Tetraethylene Glycol → Thiophene

HRID 981779Notes

Reaction equation

HRID 981779 reaction equation
[CH2:1](O)[CH2:2][O:3][CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][OH:12].[OH-:14].[Na+].[K].Br[CH2:18][C:19]1[CH:23]=[CH:22][S:21][CH:20]=1>O1CCCC1.C(Cl)CCC>[CH2:18]([O:12][CH2:11][CH2:10][O:9][CH2:8][CH2:7][O:6][CH2:5][CH2:4][O:3][CH:2]([OH:14])[CH3:1])[CH2:19][CH2:23][CH3:22].[S:21]1[CH:22]=[CH:23][CH:19]=[CH:20]1

Participants

8

Reactant 4

HCID 8200Tetraethylene GlycolHCID 14798Sodium HydroxideHCID 5207033-(Bromomethyl)thiopheneHCID 5462222Potassium

Product 2

HCID 8030ThiopheneYield 57%HCID 131716797HCID 131716797, compound

Reagents, catalysts & solvents 2

HCID 8005Butyl ChlorideSolventHCID 8028TetrahydrofuranSolvent

Procedure

Butoxyethoxyethoxyethoxyethanol (25.0 g, 0.1 mol) was prepared from tetraethylene glycol, sodium hydroxide and butyl chloride (10:1:1) by a method known in the art and then reacted with potassium metal (3.9 g, 0.1 mol) at room temperature for 1.5 hours in tetrahydrofuran. 3-(Bromomethyl)thiophene (17.7 g, 0.1 mol) was added dropwise, and the mixture stirred under reflux for 24 hours. After cooling and filtration the tetrahydrofuran was removed in vacuo and the residue dissolved in methylene chloride, washed with water and dried with potassium carbonate. The solvent was removed and the crude oil distilled to give 3-butoxyethoxyethoxyethoxyethoxymethyl)thiophene (25.7 g, 57%). B.p. 162°-163° C./0.15 mm Hg. (Found: C, 58.6; H, 8.7; S, 9.5. Calculated for C17H30O5S: C, 58.9; H, 8.7; S, 9.3%); EI m/e Intensity (%): 346 (9, M+), 97 (100, C4H3S.CH2), 57 (75, C4H9); δH(CDCl3): 7.26 (1H, m) 7.20 (1H, m), 7.06 (1H, m), 4.56 (2H, s) 3.65 (16H, m), 3.45 (2H, t), 1.53 (2H, m), 1.34 (2H, m) and 0.91 (3H, t); δC(CDCl3): 13.6, 18.9, 31.4, 68.1, 69.0, 69.8, 70.0, 70.3, 122.5, 125.5, 126.7, 139.1 ppm.

Workup

  1. temperatureunder reflux for 24 hours
  2. temperatureAfter cooling
  3. filtrationfiltration the tetrahydrofuran
  4. customwas removed in vacuo
  5. dissolutionthe residue dissolved in methylene chloride
  6. washwashed with water
  7. dry with materialdried with potassium carbonate
  8. customThe solvent was removed
  9. distillationthe crude oil distilled

Sources & evidence

ORD record
ord-cdc01017319045f89cf35ed4fa14b99a
Source dataset
uspto-grants-1991_02
Patent number
US04992559

Reaction notes

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