Dibromomethane → HCID 14867441, compound

HRID 1075998Notes

Reaction equation

HRID 1075998 reaction equation
C(Br)Br.C(=O)(O)[O-].[Na+].[CH3:9]N(C)C=O.[C:14]1([CH3:24])[CH:19]=[CH:18][C:17]([NH:20][C:21](=[S:23])[S-:22])=[CH:16][CH:15]=1.[NH4+]>O>[C:14]1([CH3:24])[CH:19]=[CH:18][C:17]([N:20]=[C:21]2[S:22][CH2:9][S:23]2)=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 3024DibromomethaneHCID 6228DimethylformamideHCID 516892Sodium BicarbonateHCID 12374892HCID 12374892, compound

Product 1

HCID 14867441HCID 14867441, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
12 °C

Procedure

In a suitable reaction vessel is mixed 6,090 grams of methylene bromide, 1,955 grams of sodium bicarbonate and 13.2 liters of dimethylformamide. The mixture is cooled to 12°C. and maintained between 12°C. and 20°C. while adding powdered ammonium p-tolyldithiocarbamate in small portions over about a 2-hour period. After stirring for an additional 4 hours at room temperature, the mixture is poured into a separatory funnel and diluted with an equal volume of water. The lower oily phase is separated and the upper aqueous DMF phase is extracted three times with 3.5 liter portions of ethylene chloride. The combined organic phase is washed with water and filtered. In a suitable vessel, the washed ethylene chloride mixture is diluted with an additional 36 liters of ethylene chloride, cooled to 10°C. to 15°C., and well stirred while adding 3,690 ml. of 37% aqueous solution of hydrochloric acid. After the mixture comes to room temperature, the solids are collected by filtration and washed with ethylene chloride and then methyl ethyl ketone. The air-dried hydrochloride salt of 2-p-tolylimino-1,3-dithietane, amounting to 3,432 grams, is finely pulverized and mixed with 14.5 liters of water. The mixture is cooled and about 2800 ml. of ammonium hydroxide is added over about 30 minutes to give a final acidity of pH 8. The solids are collected by filtration, washed with water, and air-dried to give 2,566 grams of 2-p-tolylimino-1,3-dithietane, melting point 54.5°C. to 55.0°C. The infrared spectrum shows C=N absorption at 1640 cm.-1.

Workup

  1. temperaturemaintained between 12°C. and 20°C.
  2. additionthe mixture is poured into a separatory funnel
  3. customThe lower oily phase is separated
  4. extractionthe upper aqueous DMF phase is extracted three times with 3.5 liter portions of ethylene chloride
  5. washThe combined organic phase is washed with water
  6. filtrationfiltered
  7. additionIn a suitable vessel, the washed ethylene chloride mixture is diluted with an additional 36 liters of ethylene chloride
  8. temperaturecooled to 10°C. to 15°C.
  9. stirringwell stirred
  10. additionwhile adding 3,690 ml
  11. customcomes to room temperature
  12. filtrationthe solids are collected by filtration
  13. washwashed with ethylene chloride
  14. additionmixed with 14.5 liters of water
  15. temperatureThe mixture is cooled
  16. additionof ammonium hydroxide is added over about 30 minutes
  17. customto give a final acidity of pH 8
  18. filtrationThe solids are collected by filtration
  19. washwashed with water
  20. customair-dried

Sources & evidence

ORD record
ord-3a572fdadd554663ad8fdbef205ad6fa
Source dataset
uspto-grants-1976_05
Patent number
US03954801

Reaction notes

Loading…