Toluene → 1-(4'-Octyloxy-4-biphenylyloxy)-4-methylpentan-2-ol

HRID 892705Notes

Reaction equation

HRID 892705 reaction equation
[H-].[Na+].[OH:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][C:13]([O:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])=[CH:12][CH:11]=2)=[CH:6][CH:5]=1.[C:25]1([CH3:31])[CH:30]=C[CH:28]=[CH:27][CH:26]=1.C1C[O:35]CC1>CN(C)C=O>[CH2:17]([O:16][C:13]1[CH:14]=[CH:15][C:10]([C:7]2[CH:6]=[CH:5][C:4]([O:3][CH2:28][CH:27]([OH:35])[CH2:26][CH:25]([CH3:31])[CH3:30])=[CH:9][CH:8]=2)=[CH:11][CH:12]=1)[CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24]

Participants

6

Reactant 4

HCID 1140TolueneHCID 8028Tetrahydrofuran2×HCID 24758Sodium hydrideHCID 104943294-Hydroxy-4'-octyloxybiphenyl

Product 1

HCID 221293021-(4'-Octyloxy-4-biphenylyloxy)-4-methylpentan-2-ol

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

THF (20 ml) was added to sodium hydride (55%) (1.7 g) and the solution was cooled, followed by adding to the solution, a solution of 4'-hydroxy-4-octyloxy-biphenyl (8 g) in THF (100 ml), successively adding a solution of 2S-2-(2'-tetrahydropyranyloxy)-4-methyl-pentyl-p-toluenesulfonate (10 g) obtained above in the item 2 in N,N-dimethylformamide (hereinafter abbreviated to DMF) (200 ml), heating the mixture at 80°-90° C. for 8 hours, cooling the resulting material, adding toluene (300 ml), washing with water, then with an alkali and further with water, concentrating, purifying the concentrate according to column chromatography using a column having activated alumina filled therein and using toluene as an eluent, concentrating the resulting elute, adding ethanol (300 ml), further adding 12M+HCl (5 ml), heating the mixture at 60° C. for 2 hours, cooling, filtering off the resulting solids, and recrystallizing from a mixed solution of ethanol with ethyl acetate to obtain S -1-(4'-octyloxy-4-biphenylyloxy)-4-methylpentan-2-ol ([α]D24 +8.2 (C 0.54, CHCl3)) (8 g). This product exhibited phase transition points of C 95° C. (S5.58° C.), S4.103° C., S3.113.1° C., S2.113.6° C., S1.115.6° C., SA.119.5° C. and I wherein C represents crystalline phase; I , isotropic liquid phase; SA, smectic A phase; S1 -S5, smectic phases whose attributions are at present unknown; and (), monotropic phase.

Workup

  1. temperaturethe solution was cooled
  2. additionby adding to the solution
  3. temperatureheating the mixture at 80°-90° C. for 8 hours
  4. temperaturecooling the resulting material
  5. washwashing with water
  6. concentrationwith an alkali and further with water, concentrating
  7. custompurifying the concentrate
  8. additionfilled
  9. concentrationconcentrating the resulting
  10. washelute
  11. additionadding ethanol (300 ml)
  12. additionfurther adding 12M+HCl (5 ml)
  13. temperaturecooling
  14. filtrationfiltering off the resulting solids
  15. customrecrystallizing from a mixed solution of ethanol with ethyl acetate

Sources & evidence

ORD record
ord-a8f18c74f0c6465bb8e8b3ac3ab0af41
Source dataset
uspto-grants-1992_06
Patent number
US05120468

Reaction notes

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