Methyl iodide → 2-Imidazolidinethione, 4,4-dimethyl-

HRID 236021Notes

Reaction equation

HRID 236021 reaction equation
NCC(N)(C)C.CI.I.C[S:11][C:12]1[NH:13][CH2:14][C:15]([CH3:18])([CH3:17])[N:16]=1.[Cl:19][C:20]1[CH:27]=[CH:26][C:23]([CH2:24][NH2:25])=[CH:22][CH:21]=1.[Na].[N:29](=[C:31]([C:37]#[N:38])[C:32](OCC)=[O:33])[OH:30]>O.C(O)(=O)C.CCO.C(Cl)Cl.C(=S)=S>[CH3:17][C:15]1([CH3:18])[CH2:14][NH:13][C:12](=[S:11])[NH:16]1.[NH2:38][C:37]1[N:25]([CH2:24][C:23]2[CH:26]=[CH:27][C:20]([Cl:19])=[CH:21][CH:22]=2)[C:12]2[N:13]([CH2:14][C:15]([CH3:18])([CH3:17])[N:16]=2)[C:32](=[O:33])[C:31]=1[N:29]=[O:30]

Participants

13

Reactant 6

HCID 6328Methyl iodide2×HCID 131282-MethylpropylenediamineHCID 660364-ChlorobenzylamineHCID 5360545SodiumHCID 6399078Ethyl 2-cyano-2-(hydroxyimino)acetateHCID 178503444HCID 178503444, compound

Product 2

HCID 30325022-Imidazolidinethione, 4,4-dimethyl-HCID 178428086HCID 178428086, compound

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 702EthanolSolvent3×HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 6348Carbon DisulfideSolvent

Procedure

4,4-Dimethylimidazoline-2-thione was prepared by adding a solution of 50 g. of 1,2-diamino-2-methylpropane in 35 ml. of methylene chloride dropwise with stirring to a solution of 43 g. of carbon disulfide in 200 ml. of methylene chloride during about 3 hrs. The product formed as a white precipitate immediately on mixing of the two solutions. The solvent was removed by distillation in vacuo and replaced with water, and the mixture was refluxed for 7 hrs. It was concentrated to one-half the original volume, clarified by filtration while hot, and the product allowed to crystallize from the filtrate, yield 60.6 g., m.p. 114°-115°. A portion of this material, 43.9 g., (0.337 mole), was treated with 47.9 g. (0.337 mole) of methyl iodide in 400 ml. of ethanol. The methyl iodide was added by dropwise addition. The mixture was then concentrated in vacuo to an oil which was mixed with i-Pr2O to induce crystallization resulting in the formation of a light yellow solid, yield 90.7 g. (99%), of 2-methylthio-4,4-dimethyl-2-imidazoline hydroiodide. A portion of this material, 27.2 g. (0.1 mole), and 14.1 g. (0.1 mole) of p-chlorobenzylamine were dissolved in 100 ml. of abs. EtOH and added to a solution of 9.0 g. (0.4 mole) of sodium in 400 ml. of abs. EtOH at the reflux temperature. The solution was stirred for 10 min. and 14.2 g. (0.1 mole) of ethyl oximinocyanoacetate was added in portions during a period of about 5 min. The reaction solution became clear and bright yellow in color. It was refluxed for 41/2 hrs. and then concentrated in vacuo to yield an oily solid. The latter was dissolved in water and treated with acetic acid resulting in formation of the desired product as a red precipitate which was collected and air dried, m.p. 214°-215°, yield 16.7 g. (50%).

Workup

  1. additionby adding a solution of 50 g
  2. customThe product formed as a white precipitate immediately
  3. additionon mixing of the two solutions
  4. customThe solvent was removed by distillation in vacuo
  5. temperaturethe mixture was refluxed for 7 hrs
  6. concentrationIt was concentrated to one-half the original volume
  7. filtrationclarified by filtration while hot, and the product
  8. customto crystallize from the filtrate, yield 60.6 g
  9. addition, (0.337 mole), was treated with 47.9 g
  10. concentrationThe mixture was then concentrated in vacuo to an oil which
  11. additionwas mixed with i-Pr2O
  12. customcrystallization
  13. customresulting in the formation of a light yellow solid, yield 90.7 g
  14. temperatureIt was refluxed for 41/2 hrs
  15. concentrationand then concentrated in vacuo
  16. customto yield an oily solid
  17. customwas collected
  18. customair dried

Sources & evidence

ORD record
ord-6abf894912444d1498d95be0b6acdcbb
Source dataset
uspto-grants-1987_02
Patent number
US04642345

Reaction notes

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