4-Ethylbenzenesulfonic acid → 2,8-Dimethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

HRID 1247541

反応式

HRID 1247541 の反応式
C(O)CC(O)C.C(C1C=CC(S(O)(=O)=O)=CC=1)C.[CH2:19]([O:21][C:22]([O:29][CH2:30][CH3:31])([O:26][CH2:27][CH3:28])[O:23][CH2:24][CH3:25])[CH3:20]>C1(C)C=CC=CC=1>[CH3:31][CH:30]1[CH2:28][CH2:27][O:26][C:22]2([O:23][CH2:24][CH2:25][CH:19]([CH3:20])[O:21]2)[O:29]1

参加物

5

反応物 3

HCID 74024-Ethylbenzenesulfonic acidHCID 78961,3-ButanediolHCID 66213Tetraethyl orthocarbonate

生成物 1

HCID 219085142,8-Dimethyl-1,5,7,11-tetraoxaspiro[5.5]undecane

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

See also U.S. Pat. No. 5,808,108. In a 500 mL RB flask equipped with a reflux condenser, a stirrer and a Dean Stark trap, 1,3-butanediol (20.0 g, 0.22 mol), and toluene (350 mL) were added. After placing under nitrogen the resulting solution was heated to reflux for two h to remove water from the mixture. The solution was cooled to RT and 4-ethylbenzenesulfonic acid (0.35 g) and tetraethylorthocarbonate (21.3 g, 0.11 mol) were added. The solution was heated to reflux and the azeotropic mixture collected; The reaction was refluxed until the temperature of the distillated reached 110° C. (boiling point of pure toluene). The collected azeotropic mixture was measured and weighed and then poured into brine and the organic phase was separated, which indicated ˜22 mL of ethanol was collected. TLC analysis indicated that the reaction was complete by the disappearance of the diol and the appearance of the product at Rf=0.59 (silica gel, EtOAc/hexanes (3/2). The reaction was cooled to RT and triethylamine (2.5 mL) added. The toluene was removed at reduced pressure (rotovap) and the resulting liquid dried under vacuum. Vacuum distillation afforded four fractions of the desired product as a water white clear liquid boiling, bp: 70–75° C. at 40 Pa. Fractions 1 and 2 were slightly impure and were combined to give 5.715 g and fractions 3 and 4 were very pure and were combined to give 10.046 g. Overall yield: 15.761 g (75.66%). 13C NMR indicated the product to be a mixture of isomers.

後処理

  1. customIn a 500 mL RB flask equipped with a reflux condenser, a stirrer
  2. temperaturewas heated
  3. temperatureto reflux for two h
  4. customto remove water from the mixture
  5. temperatureThe solution was heated
  6. temperatureto reflux
  7. customthe azeotropic mixture collected
  8. temperatureThe reaction was refluxed until the temperature of the
  9. customdistillated reached 110° C.
  10. additionpoured into brine
  11. customthe organic phase was separated
  12. customwas collected
  13. temperatureThe reaction was cooled to RT
  14. additiontriethylamine (2.5 mL) added
  15. customThe toluene was removed at reduced pressure (rotovap)
  16. customthe resulting liquid dried under vacuum
  17. distillationVacuum distillation

出典と根拠

ORDレコード
ord-84e278e65dbf44ee93c60cd68f0e49c3
出典データセット
uspto-grants-2006_10
特許番号
US07129290B2

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