1,4-Dibromobutane → 1,1-Dimethylethyl 4-{4-[(4-bromobutyl)oxy]butyl}benzoate

HRID 1675669Notes

Reaction equation

HRID 1675669 reaction equation
[OH:1][CH2:2][CH2:3][CH2:4][CH2:5][C:6]1[CH:18]=[CH:17][C:9]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])=[CH:8][CH:7]=1.[Br:19][CH2:20][CH2:21][CH2:22][CH2:23]Br.[OH-].[Na+]>S(=O)(=O)(O)[O-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[Br:19][CH2:20][CH2:21][CH2:22][CH2:23][O:1][CH2:2][CH2:3][CH2:4][CH2:5][C:6]1[CH:18]=[CH:17][C:9]([C:10]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:11])=[CH:8][CH:7]=1

Participants

6

Reactant 3

HCID 80561,4-DibromobutaneHCID 14798Sodium HydroxideHCID 10422229Benzoic acid, 4-(4-hydroxybutyl)-, 1,1-dimethylethyl ester2×

Product 1

HCID 580247741,1-Dimethylethyl 4-{4-[(4-bromobutyl)oxy]butyl}benzoate

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 962WaterSolvent

Procedure

To 1,1-dimethylethyl 4-(4-hydroxybutyl)benzoate (0.85 g, 3.4 mmol, e.g. which can be as prepared in Intermediate 23) was added 1,4-dibromobutane (1.22 ml, 10.2 mmol, 3 equivalents, commercially available e.g. from Aldrich), tetra-n-butylammonium bisulphate (0.034 g, 0.1 mmol, 0.03 equivalents) and aqueous sodium hydroxide solution (50% w/v NaOH, 5 ml). The resultant biphasic mixture was stirred at room temperature over the weekend (this can be e.g. about 64 hours), diluted with water (20 ml) and extracted with diethyl ether (50 ml). The organic extract washed with water (20 ml), dried (Na2SO4) and evaporated to dryness. The residue was purified by passing through a 50 g silica SPE cartridge eluting with cyclohexane (100 ml), 9:1 cyclochexane:ethyl acetate (100 ml), 4:1 cyclohexane:ethyl acetate (200 ml) and 1:1 cyclohexane:ethyl acetate (100 ml). The 4:1 cyclohexane:ethyl acetate fraction containing the product was evaporated to give the title compound (1.05 g). LCMS showed TRET=4.14 min with: MH+=385 (trace), and [MH]++18 adduct=402/404 (Bromine isotope pattern).

Workup

  1. custome.g. about 64 hours
  2. extractionextracted with diethyl ether (50 ml)
  3. extractionThe organic extract
  4. washwashed with water (20 ml)
  5. dry with materialdried (Na2SO4)
  6. customevaporated to dryness
  7. customThe residue was purified
  8. washeluting with cyclohexane (100 ml), 9:1 cyclochexane
  9. additionThe 4:1 cyclohexane:ethyl acetate fraction containing the product
  10. customwas evaporated

Sources & evidence

ORD record
ord-9bfdf8894ebe480a9e5b4cab8ce862be
Source dataset
uspto-grants-2011_08
Patent number
US08003663B2

Reaction notes

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