Hydrochloric Acid → 4'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acid

HRID 1762772Notes

Reaction equation

HRID 1762772 reaction equation
C(OC(C1C=CC(C2C=CC(O)=CC=2)=CC=1)=O)C.[OH-].[K+].CC(OS(C1C=CC(C)=CC=1)(=O)=O)CCCCCC.Cl.C([O:43][C:44]([C:46]1[CH:51]=[CH:50][C:49]([C:52]2[CH:57]=[CH:56][C:55]([O:58][CH:59]([CH3:66])[CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH3:65])=[CH:54][CH:53]=2)=[CH:48][CH:47]=1)=[O:45])C.[OH-].[Na+]>C(O)C.O.C1(C)C=CC=CC=1>[CH3:66][CH:59]([O:58][C:55]1[CH:56]=[CH:57][C:52]([C:49]2[CH:48]=[CH:47][C:46]([C:44]([OH:45])=[O:43])=[CH:51][CH:50]=2)=[CH:53][CH:54]=1)[CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH3:65]

Participants

10

Reactant 6

HCID 313Hydrochloric Acid2×HCID 14797Potassium HydroxideHCID 14798Sodium HydroxideHCID 3912199p-Toluenesulfonic acid 1-methylheptyl esterHCID 4049156Ethyl 4'-hydroxy-4-biphenylcarboxylateHCID 136436484'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acid ethyl 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 (38.7 g, 0.160 mol) was dissolved in ethanol (200 ml), followed by further adding and dissolving KOH (9 g, 0.160 mol), adding optically active p-toluenesulfonic acid 1-methyl-heptyl ester obtained above (50 g, 0.176 mol), keeping the mixture under reflux for 4 hours, cooling, adding toluene (200 ml) and 6N-HCl (50 ml), washing the toluene layer with a 2N-NaOH aqueous solution, washing 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 (38.6 g, 0.109 mol), which was dissolved in ethanol (6 ml), NaOH (5.3 g, 0.130 mol) and water (26 ml), following by heating the solution under reflux for 10 minutes to deposit crystals, cooling, adding 6N-HCl (20 ml), separating crystals by filtering, and recrystallizing from acetic acid to obtain optically active 4'-(1-methyl-heptyloxy)-4-biphenylcarboxylic acid (23.4 g). This product exhibited liquid crystal phases and its phase transition points, C-SC* point, SC*-Ch point and Ch-I point were 160° C., 177° C. and 196° C., respectively.

Workup

  1. additionby further adding
  2. customobtained above (50 g, 0.176 mol)
  3. temperatureunder reflux for 4 hours
  4. temperaturecooling
  5. washwashing the toluene layer with a 2N-NaOH aqueous solution
  6. washwashing with water till the washing water
  7. distillationdistilling off toluene
  8. customto obtain as a residue
  9. temperatureby heating the solution
  10. temperatureunder reflux for 10 minutes
  11. temperaturecooling
  12. customseparating crystals
  13. filtrationby filtering
  14. customrecrystallizing from acetic acid

Sources & evidence

ORD record
ord-fa9b3033ce3242a388a40fda83688ca8
Source dataset
uspto-grants-1989_05
Patent number
US04834907

Reaction notes

Loading…