2-Bromomesitylene → 1,3-Dimesityltriazene

HRID 1477253노트

반응식

HRID 1477253 반응식
[C:1]1([Mg]Br)[C:8]([CH3:9])=[CH:7][C:5]([CH3:6])=[CH:4][C:2]=1[CH3:3].[Li+].[Cl-].[Mg].BrC1C(C)=CC(C)=CC=1C.[N:25]([C:28]1[C:33]([CH3:34])=[CH:32][C:31]([CH3:35])=[CH:30][C:29]=1[CH3:36])=[N+:26]=[N-:27]>C1COCC1>[C:2]1([CH3:3])[CH:4]=[C:5]([CH3:6])[CH:7]=[C:8]([CH3:9])[C:1]=1[N:27]=[N:26][NH:25][C:28]1[C:33]([CH3:34])=[CH:32][C:31]([CH3:35])=[CH:30][C:29]=1[CH3:36]

참가 물질

7

반응물 5

HCID 684732-BromomesityleneHCID 167030Benzene, 2-azido-1,3,5-trimethyl-HCID 433294Lithium Chloride2회HCID 5462224MagnesiumHCID 178425415HCID 178425415, 화합물

생성물 1

HCID 153301851,3-Dimesityltriazene수율 92%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

A THF solution of MesMgBr.LiCl is first prepared by an adaptation the procedure of Knochel et al. To a stirred suspension of magnesium turnings (0.72 g, 30 mmol) and anhydrous LiCl (1.26 g, 30 mmol) in anhydrous THF (40 mL) is added 2-bromomesitylene (5.05 mL, 33 mmol). The exothermic reaction initiates slowly and is allowed to stir overnight at room temperature. To the resulting mixture, which is cooled to 0° C., is added 2-azidomesitylene (4.59 g, 28.5 mmol). Stirring is continued for 1 hour at 0° C., and then an additional 1 hour while allowing to warm to room temperature. The reaction mixture is quenched by pouring the contents into water. A minimum of aqueous NH4Cl is added to neutralize the pH, and the organic products are extracted with Et2O. After washing the combined organic layers with brine, solvents are evaporated at room temperature under reduced pressure to afford a crude product that is recrystallized from Et2O-MeOH to afford 8b (7.41 g, 92%) as off-white needles over 2 crops. 1H-NMR (CDCl3, 300 MHz): δ=9.14 (br s, 1H), 6.93 (br s, 4H), 2.32-2.30 (br m, 18H). M.p.: 92-94° C. (dec). Characterization data for 8b are consistent with literature values.

후처리

  1. customThe exothermic reaction initiates slowly
  2. temperatureTo the resulting mixture, which is cooled to 0° C.
  3. stirringStirring
  4. waitis continued for 1 hour at 0° C.
  5. customan additional 1 hour
  6. temperatureto warm to room temperature
  7. customThe reaction mixture is quenched
  8. additionby pouring the contents into water
  9. additionA minimum of aqueous NH4Cl is added
  10. extractionthe organic products are extracted with Et2O
  11. washAfter washing the combined organic layers with brine, solvents
  12. customare evaporated at room temperature under reduced pressure
  13. customto afford a crude product that
  14. customis recrystallized from Et2O-MeOH

출처 및 근거

ORD 기록
ord-cada21df4a7f4aec89eda01877d075c7
출처 데이터셋
uspto-grants-2016_08
특허 번호
US09403781B2

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