Phenyl chloroformate → Phenyl (4-cyano-3-ethoxy-5-isothiazolyl)carbamate

HRID 1439322Notes

Reaction equation

HRID 1439322 reaction equation
[NH2:1][C:2]1[S:6][N:5]=[C:4]([O:7][CH2:8][CH3:9])[C:3]=1[C:10]#[N:11].Cl[C:13]([O:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:14]>C1(C)C=CC=CC=1>[C:10]([C:3]1[C:4]([O:7][CH2:8][CH3:9])=[N:5][S:6][C:2]=1[NH:1][C:13](=[O:14])[O:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)#[N:11]

Participants

4

Reactant 2

HCID 15891Phenyl chloroformate2×HCID 213968195-Amino-4-cyano-3-ethoxyisothiazole

Product 1

HCID 54236272Phenyl (4-cyano-3-ethoxy-5-isothiazolyl)carbamateYield 40.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 16.6 g of 5-amino-4-cyano-3-ethoxyisothiazole and 30.7 g of phenyl chloroformate in 100 ml of toluene under nitrogen atmosphere was stirred and heated at 100° for about 16 hours. After this time, thin-layer chromatography indicated that the reaction was 50% complete. An additional 15 ml of phenyl chloroformate was added and heating (100°) continued for an additional 24 hours; at this time thin-layer chromatography indicated 80% reaction. After an additional 6 hours, 90% reaction was indicated. The mixture was allowed to cool to 5° and filtered. The solid filter cake was washed with toluene and recrystallized from acetic acid, then ethanol, to give 11.5 g of phenyl (4-cyano-3-ethoxy-5-isothiazolyl)carbamate, m.p. 252°-253°. The nmr spectrum was consistent with the assigned structure.

Workup

  1. temperatureheated at 100° for about 16 hours
  2. temperatureheating (100°)
  3. custom80% reaction
  4. waitAfter an additional 6 hours
  5. custom90% reaction
  6. temperatureto cool to 5°
  7. filtrationfiltered
  8. filtrationThe solid filter cake
  9. washwas washed with toluene
  10. customrecrystallized from acetic acid

Sources & evidence

ORD record
ord-7b59006193a942c883d9024a01ef2f8b
Source dataset
uspto-grants-1977_11
Patent number
US04059433

Reaction notes

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