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Acetonitrile → 5-difluoromethyl-4-{5-(3-ethyl-3-methoxy-1-pentynyl)-2-methylbenzyl)-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

HRID 1883625
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HRID 1883625 반응식
Br[C:2]1[CH:3]=[CH:4][C:5]([CH3:19])=[C:6]([CH:18]=1)[CH2:7][N:8]1[C:12]([CH:13]([F:15])[F:14])=[N:11][N:10]([CH3:16])[C:9]1=[O:17].[CH2:20]([C:22]([O:27][CH3:28])([CH2:25][CH3:26])[C:23]#[CH:24])[CH3:21].C(N(CC)CC)C.C(#N)C>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.COC(C)(C)C>[F:14][CH:13]([F:15])[C:12]1[N:8]([CH2:7][C:6]2[CH:18]=[C:2]([C:21]#[C:20][C:22]([CH2:25][CH3:26])([O:27][CH3:28])[CH2:23][CH3:24])[CH:3]=[CH:4][C:5]=2[CH3:19])[C:9](=[O:17])[N:10]([CH3:16])[N:11]=1
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참가 물질

9

반응물 4

HCID 6342AcetonitrileHCID 8471TriethylamineHCID 5660771-Pentyne, 3-ethyl-3-methoxy-HCID 129940064-(5-bromo-2-methylbenzyl)-5-difluoromethyl-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one2회

생성물 1

HCID 235082285-difluoromethyl-4-{5-(3-ethyl-3-methoxy-1-pentynyl)-2-methylbenzyl)-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one수율 84.5%

시약·촉매·용매 4

HCID 11776Triphenylphosphine촉매HCID 83717Copper iodide촉매HCID 178418476HCID 178418476, 화합물촉매HCID 15413tert-Butyl methyl ether용매

실험 절차

332 mg (1.00 mmol) of 4-(5-bromo-2-methylbenzyl)-5-difluoromethyl-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (Compound 40), 378 mg (3.00 mmol) of 3-ethyl-3-methoxy-1-pentine, 14 mg (0.020 mmol) of PdCl2(PPh3)2, 9.5 mg (0.050 mmol) of copper iodide (I), 15.7 mg (0.060 mmol) of triphenylphosphine and 0.5 ml of triethylamine were added to 4.0 ml of acetonitrile, and the mixture was heated under reflux for 5 hours in nitrogen atmosphere. After cooling to room temperature, t-butyl methyl ether was added to the reaction solution, and the mixture was washed with water and dried over anhydrous magnesium sulfate, then, concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (eluant: hexane/ethyl acetate=2/1 (v/v)), to obtain 319 mg of 5-difluoromethyl-4-{5-(3-ethyl-3-methoxy-1-pentynyl)-2-methylbenzyl}-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (Compound 277).

후처리

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 5 hours in nitrogen atmosphere
  3. washthe mixture was washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure

출처 및 근거

ORD 기록
ord-f5ccff407d1c4cce9bfac854c4df7d41
출처 데이터셋
uspto-grants-2004_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06762197B2

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