Ethylene Glycol → HCID 86737810, compound

HRID 1680625Notes

Reaction equation

HRID 1680625 reaction equation
C[O:2][C:3](=O)[CH2:4][C:5](=[O:12])[CH2:6][CH2:7][C:8]([O:10]C)=[O:9].[CH2:14]([OH:17])[CH2:15][OH:16].O.[OH-].[K+]>C1C=CC=CC=1.C(O)C.C1(C)C=CC(S(O)(=O)=O)=CC=1>[CH2:14]1[O:17][C:3]([OH:2])([CH2:4][C:5](=[O:12])[CH2:6][CH2:7][C:8]([OH:10])=[O:9])[O:16][CH2:15]1

Participants

8

Reactant 4

HCID 174Ethylene GlycolHCID 962Water2×HCID 14797Potassium HydroxideHCID 79561Dimethyl 3-oxoadipate

Product 1

HCID 86737810HCID 86737810, compoundYield 100.3%

Reagents, catalysts & solvents 3

HCID 6101p-Toluenesulfonic acidCatalystHCID 241BenzeneSolventHCID 702EthanolSolvent

Procedure

A solution of 4.00 g (21 mmol) of 3-ketohexanedioic acid dimethyl ester [B. J. Whitlock and H. W. Whitlock, J. Org. Chem., 39:3144 (1974)] in 100 mL of benzene was refluxed in the presence of 14.5 g (230 mmol) of ethylene glycol and 100 mg of p-toluene-sulfonic acid while water was azeotropically removed in a Dean-Stark trap. After 2.5 h, the mixture was cooled and washed with equal volumes of saturated sodium bicarbonate solution and water. The benzene layer was dried (MgSO4) and reduced to dryness to leave a clear oil; IR (neat) 1740 cm-1, NMR (CDCl3) δ2.30 (A2B2 multiplet, 4), 2.60 (s,2), 3.65 (s,6), and 3.95 (s,4). The oily ketal was immediately hydrolyzed under reflux for 1.5 h in a solution of 4.4 g of 86% KOH in 50 mL of 95% ethanol. After cooling, the slight precipitate formed was dissolved by adding a small amount of water. Sufficient cation exchange resin AG50W-X8 (H+) was added to neutralize the base (pH~6.5) and removal of the resin afforded a filtrate which was reduced to dryness to leave 4.3 g (99%) of 3-ketohexanedioic acid ethylene ketal as a yellowish oil which yielded a very hygroscopic solid after trituration with acetone; IR 1720 cm-1 (broad); NMR δ(D2O) 2.20 (A2B2 multiplet, 4), 2.60 (s,2), and 4.0 (s,4). This compound was not further characterized and used as such in the following step.

Workup

  1. customwas azeotropically removed in a Dean-Stark trap
  2. temperaturethe mixture was cooled
  3. washwashed with equal volumes of saturated sodium bicarbonate solution and water
  4. dry with materialThe benzene layer was dried (MgSO4)
  5. customto leave a clear oil
  6. temperatureAfter cooling
  7. customthe slight precipitate formed
  8. dissolutionwas dissolved
  9. addition(H+) was added
  10. customthe base (pH~6.5) and removal of the resin
  11. customafforded a filtrate which

Sources & evidence

ORD record
ord-d7fe94eadb0d468d803936ae5327abfc
Source dataset
uspto-grants-1981_06
Patent number
US04275057

Reaction notes

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