Sulfuric Acid → HCID 19901371, compound

HRID 2372665Notes

Reaction equation

HRID 2372665 reaction equation
C1(C)C=CC(S([O:10][C:11]2[CH:16]=[CH:15][C:14]([C:17]3[CH:22]=[CH:21][C:20]([CH:23]=[O:24])=[CH:19][CH:18]=3)=[CH:13][CH:12]=2)(=O)=O)=CC=1.[CH2:26]([CH:32]([CH2:35]O)[CH2:33][OH:34])[CH2:27][CH2:28][CH2:29][CH2:30][CH3:31].S(=O)(=O)(O)O>C1(C)C=CC=CC=1.ClCCl>[CH2:26]([CH:32]1[CH2:35][O:24][CH:23]([C:20]2[CH:19]=[CH:18][C:17]([C:14]3[CH:13]=[CH:12][C:11]([OH:10])=[CH:16][CH:15]=3)=[CH:22][CH:21]=2)[O:34][CH2:33]1)[CH2:27][CH2:28][CH2:29][CH2:30][CH3:31]

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 2684842-hexylpropane-1,3-diolHCID 19901373HCID 19901373, compound

Product 1

HCID 19901371HCID 19901371, compoundYield 71.2%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 6344DichloromethaneSolvent

Procedure

A solution of 2.82 g of 4'-(p-toluenesulphonyloxy)biphenyl-4-carboxaldehyde and 1.54 g of 2-hexyl-1,3-propane-diol in 50 ml of toluene was treated with 3 drops of 10% (vol.) sulphuric acid. The mixture was heated to boiling for 1.5 hours, with about 50 ml of damp toluene being distilled off and 30 ml of fresh toluene being simultaneously added dropwise. Then, 10 drops of triethylamine were added to the reaction mixture. After cooling the mixture was washed with 10 ml of lN sodium hydrogen carbonate solution and three times with 20 ml of water each time, dried over sodium sulphate and concentrated. The resulting crude 5-hexyl-2-[4'-(p-toluenesulphonyloxy)-4-biphenylyl]m-dioxane (4.26 g) was dissolved in 160 ml ethanol. The solution was treated with a solution of 2.64 g of potassium hydroxide in 27 ml of water and heated to boiling for 1.8 hours while stirring. After cooling the reaction mixture was neutralized (to pH 6) with 1.9 ml of glacial acetic acid and concentrated to about 20 ml. The suspension obtained was diluted with 80 ml of dichloromethane and the organic phase was washed twice with 20 ml of water each time, dried over sodium sulphate and concentrated. Chromatography of the residue (2.80 g) on g of silica gel with toluene/acetone (vol. 19:1) gave 1.94 g of 5-hexyl-2-(4'-hydroxy-4-biphenylyl)-m-dioxane.

Workup

  1. temperatureThe mixture was heated
  2. distillationdistilled off
  3. addition30 ml of fresh toluene being simultaneously added dropwise
  4. additionThen, 10 drops of triethylamine were added to the reaction mixture
  5. temperatureAfter cooling the mixture
  6. washwas washed with 10 ml of lN sodium hydrogen carbonate solution and three times with 20 ml of water each time
  7. dry with materialdried over sodium sulphate
  8. concentrationconcentrated
  9. dissolutionThe resulting crude 5-hexyl-2-[4'-(p-toluenesulphonyloxy)-4-biphenylyl]m-dioxane (4.26 g) was dissolved in 160 ml ethanol
  10. additionThe solution was treated with a solution of 2.64 g of potassium hydroxide in 27 ml of water
  11. temperatureheated
  12. temperatureAfter cooling the reaction mixture
  13. concentrationconcentrated to about 20 ml
  14. customThe suspension obtained
  15. washthe organic phase was washed twice with 20 ml of water each time
  16. dry with materialdried over sodium sulphate
  17. concentrationconcentrated

Sources & evidence

ORD record
ord-599fb20c3a2f4294b280614fa349b4b4
Source dataset
uspto-grants-1992_03
Patent number
US05100577

Reaction notes

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