Ethylene Glycol → Diethyl 1,4-dioxaspiro[4.5]decane-8,8-dicarboxylate

HRID 75719Notes

Reaction equation

HRID 75719 reaction equation
[O:1]=[C:2]1[CH2:7][CH2:6][C:5]([C:13]([O:15][CH2:16][CH3:17])=[O:14])([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][CH2:3]1.[CH2:18](O)[CH2:19][OH:20].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>C1C=CC=CC=1.CCOCC>[O:20]1[C:2]2([CH2:3][CH2:4][C:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])([C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH2:6][CH2:7]2)[O:1][CH2:18][CH2:19]1

Participants

6

Reactant 3

HCID 174Ethylene GlycolHCID 521998p-Toluenesulfonic acid monohydrateHCID 27760711,1-Diethyl 4-oxocyclohexane-1,1-dicarboxylate

Product 1

HCID 67170753Diethyl 1,4-dioxaspiro[4.5]decane-8,8-dicarboxylateYield 100%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Procedure

The procedure described in Pearson at al., J. Org. Chem., 1997, 62, 5284 was followed with a minor modification. A mixture of diethyl 4-oxocyclohexane-1,1-dicarboxylate, Intermediate 2, (120.6 g, 463 mmol), ethane-1,2-diol (110 mL, 1973 mmol), and para-toluene sulfonic acid mono hydrate (1.0 g, 5.26 mmol) in Benzene (250 mL) was stirred at room temp under N2 for 2 days. The mixture was diluted with Et2O (1 L) and washed with water (300 mL×3), sat'd NaHCO3 (100 mL) and then with brine, dried (MgSO4), and concentrated to dryness to provide the title compound (132.7 g, 463 mmol, 100% yield) as an amber oil HPLC: 2.38 min (AP 70% at 220 nm). LCMS: m/z 287 (M+H). 1H NMR (500 MHz, CDCl3) δ ppm 1.17 (6H, t, J=7.2 Hz, 9,12-CH3), 1.60 (4H, t, J=6.4 Hz, 2,6-CH2), 2.09 (4H, t, J=6.4 Hz, 3,5-CH2), 3.86 (4H, s, 13,14-OCH2), 4.11 (4H, q, J=7.2 Hz, 8,11-OCH2). 13C NMR (126 MHz, CDCl3) δ ppm 14.1 (9,12-CH3), 29.0 (3,5-CH2), 31.6 (2,6-CH2), 53.9 (4-C), 61.3 (8,11-OCH2), 64.3 (13,14-OCH2), 107.7 (1-OCO), 171.2 (7,10-OC═O).

Workup

  1. washwashed with water (300 mL×3), sat'd NaHCO3 (100 mL)
  2. dry with materialwith brine, dried (MgSO4)
  3. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-9d44d9a504fe4a0badb77adaa7c8c8f7
Source dataset
uspto-grants-2014_09
Patent number
US08835411B2

Reaction notes

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