Nitrogen → HCID 10014629, compound

HRID 1742092Notes

Reaction equation

HRID 1742092 reaction equation
Cl.[N+:2]([C:5]1[CH:12]=[CH:11][C:8]([CH2:9][NH2:10])=[CH:7][CH:6]=1)([O-:4])=[O:3].C(N(CC)CC)C.N#N.[C:22](=[S:24])=[S:23].[CH3:25]I>CO>[N+:2]([C:5]1[CH:6]=[CH:7][C:8]([CH2:9][NH:10][C:22](=[S:24])[S:23][CH3:25])=[CH:11][CH:12]=1)([O-:4])=[O:3]

Participants

7

Reactant 5

HCID 947NitrogenHCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 8471TriethylamineHCID 112524674-Nitrobenzylamine hydrochloride

Product 1

HCID 10014629HCID 10014629, compoundYield 97.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent3×

Procedure

To a stirred solution of 150 g (795 mmole) of 4-nitrobenzylamine hydrochloride and 243 ml (176 g, 1.75 mole) of triethylamine in 780 ml of methanol was added gradually (under N2) a solution of 54 ml (68.9 g, 906 mmole) of carbon disulfide in 300 ml of methanol. The internal temperature was maintained below 30° C. during the addition, which took 75 minutes. After an additional hour at room temperature, the reaction mixture was cooled to -10° C. in an ice-MeOH bath as a solution of 50 ml (113 g, 795 mmole) of methyl iodide in 125 ml of methanol was gradually added over about 20 minutes. The cooling bath was removed, and the mixture was allowed to stir at room temperature for 2 hours. It was then concentrated in vacuo to a volume of approximately 500 ml and partioned between 2 L of ether and 2 L of 0.2 N HCl. The ethereal phase was washed with 2 L of saturated aqueous NAGl, dried over. MgSO4, filtered and concentrated to give a yellow solid. Trituration with petroleum ether and drying afforded 187 g (97%) of methyl N-(4-nitrobenzyl)dithiocarbamate, mp 106°-107° C., satisfactory purity by TLC in 2:1 hexane EtOAc; mass spectrum (FAB) m/e 243 (M+1)+.

Workup

  1. temperatureThe internal temperature was maintained below 30° C. during the addition, which
  2. waitAfter an additional hour at room temperature
  3. additionwas gradually added over about 20 minutes
  4. customThe cooling bath was removed
  5. concentrationIt was then concentrated in vacuo to a volume of approximately 500 ml
  6. washThe ethereal phase was washed with 2 L of saturated aqueous NAGl
  7. customdried over
  8. filtrationMgSO4, filtered
  9. concentrationconcentrated
  10. customto give a yellow solid
  11. dry with materialTrituration with petroleum ether and drying

Sources & evidence

ORD record
ord-5ce8fe30d1a247e99e52eb432c8d3438
Source dataset
uspto-grants-1994_08
Patent number
US05336778

Reaction notes

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