl 2-acetoxy-4-(bromomethyl)benzoate

Produkt 1

HCID 22556073Methyl 4-aminomethylsalicylate hydrochloride

Reaktionsbedingungen

Temperatur
20 °C

Versuchsvorschrift

A stirred solution of methyl 2-acetoxy-4-bromomethylbenzoate (Regnier G, Canevari R, Le Douarec J-C, Bull. Soc. Chim. Fr, 1966:2821) (10.7 g) and hexamethylenetetramine (17.1 g) in CHCl3 (150 mL) was refluxed for 5 hours, then the solvent was removed (method of Meindl W, v Angerer E, Ruckdeschel G, Schonenberger H, Arch. Pharm. (Weinheim) 1982;315:941). The residue was stirred with MeOH (60 mL) and concentrated HCl (30 mL) at 20° C. for 10 minutes, then the solvent removed. Treatment of the solid residue twice more with HCl/MeOH and evaporation gave a solid, which was washed with CH2Cl2, then treated with saturated KHCO3 solution. The base was extracted with EtOAc and CH2Cl2, then the solvents removed. The crude hydrochloride salt (5.30 g, 70% pure) was precipitated from an ethereal solution of the base upon the addition of HCl gas. A subsample of the above crude base was purified by chromatography on silica gel, eluting with EtOAc/light petroleum (1:2). Acidification of a solution of the purified base gave pure methyl 4-(aminomethyl) -2-hydroxybenzoate hydrochloride; mp (CH2Cl2 /light petroleum) 225°-227° C.

Aufarbeitung

  1. customthe solvent was removed (method of Meindl W, v Angerer E, Ruckdeschel G, Schonenberger H, Arch. Pharm. (Weinheim) 1982;315:941)
  2. customthe solvent removed
  3. customTreatment of the solid residue twice more with HCl/MeOH and evaporation
  4. customgave a solid, which
  5. washwas washed with CH2Cl2
  6. additiontreated with saturated KHCO3 solution
  7. extractionThe base was extracted with EtOAc and CH2Cl2
  8. customthe solvents removed
  9. customThe crude hydrochloride salt (5.30 g, 70% pure) was precipitated from an ethereal solution of the base upon the addition of HCl gas
  10. customA subsample of the above crude base was purified by chromatography on silica gel
  11. washeluting with EtOAc/light petroleum (1:2)

Quellen und Nachweise

ORD-Eintrag
ord-2801c0cadffb43e89ee022d9fbc52726
Quelldatensatz
uspto-grants-1995_11
Patentnummer
US05464861

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