Trichloromethanethiol → 3-(4-Bromophenyl)-5-chloro-1,2,4-thiadiazole

HRID 1436443Notes

Reaction equation

HRID 1436443 reaction equation
Cl.[Br:2][C:3]1[CH:8]=[CH:7][C:6]([C:9](=[NH:11])[NH2:10])=[CH:5][CH:4]=1.C(N(CC)CC)C.[Cl:19][C:20]([SH:23])(Cl)Cl>C(Cl)Cl>[Br:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[N:10]=[C:20]([Cl:19])[S:23][N:11]=2)=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 6390TrichloromethanethiolHCID 8471TriethylamineHCID 122077144-Bromobenzene-1-carboximidamide--hydrogen chloride (1/1)

Product 1

HCID 118326413-(4-Bromophenyl)-5-chloro-1,2,4-thiadiazoleYield 28%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

4-Bromobenzenecarboximidamide hydrochloride (1.00 g, 4.25 mmol), prepared in the previous step, was suspended in methylene chloride (25 mL) and triethylamine (6.1 mL, 42.5 mmol) was added and the mixture was cooled to 0° C. Perchloromethyl mercaptan (0.47 g, 4.25 mmol) was added slowly, the mixture was stirred for 30 min, warmed to 25° C. and stirred 4 h. The mixture was diluted with methylene chloride, filtered through the Celite™ reagent, and concentrated. Flash chromatography (2% acetone in hexane) afforded 3-(4-bromophenyl)-5-chloro-1,2,4-thiadiazole (327 mg, 28%). HRMS: calcd for C8H4BrClN2S, 273.89671; found (EI, M+.), 273.8968; Analytical HPLC: purity 100% at 210-370 nm, 11.2 min; 100% at 272 nm, 11.2 min; the Xterra® RP18 column, 3.5μ, 150×4.6 mm column, 1.2 mL/min, 85/15-5/95 (Ammon. Form. Buff. pH=3.5/ACN+MeOH) for 10 min, hold 4 min.

Workup

  1. temperaturewarmed to 25° C.
  2. stirringstirred 4 h
  3. filtrationfiltered through the Celite™ reagent
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-67a846e3c7184bf68bc721306029be22
Source dataset
uspto-grants-2009_11
Patent number
US07618990B2

Reaction notes

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