Methyl chloroformate → Thiophamine

HRID 1415621Notes

Reaction equation

HRID 1415621 reaction equation
Cl[C:2]([O:4][CH3:5])=[O:3].[S-:6][C:7]#[N:8].[K+].[C:10]1([NH2:17])[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[NH2:16]>C(#N)C>[CH3:5][O:4][C:2]([NH:8][C:7]([NH:16][C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=1[NH2:17])=[S:6])=[O:3]

Participants

5

Reactant 3

HCID 6586Methyl chloroformateHCID 7243O-PhenylenediamineHCID 516872Potassium thiocyanate

Product 1

HCID 3032830ThiophamineYield 27.2%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

Methyl chloroformate (23.6 g; 0.25 mole) was added dropwise to a stirred suspension of potassium thiocyanate (24.2 g; 0.25 mole) in dry acetonitrile (100 ml). The temperature of the reaction mixture rose spontaneously to 50° C. and stirring was continued for two hours at 45° C. to 50° C. The reaction mixture was then filtered and the clear filtrate was added dropwise during fifteen minutes to a suspension of o-phenylenediamine (27 g; 0.25 mole) in dry acetonitrile (20 ml), the temperature during the addition being maintained between 15° C. and 20° C. by external cooling. When the addition was complete, the reaction mixture was stirred at laboratory temperature for two hours, filtered, and the crude solid product was crystallised from ethanol to give colourless needles of 1-methoxycarbonyl-3-(2-aminophenyl)-thiourea (15.3 g), m.p. 183.5°-184.5° C. (with decomposition).

Workup

  1. customrose spontaneously to 50° C.
  2. filtrationThe reaction mixture was then filtered
  3. additionthe temperature during the addition
  4. temperaturebeing maintained between 15° C. and 20° C. by external cooling
  5. additionWhen the addition
  6. stirringthe reaction mixture was stirred at laboratory temperature for two hours
  7. filtrationfiltered
  8. customthe crude solid product was crystallised from ethanol

Sources & evidence

ORD record
ord-76fe164f457f4aa9ab6b28b16e2c3693
Source dataset
uspto-grants-1977_01
Patent number
US04005217

Reaction notes

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