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

HRID 1385636노트

반응식

HRID 1385636 반응식
[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

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 72391,2-Dichlorobenzene용매

반응 조건

온도
145 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-f185257daf2c469588bc5c78142b2890
출처 데이터셋
uspto-grants-2001_07
특허 번호
US06262305B1

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