Aluminum(III) Chloride → 1-Methyl-3-(2-chloro-6-fluorophenyl)-5-(3,4,5-trichloro-2-thienyl)-1H-1,2,4-triazole

HRID 850035Notes

Reaction equation

HRID 850035 reaction equation
[CH3:1][N:2](S(C1C=CC=CC=1)(=O)=O)[N:3]=[C:4](Cl)[C:5]1[C:10]([F:11])=[CH:9][CH:8]=[CH:7][C:6]=1[Cl:12].[C:23]([C:25]1[S:26][C:27]([Cl:32])=[C:28]([Cl:31])[C:29]=1[Cl:30])#[N:24].[Cl-].[Al+3].[Cl-].[Cl-]>ClC1C=CC=CC=1Cl>[Cl:12][C:6]1[CH:7]=[CH:8][CH:9]=[C:10]([F:11])[C:5]=1[C:4]1[N:24]=[C:23]([C:25]2[S:26][C:27]([Cl:32])=[C:28]([Cl:31])[C:29]=2[Cl:30])[N:2]([CH3:1])[N:3]=1

Participants

5

Reactant 3

HCID 6451240Aluminum(III) ChlorideHCID 117459463,4,5-Trichloro-2-thiophenecarbonitrileHCID 53760501N-methyl-N-phenylsulfonyl-2-chloro-6-fluorobenzohydrazonoyl chloride

Product 1

HCID 118113871-Methyl-3-(2-chloro-6-fluorophenyl)-5-(3,4,5-trichloro-2-thienyl)-1H-1,2,4-triazoleYield 55.3%

Reagents, catalysts & solvents 1

HCID 72391,2-DichlorobenzeneSolvent

Conditions

Temperature
145 °C

Procedure

To a mixture of N-methyl-N-benzenesulfonyl-2-chloro-6-fluorobenzhydrazonoyl chloride (47.5 g, 0.131 mol) and 2-cyano-3,4,5-trichlorothiophene (26.5 g 0.125 mol in o-dichlorobenzene (18 mL), was added aluminum chloride (11.1 g, 0.083 mol). The mixture was lowered into a preheated oil bath maintained at 140-150° C. The mixture was allowed to remain in the hot oil bath 40 min and was then removed from the bath and stirred for 2 hr as it gradually cooled. The reaction mixture was poured into 2N sodium hydroxide (300 mL-enough to dissolve the aluminum salts) and extracted with methylene chloride (3×250 mL). The organic phases were combined, washed with brine, dried (MgSO4), and the solvent removed in vacuo to give the crude product. The residue was placed on silica gel (150 g) and then chromatographed using ethyl acetate/hexanes as eluant to obtain 39.7 g (55.3% yield) of the title compound; 99.4% pure by GC analysis; mp 129-130° C.; 1H NMR (CDCl3) δ 7.3 (m, 2H), 7.1 (m, 1H), 4.0 (s, 3H); Anal. for C13H6Cl4FN3S: Calcd. C, 39.32; H, 1.52; N, 10.58. Found C, 39.08; H, 1.30; N, 10.34.

Workup

  1. customThe mixture was lowered into a preheated oil bath
  2. customto remain in the hot oil bath 40 min
  3. customwas then removed from the bath
  4. temperaturegradually cooled
  5. additionThe reaction mixture was poured into 2N sodium hydroxide (300 mL-enough
  6. dissolutionto dissolve the aluminum salts) and
  7. extractionextracted with methylene chloride (3×250 mL)
  8. washwashed with brine
  9. dry with materialdried (MgSO4)
  10. customthe solvent removed in vacuo
  11. customto give the crude product
  12. customchromatographed

Sources & evidence

ORD record
ord-bf2dd44e09874340b7290e5367635c49
Source dataset
uspto-grants-2000_01
Patent number
US06015826

Reaction notes

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