Potassium Hydroxide → 4'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acid

HRID 1789312Notes

Reaction equation

HRID 1789312 reaction equation
C(OC(C1C=CC(C2C=CC(O)=CC=2)=CC=1)=O)C.[OH-].[K+].CC(OS(C1C(C)=CC=CC=1)(=O)=O)CCCCCC.C([O:42][C:43]([C:45]1[CH:50]=[CH:49][C:48]([C:51]2[CH:56]=[CH:55][C:54]([O:57][CH:58]([CH3:65])[CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH3:64])=[CH:53][CH:52]=2)=[CH:47][CH:46]=1)=[O:44])C.[OH-].[Na+]>C(O)C.O.C1(C)C=CC=CC=1>[CH3:65][CH:58]([O:57][C:54]1[CH:55]=[CH:56][C:51]([C:48]2[CH:47]=[CH:46][C:45]([C:43]([OH:44])=[O:42])=[CH:50][CH:49]=2)=[CH:52][CH:53]=1)[CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH3:64]

Participants

9

Reactant 5

HCID 14797Potassium HydroxideHCID 14798Sodium HydroxideHCID 4049156Ethyl 4'-hydroxy-4-biphenylcarboxylateHCID 136436484'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acid ethyl esterHCID 19990276Toluenesulfonic acid 1-methyl-heptyl ester

Product 1

HCID 136436504'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acidYield 65.8%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

On the other hand, 4-hydroxy-4'-biphenylcarboxylic acid ethyl ester (IV) (38.7 g, 0.160 mol) was dissolved in ethanol (200 ml), and KOH (9 g, 0.160 mol) was added to and dissolved in the solution, followed by adding optically active toluenesulfonic acid 1-methyl-heptyl ester (50 g, 0.176 mol) obtained above, keeping the mixture under reflux for 4 hours, then cooling, adding toluene (200 ml) and 6N--HCl (50 ml), washing the resulting toluene layer with 2N--NaOH aqueous solution and further with water till the washing water became neutral, and distilling off toluene to obtain as a residue, optically active 4'-(1-methyl-heptyloxy)-4-biphenylcarboxylic acid ethyl ester (V) (38.6 g). This product (38.6 g, 0.109 mol) was dissolved in ethanol (6 ml), NaOH (5.3 g, 0.130 mol) and water (26 ml), followed by heating the solution under reflux for 10 minutes to deposit crystals, cooling, adding 6N--HCl (20 ml) to filter off crystals and further recrystallizing from acetic acid to obtain optically active 4'-(1-methyl-heptyloxy)-4-biphenylcarboxylic acid (VI) (23.4 g). This product exhibited liquid crystal phases and the phase transition points were as follows: C-SC* point 160° C., SC*-Ch point 177° C. and Ch-I point 196° C.

Workup

  1. dissolutiondissolved in the solution
  2. customobtained above,
  3. temperatureunder reflux for 4 hours
  4. temperaturecooling
  5. washHCl (50 ml), washing the resulting toluene layer with 2N
  6. distillationdistilling off toluene
  7. customto obtain as a residue
  8. temperatureby heating the solution
  9. temperatureunder reflux for 10 minutes
  10. temperaturecooling
  11. additionadding 6N
  12. filtrationHCl (20 ml) to filter off crystals
  13. customfurther recrystallizing from acetic acid

Sources & evidence

ORD record
ord-1f7059ca42634837b7b995e414e4f63a
Source dataset
uspto-grants-1987_08
Patent number
US04689176

Reaction notes

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