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

HRID 1789313Notes

Reaction equation

HRID 1789313 reaction equation
BrC1C=CC(C2C=CC(OC(=O)C3C=CC(OC(C)CCCCCC)=CC=3)=CC=2)=CC=1.C(OC(C1C=CC(C2C=CC(O)=CC=2)=CC=1)=O)C.[OH-].[K+].FC1C=CC([O:59][C:60]([C:62]2[CH:67]=[CH:66][C:65]([C:68]3[CH:73]=[CH:72][C:71]([O:74][CH:75]([CH3:82])[CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH3:81])=[CH:70][CH:69]=3)=[CH:64][CH:63]=2)=[O:61])=CC=1.C(OC(C1C=CC(C2C=CC(OC(C)CCCCCC)=CC=2)=CC=1)=O)C.[OH-].[Na+].Cl>CO.O.C(O)C.C1(C)C=CC=CC=1>[CH3:82][CH:75]([O:74][C:71]1[CH:72]=[CH:73][C:68]([C:65]2[CH:64]=[CH:63][C:62]([C:60]([OH:61])=[O:59])=[CH:67][CH:66]=2)=[CH:69][CH:70]=1)[CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH3:81]

Participants

12

Reactant 7

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 14798Sodium HydroxideHCID 4049156Ethyl 4'-hydroxy-4-biphenylcarboxylateHCID 136436484'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acid ethyl esterHCID 139545494'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acid p-fluorophenyl esterHCID 53700258p-(1-Methylheptyloxy)benzoic acid 4'-bromo-4-biphenylyl ester

Product 1

HCID 136436504'-(1-Methyl-heptyloxy)-4-biphenylcarboxylic acidYield 12%

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

Preparation of optically active p-(1-methylheptyloxy)benzoic acid 4'-bromo-4-biphenylyl ester (a compound of the formula (I) wherein l=1, m=1, R=C6H13, X=Br and Y, Z=H; Sample No. 9) P-hydroxybenzoic acid methyl ester (IV) (28.5 g, 0.187 mol) was dissolved in methanol (120 ml), and KOH (10.1 g, 0.187 mol) was added to and dissolved in the solution, followed by adding to the resulting solution, optically active p-toluenesulfonic acid 1-methyl-heptyl ester (III) (58.6 g, 0.206 mol) obtained in Example 1, 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 then with water till the washing water became neutral and distilling off toluene to obtain as a residue, optically active p-(1-methyl-heptyloxy)benzoic acid methyl ester (V) (14.2 g). This ester (14.2 g, 0.054 mol) was dissolved together with ethanol (5 ml), NaOH (3.2 g, 0.081 mol) and water (20 ml), followed by heating the solution under reflux for one hour, then cooling, pouring the reaction fluid in 6N--HCl aqueous solution (50 ml) with stirring, filtering off deposited crysrals and recrystallizing from ethanol to obtain optically active p-(1-methyl-butyloxy)benzoic acid (VI) (8.1 g) having a melting point of 61.2°~63.1° C. To this product (7.5 g, 0.030 mol) was added thionyl chloride (6.0 g, 0.047 mol), followed by heating the mixture under reflux for one hour, and distilling off excess thionyl chloride to obtain opticaly active p-(1-methyl-heptyloxy)benzoic acid chloride (VII) (5.8 g).

Workup

  1. dissolutiondissolved in the solution
  2. temperatureunder reflux for 4 hours
  3. temperaturecooling
  4. washHCl (50 ml), washing the resulting toluene layer with 2N
  5. distillationdistilling off toluene
  6. customto obtain as a residue
  7. temperatureby heating the solution
  8. temperatureunder reflux for one hour
  9. temperaturecooling
  10. additionpouring the reaction fluid in 6N
  11. filtrationfiltering off
  12. customrecrystallizing from ethanol

Sources & evidence

ORD record
ord-05c7a79b32a14c249690b3af58161101
Source dataset
uspto-grants-1987_08
Patent number
US04689176

Reaction notes

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