Sodium Hydroxide → 1-Bromo-3-chloro-2,2,5,5-tetramethylimidazolidin-4-one

HRID 345628Notes

Reaction equation

HRID 345628 reaction equation
CC1(C)NC(=O)C(C)(C)N1.[OH-].[Na+].BrBr.[H][H].[Cl:17]Cl.[Br:19][N:20]1[C:24]([CH3:26])([CH3:25])[C:23](=[O:27])[N:22](Br)[C:21]1([CH3:30])[CH3:29].[K+].[Br-]>O>[Br:19][N:20]1[C:24]([CH3:26])([CH3:25])[C:23](=[O:27])[N:22]([Cl:17])[C:21]1([CH3:30])[CH3:29]

Participants

9

Reactant 7

HCID 14798Sodium Hydroxide2×HCID 24408Bromine3×HCID 24526Chlorine2×HCID 253877Potassium BromideHCID 98127982,2,5,5-Tetramethyl-4-imidazolidinoneHCID 147747041,3-Dibromo-2,2,5,5-tetramethylimidazolidin-4-oneHCID 178418361HCID 178418361, compound

Product 1

HCID 147747051-Bromo-3-chloro-2,2,5,5-tetramethylimidazolidin-4-one

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Procedure

6.4 Grams (0.045 mole) of 2,2,5,5-tetramethylimidazolidin-4-one prepared as in example 2 was dissolved in 55 milliliters of 1 Normal sodium hydroxide solution (0.055 mole) in a 250 milliliter flask. While maintaining the reaction mixture at a temperature of 5°-10° C. by use of an ice bath and stirring, 4.0 grams (0.025 mole) of liquid bromine was added dropwise. The reaction mixture was stirred at ice bath temperature for an additional 1 hour and then for 1-2 hours at cold water bath conditions (10°-20° C.). Following cooling the mixture below 10° C. again, 50 milliliters of 1 Normal sodium hydroxide solution (0.05 mole) was added, and chlorine gas was bubbled in while stirring at 5°-10° C. until the pH reached 6-7. The 1-bromo-3-chloro-2,2,5,5-tetramethylimidazolidin-4-one product precipitated as a white solid. The product was recovered by suction filtration and purified by recrystallization from hexane. The product yield was 11.2 grams or 97% of that theoretically expected. Elemental analysis of the product gave the following results: (calculated/found) % carbon 32.88/32.68, % hydrogen 4.70/4.74, % nitrogen 10.96/10.83, % bromine 31.31/33.37, % chlorine 13.89/12.67. The rather high and low found values as compared to the theoretical values for bromine and chlorine, respectively, indicate that the product was contaminated with a small amount of 1,3-dibromo-2,2,5,5-tetramethylimidazolidin-4-one. The product was found to have a solubility in water ranging from 0.102 grams in 100 milliliters of water at 3° C. to 0.193 grams in 100 milliliters of water at 37° C. The product had a melting point of 88° C.±2° C. Analysis of the product by proton NMR and infrared spectroscopy yielded the following results: 1H NMR (CCl4) δ=1.34 (S,6H), δ =1.50 (S,6H); IR (KBr) 1700, 2950 cm-1.

Workup

  1. temperatureWhile maintaining the reaction mixture at a temperature of 5°-10° C. by use of an ice bath
  2. stirringThe reaction mixture was stirred at ice bath temperature for an additional 1 hour
  3. temperatureFollowing cooling the mixture below 10° C. again
  4. customchlorine gas was bubbled in
  5. stirringwhile stirring at 5°-10° C. until the pH
  6. customThe 1-bromo-3-chloro-2,2,5,5-tetramethylimidazolidin-4-one product precipitated as a white solid
  7. filtrationThe product was recovered by suction filtration
  8. custompurified by recrystallization from hexane
  9. customElemental analysis of the product gave the
  10. customfollowing results
  11. customat 37° C
  12. customyielded the
  13. customfollowing results

Sources & evidence

ORD record
ord-5e8c1b69e7794a37bdfd84a59d97b48b
Source dataset
uspto-grants-1991_10
Patent number
US05057612

Reaction notes

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