Hydrochloric Acid → Dimethyl 3-cyanobenzene-1,2-dicarboxylate

HRID 2103454

Reaction equation

HRID 2103454 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6](N)[C:5]=1[C:11]([O:13][CH3:14])=[O:12].Cl.N([O-])=O.[Na+].C(=O)([O-])[O-].[Na+].[Na+].[C:27]([Cu])#[N:28].[C-]#N.[K+]>O>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:27]#[N:28])[C:5]=1[C:11]([O:13][CH3:14])=[O:12]

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 9032Potassium CyanideHCID 10340Sodium CarbonateHCID 13399384Dimethyl 3-aminobenzene-1,2-dicarboxylateHCID 23668193Sodium NitriteHCID 178418546HCID 178418546, compound

Product 1

HCID 21988554Dimethyl 3-cyanobenzene-1,2-dicarboxylateYield 69.6%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Procedure

To a stirred suspension of methyl-3-amino-2-(methoxycarbonyl)benzoate (17.0 g, 81 mmol) in a mixture of concentrated HCl (44 ml) and water (440 ml) at 4° C. was added a solution of NaNO2 (6.73 g, 97 mmol) in water (25 ml) dropwise at 4-5° C. Stirring was continued for 30 min at 4° C. The mixture was then carefully neutralized with sat. sodium carbonate to pH 6. A stirred solution of CuCN (9.46 g, 105 mmol) and KCN (6.38 g, 105 mmol) in water (150 ml) was warmed to 60° C. The cold neutralized diazonium solution was then added in small portions at a time with vigorous stirring. The mixture was stirred at 60° C. for 1 hour and then cooled to room temperature. The mixture was extracted with dichloromethane (4×150 ml) and the combined dichloromethane extracts were washed with water (2×100 ml), brine (100 ml) and dried. The solvent was removed in vacuo and the product was purified by chromatography (dichloromethane) to afford 12.36 g (65%) of the product as a light yellow solid: 1H NMR (CDCl3) δ 8.19 (d, J=7.9 Hz, 1H), 7.8.9 (d, J=7.4 Hz, 1H), 7.64 (t, J=8.0 Hz, 1H), 4.03 (s, 3H), 3.94 (s, 3H).

Workup

  1. stirringThe mixture was stirred at 60° C. for 1 hour
  2. extractionThe mixture was extracted with dichloromethane (4×150 ml)
  3. washthe combined dichloromethane extracts were washed with water (2×100 ml), brine (100 ml)
  4. customdried
  5. customThe solvent was removed in vacuo
  6. customthe product was purified by chromatography (dichloromethane)

Sources & evidence

ORD record
ord-ac8bbb13af314afba7b5855bfee89f4d
Source dataset
uspto-grants-2009_08
Patent number
US07576104B2

Linked notes

Loading…