Diethylene Glycol → 4-octyloxy-4'-((S)-3-methyl-pentyl)biphenyl

HRID 653382Notes

Reaction equation

HRID 653382 reaction equation
[CH2:1]([O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[CH:21]=[CH:20][C:19]([C:22](=O)[CH2:23][C@@H:24]([CH3:27])[CH2:25][CH3:26])=[CH:18][CH:17]=2)=[CH:12][CH:11]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].O.NN.C(O)COCCO.[OH-].[K+]>O>[CH2:1]([O:9][C:10]1[CH:11]=[CH:12][C:13]([C:16]2[CH:21]=[CH:20][C:19]([CH2:22][CH2:23][C@@H:24]([CH3:27])[CH2:25][CH3:26])=[CH:18][CH:17]=2)=[CH:14][CH:15]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]

Participants

6

Reactant 4

HCID 8117Diethylene GlycolHCID 14797Potassium HydroxideHCID 24654Hydrazine hydrate (1:1)HCID 136850704-octyloxy-4'-((S)-3-methyl-pentanoyl)biphenyl

Product 1

HCID 136850734-octyloxy-4'-((S)-3-methyl-pentyl)biphenylYield 56.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

4-Octyloxy-4'-((S)-3-methyl-pentanoyl)biphenyl (24.6 g, 0.065 mol) obtained in Example 23 described later, 80% hydrazine hydrate (50 ml) and diethylene glycol (85 ml) were placed in a 500 ml three-neck flask, followed by heating with stirring, keeping the mixture at 120° C. for one hour, then cooling, adding, at a stroke, a solution of potassium hydroxide (8.8 g, 0.157 mol) in water (5 ml) while keeping the temperature at 50° C., distilling off so that the temperature of the system might become 200° C., reacting at 200° C. for 4 hours, then cooling, adding water (200 ml) and toluene (50 ml), transferring the contents into a separating funnel, water-washing the organic layer till the washing liquid became neutral, distilling off the solvent, distilling under reduced pressure to collect a fraction having a boiling point of 210°-213° C./3 mmHg, and recrystallizing it from ethyl alcohol (20 ml) and ethyl acetate (5 ml) to obtain 4-octyloxy-4'-((S)-3-methyl-pentyl)biphenyl (IIIb1) (13.5 g) which was a smectic liquid crystal exhibiting SC* phase and SH* phase, and whose phase transition points were as follows as shown in Table 2, column of Example 24: C-S1 point, 43.0° C.; Sl-SH* point, 57.9° C.; SH*-SC* point, 62.5° C; SC*-I point, 65.1° C.

Workup

  1. temperatureby heating
  2. customat 120° C.
  3. customfor one hour
  4. temperaturecooling
  5. additionadding, at a stroke
  6. customat 50° C.
  7. distillationdistilling off so that the temperature of the system
  8. custommight become 200° C.
  9. temperaturecooling
  10. additionadding water (200 ml) and toluene (50 ml)
  11. washwater-washing the organic layer till the washing liquid
  12. distillationdistilling off the solvent
  13. distillationdistilling under reduced pressure
  14. customto collect a fraction
  15. customrecrystallizing it from ethyl alcohol (20 ml) and ethyl acetate (5 ml)

Sources & evidence

ORD record
ord-1a04ffe6852648d0995e950c111cfea7
Source dataset
uspto-grants-1987_06
Patent number
US04676925

Reaction notes

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