4-Bromoanisole → HCID 14669906, compound

HRID 619978Notes

Reaction equation

HRID 619978 reaction equation
Cl[C:2]1[N:3]=[N:4][C:5]([C:8]2[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][CH3:16])=[CH:10][CH:9]=2)=[CH:6][CH:7]=1.Br[C:18]1[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=1.[Mg]>O1CCCC1.Cl[Ni]Cl>[CH3:25][O:24][C:21]1[CH:22]=[CH:23][C:18]([C:2]2[N:3]=[N:4][C:5]([C:8]3[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][CH3:16])=[CH:10][CH:9]=3)=[CH:6][CH:7]=2)=[CH:19][CH:20]=1

Participants

6

Reactant 3

HCID 77304-BromoanisoleHCID 5462224MagnesiumHCID 21790554HCID 21790554, compound

Product 1

HCID 14669906HCID 14669906, compound

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-10 °C

Procedure

3-Chloro-6-(4'-propylphenyl)-pyridazine prepared according to a method disclosed in a known literature (m.p.: 127.6°-129.6° C.) (60.0 g) was dissolved in tetrahydrofuran (THF) (700 ml), followed by adding NiCl2 (dppp) (2.5 g) as a catalyst, agitating the mixture at -10° C. for 15 minutes, dropwise adding therto a Grignard reagent obtained by reacting p-bromoanisole (96.5 g) with magnesium in THF, agitating the mixture in an ice bath for one hour, removing the ice bath, agitating it at room temperature for 3 hours, allowing it to stand overnight, adding toluene (500 ml), further adding 6N-hydrochloric acid, separating the resulting organic layer, washing it with water, then with an alkali and further with water till the washing water became neutral, drying with MgSO4, distilling off toluene, purifying the residue according to column chromatography using activated alumina (300 g) and toluene as an eluent, concentrating, and recrystallizing from ethyl acetate (700 ml) to obtain 3-(4'-methoxyphenyl)-6-(4'-propylphenyl)-pyridazine (70 g). This product had a m.p. of 155.9° C., exhibited nematic phase and formed an isotropic liquid at 254° C.

Workup

  1. customobtained
  2. stirringagitating the mixture in an ice bath for one hour
  3. customremoving the ice bath
  4. stirringagitating it at room temperature for 3 hours
  5. waitto stand overnight
  6. additionadding toluene (500 ml)
  7. additionfurther adding 6N-hydrochloric acid
  8. customseparating the resulting organic layer
  9. washwashing it with water
  10. dry with materialdrying with MgSO4
  11. distillationdistilling off toluene
  12. custompurifying the residue
  13. concentrationconcentrating
  14. customrecrystallizing from ethyl acetate (700 ml)

Sources & evidence

ORD record
ord-2a8a9da0f3fe445695f3e988d155d104
Source dataset
uspto-grants-1989_04
Patent number
US04818430

Reaction notes

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