Ethyl chloroformate → HCID 178469236, compound

HRID 1789582Notes

Reaction equation

HRID 1789582 reaction equation
[C:1]([N:3]=[C:4]1[NH:9][CH:8]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([N+:16]([O-:18])=[O:17])[CH:11]=2)[C:7]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[C:6]([CH3:24])[NH:5]1)#[N:2].Cl[C:26]([O:28][CH2:29][CH3:30])=[O:27]>O1CCCC1.N1C=CC=CC=1>[C:1]([N:3]=[C:4]1[NH:5][C:6]([CH3:24])=[C:7]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH:8]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([N+:16]([O-:18])=[O:17])[CH:11]=2)[N:9]1[C:26]([O:28][CH2:29][CH3:30])=[O:27])#[N:2]

Participants

5

Reactant 2

HCID 10928Ethyl chloroformateHCID 178469235HCID 178469235, compound

Product 1

HCID 178469236HCID 178469236, compoundYield 84.7%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A suspension of 1,2,3,4-tetrahydro-2-cyanoimino-6-methyl-4-(3-nitrophenyl)-5-pyrimidinecarboxylic acid, ethyl ester (565 mg, 1.72 mmoles) in dry tetrahydrofuran (70 ml) and pyridine (2.0 ml) was cooled to 0° C. and treated with ethyl chloroformate (0.17 ml, 2.24 mmoles) dropwise under argon. After the addition was completed, the cooling bath was removed and the reaction was allowed to stir at room temperature for 13 hours. Dry dimethylformamide (2.0 ml) was added and the reaction suspension became a homogeneous solution. It was then treated with triethylamine (0.5 ml) followed by ethyl chloroformate (0.1 ml). The reaction was allowed to stir at room temperature for 1 hour and then diluted with ethyl acetate. It was washed with 1N hydrochloric acid, water, sodium bicarbonate solution and brine. After drying over anhydrous magnesium sulfate, the solvent was evaporated. The residue was purified by flash chromatography (10% ethyl acetate in dichloromethane) to provide a light yellow foam (585 mg). This material was combined with another batch of the same product and was crystallized from isopropyl ether-dichloromethane to yield the title compound, melting point 173.5°-175° C.

Workup

  1. additionAfter the addition
  2. customthe cooling bath was removed
  3. additionDry dimethylformamide (2.0 ml) was added
  4. additionIt was then treated with triethylamine (0.5 ml)
  5. stirringto stir at room temperature for 1 hour
  6. additiondiluted with ethyl acetate
  7. washIt was washed with 1N hydrochloric acid, water, sodium bicarbonate solution and brine
  8. dry with materialAfter drying over anhydrous magnesium sulfate
  9. customthe solvent was evaporated
  10. customThe residue was purified by flash chromatography (10% ethyl acetate in dichloromethane)

Sources & evidence

ORD record
ord-8e9a015962e348fea4c386a2ccfd19ac
Source dataset
uspto-grants-1987_08
Patent number
US04689414

Reaction notes

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