Toluene → Nonadeca-2,13-diene

HRID 481156

반응식

HRID 481156 반응식
COC([C:5]1([C:10](OC)=O)[CH2:9][CH:8]=[CH:7][CH2:6]1)=O.[C:14]1([CH3:20])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(OC(O[CH2:32][CH3:33])(OCC)OCC)C>C(O)C.O>[CH3:9][CH:5]=[CH:6][CH2:7][CH2:32][CH2:33][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:14][CH:20]=[CH:6][CH2:7][CH2:8][CH2:9][CH2:5][CH3:10]

참가 물질

6

반응물 3

HCID 1140TolueneHCID 66213Tetraethyl orthocarbonateHCID 699253Dimethyl 3-cyclopentene-1,1-dicarboxylate

생성물 1

HCID 86584272Nonadeca-2,13-diene수율 62%

시약·촉매·용매 2

HCID 702Ethanol용매2회HCID 962Water용매

실험 절차

To a three-necked round-bottomed flask, equipped with a Dean-Stark trap (20 mL), a reflux condenser, a thermometer and a magnetic stir bar, was placed diol 1 (14.8 g, 115.5 mmol) and 370 mL of toluene under an atmosphere of N2. The mixture was brought to reflux and maintained at reflux temperature for 2 hours to azeotropically remove any moisture. About 100 mL (5×20 mL) of azeotropic mixture was collected in the Dean-Stark trap. The mixture was then allowed to slowly cool to room temperature and 0.2 g of anhydrous para-toluenesulfonic acid (PTSA) was added, followed by dropwise addition of tetraethylorthocarbonate (TEOC, 4563-91-2, 99.1%, 12.2 mL, 57.8 mmol). The resulting mixture was brought to reflux to azeotropically remove ethanol generated during this reaction. The azeotropic mixture was shaken with sale water to determine the amount (volume) of ethanol collected. After a total of 140 mL of azeotropic mixture (12.5 mL of ethanol) was collected, the reaction mixture was allowed to reflux for an additional 2 hours and then allowed to stir at 102° C. overnight. The reaction mixture was allowed to slowly cool to room temperature and then neutralized by the addition of 1 mL of triethylamine. The resulting mixture was allowed to stir at room temperature for an additional 30 min, and was stripped off solvents to give an off white solid. The crude material was then purified by flash chromatography (silica gel, CH2Cl2/hexanes 2/1 v/v) or by recrystallization from refluxing toluene. The desired product 7,9,17,18-tetroaxatrispiro[4.2.2.4.2.2]nonadeca-2,13-diene (DCP 3) was obtained as white crystals in 62% yield. Mp (DSC) 174.53° C.; 1H-NMR (CDCl3, 300 MHz) δ 5.61 (s, 2H), 3.82 (s, 4H), 2.29 (s, 4H); 13C-NMR (CDCl3, 300 MHz) δ 28.53, 114.14, 71.07, 39.79; FT-IR (CH2Cl2) (cm−1) 3052, 2947, 2928, 2880, 2842, 1614, 1481, 1267, 1210, 1171, 1014, 990, 738, 671; Anal. Calcd for C15H20O4: C, 68.16; H, 763; Found: C, 68.18; H, 7.81.

후처리

  1. customTo a three-necked round-bottomed flask, equipped with a Dean-Stark trap (20 mL), a reflux condenser
  2. temperatureto reflux
  3. temperaturemaintained
  4. temperatureat reflux temperature for 2 hours
  5. customto azeotropically remove any moisture
  6. customAbout 100 mL (5×20 mL) of azeotropic mixture was collected in the Dean-Stark trap
  7. addition0.2 g of anhydrous para-toluenesulfonic acid (PTSA) was added
  8. customgenerated during this reaction
  9. customcollected
  10. customAfter a total of 140 mL of azeotropic mixture (12.5 mL of ethanol) was collected
  11. temperatureto reflux for an additional 2 hours
  12. temperatureto slowly cool to room temperature
  13. additionneutralized by the addition of 1 mL of triethylamine
  14. stirringto stir at room temperature for an additional 30 min
  15. customto give an off white solid
  16. customThe crude material was then purified by flash chromatography (silica gel, CH2Cl2/hexanes 2/1 v/v) or by recrystallization
  17. temperaturefrom refluxing toluene

출처 및 근거

ORD 기록
ord-23596f0118e54798ac0826c70b371510
출처 데이터셋
uspto-grants-2003_11
특허 번호
US06653486B2

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