Diethylene Glycol → HCID 178448004, compound

HRID 1165113Notes

Reaction equation

HRID 1165113 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][C:7]([C@H:10]2[CH2:15][CH2:14][C@H:13]([C@H:16]3[CH2:21][CH2:20][C@H:19]([CH2:22][CH2:23][CH3:24])[CH2:18][CH2:17]3)[CH2:12][CH2:11]2)=[CH:6][C:5]=1[F:25])(=O)[CH3:2].C(O)COCCO.O.NN.[OH-].[K+]>O>[CH2:1]([C:4]1[CH:9]=[CH:8][C:7]([C@H:10]2[CH2:11][CH2:12][C@H:13]([C@H:16]3[CH2:21][CH2:20][C@H:19]([CH2:22][CH2:23][CH3:24])[CH2:18][CH2:17]3)[CH2:14][CH2:15]2)=[CH:6][C:5]=1[F:25])[CH3:2]

Participants

6

Reactant 4

HCID 8117Diethylene GlycolHCID 14797Potassium HydroxideHCID 24654Hydrazine hydrate (1:1)HCID 178448006HCID 178448006, compound

Product 1

HCID 178448004HCID 178448004, compoundYield 66.6%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Successively, anhydrous aluminum chloride (30.8 g, 0.23 mol) was dissolved in nitrobenzene (150 ml), followed by adding to the solution, the total quantity of the above compound 3-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]fluorobenzene (38.7 g) at room temperature, dissolving the mixture together with stirring, adding acetyl chloride (27.3 g, 0.348 mol) over 15 minutes, reacting the mixture on heating at a reaction temperature of 35°-40° C. for 2 hours, adding the reaction solution after completion of the reaction to a mixture of 6N hydrochloric acid (50 ml) with ice water (500 g) to subject them to decomposition reaction, adding toluene (500 ml) to extract the resulting oily layer, washing the extract solution with an aqueous solution of sodium hydrogen carbonate, further washing it with water until the washing water became neutral, distilling off toluene and nitrobenzene and recrystallizing the residue from ethyl acetate to obtain 2-acetyl-5-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]fluorobenzene (a compound of the formula (VII) wherein R1 =C3H7 and R"=CH3) (23.8 g). This product exhibited liquid crystal phases and had a crystal-nematic phase transition point (C-N point) of 90.5° C. and a nematic phase-isotropic liquid phase transition point (N-I point) of 204.7° C. (iii) Successively, the compound 2-acetyl-5-[trans-4-(trans-4-propylcyclohexyl) cyclohexyl]fluorobenzene (23.8 g) was added to diethylene glycol (100 ml), followed by agitating the mixture, adding hydrazine hydrate (17.9 g) and potassium hydroxide (20.1 g), gradually raising the temperature with stirring to react the mixture at 180° C. for 3 hours, allowing the resulting material to cool down to room temperature, adding water (500 ml), extracting the deposited crystals with toluene (100 ml), washing the extract solution with water, drying it over anhydrous sodium sulfate, distilling off toluene and recrystallizing from ethyl acetate to obtain 2-ethyl-5-[trans-4-(trans-4-propylcyclohexyl)cyclohexyl]fluorobenzene (15.2 g).

Workup

  1. customa crystal-nematic phase transition point (C-N point) of 90.5° C.
  2. temperaturegradually raising the temperature
  3. stirringwith stirring
  4. customto react the mixture at 180° C. for 3 hours
  5. extractionextracting the deposited crystals with toluene (100 ml)
  6. washwashing the extract solution with water
  7. dry with materialdrying it over anhydrous sodium sulfate
  8. distillationdistilling off toluene
  9. customrecrystallizing from ethyl acetate

Sources & evidence

ORD record
ord-640f43dc92524c178d58c3d8d45ab66c
Source dataset
uspto-grants-1990_03
Patent number
US04908152

Reaction notes

Loading…