Hexamethyldisilazane → 1-methyl-2-[(4-nitrobenzyl)thio]-1H-imidazole

HRID 2413338Notes

Reaction equation

HRID 2413338 reaction equation
[CH3:1][N:2]1[CH:6]=[CH:5][N:4]=[C:3]1[SH:7].C[Si](C)(C)N[Si](C)(C)C.[N+:17]([C:20]1[CH:27]=[CH:26][C:23]([CH2:24]Br)=[CH:22][CH:21]=1)([O-:19])=[O:18].CN1C=CN=C1S[Si](C)(C)C>C(OCC)(=O)C.S1(C2C(=CC=CC=2)C(=O)N1)(=O)=O.CN(C)P(=O)(N(C)C)N(C)C.C1(C)C=CC=CC=1>[CH3:1][N:2]1[CH:6]=[CH:5][N:4]=[C:3]1[S:7][CH2:24][C:23]1[CH:26]=[CH:27][C:20]([N+:17]([O-:19])=[O:18])=[CH:21][CH:22]=1

Participants

9

Reactant 4

HCID 13838HexamethyldisilazaneHCID 660114-Nitrobenzyl bromideHCID 204308091-Methyl-2-[(trimethylsilyl)sulfanyl]-1H-imidazoleHCID 178480602HCID 178480602, compound

Product 1

HCID 7126051-methyl-2-[(4-nitrobenzyl)thio]-1H-imidazoleYield 89%

Reagents, catalysts & solvents 4

HCID 5143SaccharinCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

A mixture consisting of 2.85 g (25 mmoles) of 1-methyl-2-mercaptoimidazole, 22 mg (0.12 mmoles) of saccharin, 20 ml of toluene and 5.2 ml (25 mmoles) of hexamethyldisilazane was refluxed for 1 hour and after cooling to room temperature, 5.40 g (25 mmoles) of 4-nitrobenzyl bromide and then 5 ml of hexamethylphosphoric triamide were added to the mixture which contained 1-methyl-2-(trimethylsilylthio)-imidazole. After stirring for 2 hours at room temperature, the mixture was diluted to 150 ml with ethyl acetate and the solution thus obtained was washed three times with 50 ml of a saturated sodium bicarbonate solution and then twice with 20 ml of water. The organic layer was dried, filtered and evaporated to dryness and the crystalline residue was washed with 100 ml of petroleum ether (boiling range 60°-80° C.) and then vacuum dried to obtain 5.54 g (89% yield) of 1-methyl-2-(4-nitrobenzylthio)-imidazole melting to 74°-77° C. Crystallization of a sample from ethanol raised the melting point to 77.5°-78.0° C.

Workup

  1. temperaturewas refluxed for 1 hour
  2. customthe solution thus obtained
  3. washwas washed three times with 50 ml of a saturated sodium bicarbonate solution
  4. customThe organic layer was dried
  5. filtrationfiltered
  6. customevaporated to dryness
  7. washthe crystalline residue was washed with 100 ml of petroleum ether (boiling range 60°-80° C.)
  8. customvacuum dried

Sources & evidence

ORD record
ord-961eac512b99479c9a70f4d0c7d8a29e
Source dataset
uspto-grants-1985_01
Patent number
US04496720

Reaction notes

Loading…