Ammonia → Methyl 4-[[(aminothioxomethyl)amino]methyl]benzoate

HRID 1373848Notes

Reaction equation

HRID 1373848 reaction equation
Cl.[NH2:2][CH2:3][C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][CH:5]=1.[C:14](N1C=CN=C1)([N:16]1C=CN=C1)=[S:15].C(N(CC)CC)C.N>C(Cl)(Cl)Cl.O.CCCCCC.CO>[CH3:11][O:10][C:8]([C:7]1[CH:6]=[CH:5][C:4]([CH2:3][NH:2][C:14]([NH2:16])=[S:15])=[CH:13][CH:12]=1)=[O:9]

Participants

9

Reactant 4

HCID 222AmmoniaHCID 8471TriethylamineHCID 802641,1'-ThiocarbonyldiimidazoleHCID 2729253Methyl 4-(aminomethyl)benzoate hydrochloride

Product 1

HCID 23023994Methyl 4-[[(aminothioxomethyl)amino]methyl]benzoateYield 91.3%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6212ChloroformSolventHCID 8058HexaneSolvent

Procedure

Under an argon atmosphere, to a suspension of methyl 4-aminomethylbenzoate hydrochloride (170.0 g, 0.843 mol) in chloroform (850 ml, 5.0 v/w) were successively added 1,1′-thiocarbonyldiimidazole (purity 90%, 166.0 g, 0.843 mol) and triethylamine (123 ml, 0.885 mol). After stirring at room temperature for 3 hr, 28% aqueous ammonia (570 ml, 8.43 mol) and methanol (170 ml, 1.0 v/w) were added and the mixture was stirred overnight. n-Hexane (1700 ml, 10.0 v/w) and water (850 ml, 5.0 v/w) were successively added to the reaction mixture and the mixture was stirred at room temperature for 3 hrs. The precipitated crystals were collected by filtration, washed successively with n-hexane (500 ml) and water (500 ml) and dried in vacuo to give the title compound (172.5 g, yield 91.3%) as a colorless solid.

Workup

  1. stirringthe mixture was stirred overnight
  2. stirringthe mixture was stirred at room temperature for 3 hrs
  3. filtrationThe precipitated crystals were collected by filtration
  4. washwashed successively with n-hexane (500 ml) and water (500 ml)
  5. customdried in vacuo

Sources & evidence

ORD record
ord-133213ae01a14a64b0ae04128d89c078
Source dataset
uspto-grants-2007_01
Patent number
US07163952B2

Reaction notes

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