Acetic Acid → HCID 19822407, compound

HRID 1030254Notes

Reaction equation

HRID 1030254 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].C[C:13]([CH3:16])([O-:15])C.[K+].[C:18]([OH:21])(=O)[CH3:19].CN1CC[CH2:25][C:24]1=[O:28]>>[CH2:10]([O:9][C:1]([C:2]1([C:3]([O:5][CH2:6][CH3:7])=[O:4])[CH2:16][CH2:13][O:15][CH2:19][CH2:18][O:21][CH2:25][CH2:24][O:28][CH2:7][CH2:6][O:5][CH2:3][CH2:2]1)=[O:8])[CH3:11]

Participants

5

Reactant 4

HCID 176Acetic AcidHCID 7761Diethyl MalonateHCID 13387N-methyl-2-pyrrolidone2×HCID 23665647Potassium tert-butoxide

Product 1

HCID 19822407HCID 19822407, compound

Conditions

Temperature
60 °C

Procedure

In an inert gas atmosphere and at room temperature, diethyl malonate (6.9 ml) is added dropwise to a stirred solution of potassium tert-butoxide (6.8 g) in dry N-methyl pyrrolidone (63 ml). After warming for 1 hour at 60° C. and cooling at room temperature, a solution of pentaethylenene glycol di-p-toluenesulphonate (25 g) n N-methyl pyrrolidone (25 ml) is dropwise added to the mixture over a period of 4 hrs, that is then heated at 80° C. for 18 hrs. After cooling at room temperature, addition of acetic acid (1ml) and removal of the solvent in vacuum, the residue is purified by chromatography on SiO2 (diethylether/hexane 9:1). The obtained diethyl 2-(14-p-toluenesulphonyloxy-3,6,9,12-tetraoxatetradecane-1-yl)-malonate (4 g) is treated again with potassium tert-butoxide (1.26 g) in dry N-methyl pyrrolidone (50 ml, total volume) using the same procedure above described. A pale yellow oil of 4,4-bis-ethoxycarbonyl-1,7,10,13-tetraoxacyclopentadecane [0.68 g; N.M.R.(CDCl3): 1.23; 2.30; 3.50-3.71; 4.20] is obtained that is treated with aqueous lithium hydroxide (0.2 g) to give 1,7,10,13-tetraoxacyclopentadecane-4,4-dicarboxylic acid (0.32 g; m.p. 107°-111° C.).

Workup

  1. temperaturecooling at room temperature
  2. temperaturethat is then heated at 80° C. for 18 hrs
  3. temperatureAfter cooling at room temperature
  4. customthe residue is purified by chromatography on SiO2 (diethylether/hexane 9:1)
  5. additionThe obtained diethyl 2-(14-p-toluenesulphonyloxy-3,6,9,12-tetraoxatetradecane-1-yl)-malonate (4 g) is treated again with potassium tert-butoxide (1.26 g) in dry N-methyl pyrrolidone (50 ml, total volume)

Sources & evidence

ORD record
ord-137fc4084b314ad4a3df98684af04f28
Source dataset
uspto-grants-1992_04
Patent number
US05104895

Reaction notes

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