Chlorotrimethylsilane → 4-Azido-2-fluoro-1-triphenylmethylimidazole

HRID 2412511Notes

Reaction equation

HRID 2412511 reaction equation
[F:1][C:2]1[N:3]([C:7]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:4]=[CH:5][N:6]=1.C([Li])(C)(C)C.C1(C)C=CC(S([N:40]=[N+:41]=[N-:42])(=O)=O)=CC=1.Cl[Si](C)(C)C>C1COCC1.C1(C)C=CC=CC=1>[N:40]([C:5]1[N:6]=[C:2]([F:1])[N:3]([C:7]([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:4]=1)=[N+:41]=[N-:42]

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 13661p-Toluenesulfonyl azideHCID 204324542-Fluoro-1-trityl-1H-imidazoleHCID 178418306HCID 178418306, compound

Product 1

HCID 204324194-Azido-2-fluoro-1-triphenylmethylimidazole

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 2-fluoro-1-triphenylmethylimidazole in THF was treated with t-butyllithium at -70° for 2 hours. A solution of toluene-p-sulphonyl azide in toluene was added, followed after 10 minutes by chlorotrimethylsilane, and the mixture allowed to come to 0°. Work-up and chromatography on magnesium silicate gave 4-azido-2-fluoro-1-triphenylmethylimidazole. This was dissolved in ether and treated with triphenylphosphine at 25°, to precipitate 2-fluoro-1-triphenylmethyl-4-(triphenylphosphimino)imidazole. A solution of this compound in EtOAc was treated for 10 minutes at 25° with propionyl chloride. Aqueous work-up, followed by magnesium silicate chromatography gave 2-fluoro-4-propionylamino-1-triphenylmethylimidazole, having the following n.m.r. in CDCl3 : 1.05 (t, 3H); 2.2 (q, 2H); 6.95 (s, 1H); 7.05-7.4 (m, 15H); 9.05 (s, 1H).

Workup

  1. customto come to 0°

Sources & evidence

ORD record
ord-afe29e8f17e14089aa0fb17bc58d73fc
Source dataset
uspto-grants-1985_01
Patent number
US04492692

Reaction notes

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