Methyl chloroformate → 2-Amino-3-(2-methyl-6-methoxycarbonylaminobenzylideneamino)pyridine

HRID 2073802

Reaction equation

HRID 2073802 reaction equation
[NH2:1][C:2]1[C:7]([NH2:8])=[CH:6][CH:5]=[CH:4][N:3]=1.[CH3:9][C:10]1[CH:17]=[CH:16][CH:15]=[C:14]([NH:18][C:19]([O:21][CH3:22])=[O:20])[C:11]=1[CH:12]=O.CC1C=CC=C(N)C=1C=O.ClC(OC)=O>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl.O.C(N(CC)CC)C>[NH2:1][C:2]1[C:7]([N:8]=[CH:12][C:11]2[C:14]([NH:18][C:19]([O:21][CH3:22])=[O:20])=[CH:15][CH:16]=[CH:17][C:10]=2[CH3:9])=[CH:6][CH:5]=[CH:4][N:3]=1

Participants

9

Reactant 4

HCID 6586Methyl chloroformateHCID 99562,3-DiaminopyridineHCID 144998232-Methyl-6-methoxycarbonylaminobenzaldehydeHCID 230465382-Amino-6-methylbenzaldehyde

Product 1

HCID 144998242-Amino-3-(2-methyl-6-methoxycarbonylaminobenzylideneamino)pyridineYield 19.6%

Reagents, catalysts & solvents 4

HCID 24193Titanium TetrachlorideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Procedure

To a solution of 2,3-diaminopyridine (546 mg) and 2-methyl-6-methoxycarbonylaminobenzaldehyde (966 mg)*, which was prepared by reacting 2-methyl-6-aminobenzaldehyde with methyl chloroformate according to a similar manner to that of Preparation 2, and triethylamine (2.5 g) in methylene chloride (26 ml) was added a 0.5M solution of titanium tetrachloride in methylene chloride (6 ml) at 0° C. and the mixture was stirred for 2 hours at the same temperature. To the mixture, water was added and the insoluble materials were removed by filtration, and the organic layer was separated. The solvent was evaporated under reduced pressure. The residue was subjected to column chromatography on silica gel (27 g), eluting with a mixture of chloroform and methanol (50:1). The fractions containing the desired product were combined and the solvent was removed under reduced pressure. The residue was triturated with diethyl ether to give 2-amino-3-(2-methyl-6-methoxycarbonylaminobenzylideneamino)pyridine (279 mg).

Workup

  1. customthe insoluble materials were removed by filtration
  2. customthe organic layer was separated
  3. customThe solvent was evaporated under reduced pressure
  4. washeluting with a mixture of chloroform and methanol (50:1)
  5. additionThe fractions containing the desired product
  6. customthe solvent was removed under reduced pressure
  7. customThe residue was triturated with diethyl ether

Sources & evidence

ORD record
ord-0170d304173d4fbaaa3ebafe0360ad10
Source dataset
uspto-grants-1990_04
Patent number
US04920129

Linked notes

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