Dimethyl Sulfoxide → 2-(4'-Hexyloxyphenyl)terephthalaldehyde

HRID 990177Notes

Reaction equation

HRID 990177 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][C:13]1[CH:18]=[CH:17][C:16]([CH2:19][OH:20])=[CH:15][C:14]=1[C:21]1[CH:26]=[CH:25][C:24]([O:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])=[CH:23][CH:22]=1.C(N(CC)CC)C>ClCCl.O>[CH2:28]([O:27][C:24]1[CH:23]=[CH:22][C:21]([C:14]2[CH:15]=[C:16]([CH:19]=[O:20])[CH:17]=[CH:18][C:13]=2[CH:12]=[O:11])=[CH:26][CH:25]=1)[CH2:29][CH2:30][CH2:31][CH2:32][CH3:33]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 153765802,5-Bishydroxymethyl-4'-hexyloxybiphenyl

Product 1

HCID 153765812-(4'-Hexyloxyphenyl)terephthalaldehyde

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-60 °C

Procedure

Oxalyl chloride (8.4 g, 5.7 ml, 66 mmol) were added to 70 ml of dichloromethane and the mixture was cooled to −60° C. A solution of DMSO (10.2 g, 9.3 ml, 131 mmol) in 30 ml dichloromethane was added dropwise over a period of 10 minutes. The mixture was stirred further for 5 minutes. A solution of 2,5-bis(hydroxymethyl)-4′-hexyloxybiphenyl (10 g, 32 mmol) (cf. D1) in 70 ml of dichloromethane was then added dropwise over a period of 15 minutes (the reaction solution became turbid). It was stirred further for 10 minutes and triethylamine (15.9 g, 21.8 ml, 157 mmol) was subsequently added dropwise. During this addition, the reaction solution became yellow and a precipitate formed. The acetone/dry ice bath was removed and the mixture was stirred for 2 hours at RT. This resulted in a light-colored solid floating on the yellow liquid phase. The mixture was admixed with 150 ml of water, stirred further for 10 minutes (the solid went into solution), the organic phase was separated off, the aqueous phase was extracted twice with dichloromethane, the combined organic phases were subsequently washed three times with water, dried over Na2SO4, filtered and subsequently evaporated to dryness on a rotary evaporator. The yellow oil crystallized after some time at RT; it was subsequently recrystallized from hexane. It took a relatively long time for the product to become solid: pale beige, microcrystalline powder, 5.67 g (57%), purity about 98%. Melting point: 44.5-45.5° C.

Workup

  1. stirringIt was stirred further for 10 minutes
  2. additionDuring this addition
  3. customa precipitate formed
  4. customThe acetone/dry ice bath was removed
  5. stirringthe mixture was stirred for 2 hours at RT
  6. customThis resulted in a light-colored solid
  7. stirringstirred further for 10 minutes (the solid
  8. customwas separated off
  9. extractionthe aqueous phase was extracted twice with dichloromethane
  10. washthe combined organic phases were subsequently washed three times with water
  11. dry with materialdried over Na2SO4
  12. filtrationfiltered
  13. customsubsequently evaporated to dryness on a rotary evaporator
  14. customThe yellow oil crystallized after some time at RT
  15. customit was subsequently recrystallized from hexane

Sources & evidence

ORD record
ord-9f31f9f7b62341a88379f32fb7e6aa10
Source dataset
uspto-grants-2002_10
Patent number
US06458909B1

Reaction notes

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