Acetonitrile → HCID 178499066, compound

HRID 1172056Notes

Reaction equation

HRID 1172056 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:10]([O:11][CH3:12])=[C:9](N)[N:8]=[C:7]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[C:16]([O:21][CH3:22])[C:15]=2[F:23])[N:6]=1)=[O:4].C(#N)C.N([O-])=[O:28].[Na+].[OH-].[Na+]>OS(O)(=O)=O>[CH3:1][O:2][C:3]([C:5]1[C:10]([O:11][CH3:12])=[C:9]([OH:28])[N:8]=[C:7]([C:14]2[CH:19]=[CH:18][C:17]([Cl:20])=[C:16]([O:21][CH3:22])[C:15]=2[F:23])[N:6]=1)=[O:4]

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 14798Sodium HydroxideHCID 23668193Sodium NitriteHCID 591269286-Amino-2-(4-chloro-2-fluoro-3-methoxyphenyl)-5-methoxypyrimidine-4-carboxylic acid methyl ester

Product 1

HCID 178499066HCID 178499066, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
25 °C

Procedure

6-Amino-2-(4-chloro-2-fluoro-3-methoxyphenyl)-5-methoxypyrimidine-4-carboxylic acid methyl ester (200 mg, 0.61 mmol) was dissolved in 20 mL of 9 molar H2SO4 plus 5 mL acetonitrile and treated in portions with NaNO2 (150 mg, 2.2 mmol). After the addition was complete, the mixture was stirred for 30 minutes at 25° C., cooled in ice-salt and treated carefully with 50% NaOH to bring the pH to ca 0.8. The precipitate was taken up by extracting with two 15 mL portions of EtOAc and the combined extracts were washed with 10 mL sat. NaCl, dried (Na2SO4) and evaporated to give the title product 150 mg (75%). Mp: 177-179° C. MS m/z 342; 1H NMR (DMSO-d6): δ 7.81 (m, 1H), 7.31 (m, 1H), 4.05 (s, 3H), 4.01 (s, 3H).

Workup

  1. additionAfter the addition
  2. extractionby extracting with two 15 mL portions of EtOAc
  3. washthe combined extracts were washed with 10 mL sat. NaCl
  4. dry with materialdried (Na2SO4)
  5. customevaporated

Sources & evidence

ORD record
ord-f7a8adda4ac14ae2bee2ce4706ab7759
Source dataset
uspto-grants-2010_11
Patent number
US07833940B2

Reaction notes

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