Hydroxylamine → N-2-Thiabicyclo[2.2.2]oct-5-en-3-ylidenehydroxylamine

HRID 2295286Notes

Reaction equation

HRID 2295286 reaction equation
[C:1](Cl)(Cl)=[S:2].[CH:5]1[CH2:10][CH2:9][CH:8]=[CH:7][CH:6]=1.[NH2:11][OH:12].Cl.NO.[OH-].[K+]>C(Cl)(Cl)Cl.O>[CH:6]12[CH2:5][CH2:10][CH:9]([CH:8]=[CH:7]1)[C:1](=[N:11][OH:12])[S:2]2

Participants

8

Reactant 5

HCID 787HydroxylamineHCID 10040ThiophosgeneHCID 116051,3-CyclohexadieneHCID 14797Potassium HydroxideHCID 443297Hydroxyamine hydrochloride

Product 1

HCID 71415470N-2-Thiabicyclo[2.2.2]oct-5-en-3-ylidenehydroxylamine

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6212ChloroformSolvent

Procedure

Thiophosgene (296 g of 85%, 2.19 m) was added dropwise to a stirred solution of 167 g (2.08 m) of 1,3-cyclohexadiene in 500 ml of chloroform. The exothermic reaction caused the temperature to rise from 25° C. to 68° C. with refluxing of the solvent. After 45 minutes, the reaction mixture was cooled and added in portions over four hours to a stirred solution of hydroxylamine (prepared from 480 g (6.9 m) of hydroxylamine hydrochloride in 175 ml water by dropwise addition at 0° C. of a solution of 434 g of 89% potassium hydroxide (6.9 m) in 250 ml of water at -15° C. After being stirred overnight, the reaction mixture was filtered and the filter cake washed with methylene chloride. The combined filtrate and washings were separated and the organic layer dried (MgSO4) and reduced in volume at about 20 Torr. After addition of carbon tetrachloride to the residue, distillation of solvent was continued at atmospheric pressure until a pot temperature of 75° C. was attained. The hot mixture was filtered. Cooling of the filtrate gave a solid which was recrystallized from carbon tetrachloride to yield 271 g of the title compound.

Workup

  1. customThe exothermic reaction
  2. customto rise from 25° C. to 68° C.
  3. temperaturewith refluxing of the solvent
  4. temperaturethe reaction mixture was cooled
  5. filtrationthe reaction mixture was filtered
  6. washthe filter cake washed with methylene chloride
  7. customThe combined filtrate and washings were separated
  8. dry with materialthe organic layer dried (MgSO4)
  9. additionAfter addition of carbon tetrachloride
  10. distillationto the residue, distillation of solvent
  11. customwas continued at atmospheric pressure until a pot temperature of 75° C.
  12. filtrationThe hot mixture was filtered
  13. temperatureCooling of the filtrate
  14. customgave a solid which
  15. customwas recrystallized from carbon tetrachloride

Sources & evidence

ORD record
ord-8f02dfa469854611bf71574e3c178b51
Source dataset
uspto-grants-1984_01
Patent number
US04424213

Reaction notes

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