Water → HCID 68008844, compound

HRID 535154Notes

Reaction equation

HRID 535154 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C([O:9][C:10](=O)[CH2:11][CH2:12][C:13]1([CH2:26][CH2:27][C:28]2([CH2:41][CH2:42][C:43](OCC)=[O:44])[C:40]3[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=3[C:34]3[C:29]2=[CH:30][CH:31]=[CH:32][CH:33]=3)[C:25]2[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=2[C:19]2[C:14]1=[CH:15][CH:16]=[CH:17][CH:18]=2)C.O.[OH-].[Na+]>CCOCC.C(OCC)(=O)C>[OH:9][CH2:10][CH2:11][CH2:12][C:13]1([CH2:26][CH2:27][C:28]2([CH2:41][CH2:42][CH2:43][OH:44])[C:29]3[CH:30]=[CH:31][CH:32]=[CH:33][C:34]=3[C:35]3[C:40]2=[CH:39][CH:38]=[CH:37][CH:36]=3)[C:25]2[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=2[C:19]2[C:14]1=[CH:15][CH:16]=[CH:17][CH:18]=2

Participants

7

Reactant 4

HCID 962Water2×HCID 14798Sodium HydroxideHCID 21226445Aluminium lithium hydride2×HCID 68008874HCID 68008874, compound

Product 1

HCID 68008844HCID 68008844, compoundYield 91.8%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A 2-neck 1-Liter round bottom flask was equipped with a condenser, a magnetic stir bar and an addition funnel. The flask was charged with 100 mL of anhydrous ether. Lithium aluminum hydride (2.30 g) was then carefully added to the flask. 3-(9-{2-[9-(2-Ethoxycarbonyl-ethyl)-9H-fluoren-9-yl]-ethyl}-9H-fluoren-9-yl)-propionic acid ethyl ester (11.3 g, 20.2 mmol) was suspended in 100 mL of anhydrous ether and added to the addition funnel. The suspension of diester was then added dropwise to the rapidly stirred lithium aluminum hydride suspension. The addition funnel was rinsed with additional portions of anhydrous ether to rinse all of the diester into the reaction flask. The reaction mixture was then refluxed for several hours and then left at ambient temperature overnight. The rapidly stirred reaction mixture was carefully treated by the dropwise addition of water (2.3 mL), followed by 15% NaOH solution (2.3 mL), and finally more water (6.9 mL). After stirring for 2 h, the ether solution was filtered from the aluminum salts. The salts were rinsed with additional portions of diethyl ether. The combined organic portions were concentrated under reduced pressure to give a white solid. The white solid was dissolved in 100 mL of ethyl acetate, washed with 1N HCl solution, water, and brine. The organic layer was dried over Na2SO4, filtered, and concentrated under reduced pressure. The resulting white solid was crystallized from hot toluene to give the title compound (2-d) (8.8 g) as white crystals. 1H NMR (CDCl3, 500 MHz) δ 7.73 (d, J=7.5 Hz, 4H), 7.36 (m, 4H), 7.28 (m, 4H), 7.00 (d, J=7.5 Hz, 4H), 3.15 (t, J=6.7 Hz, 4H), 1.65 (m, 4H), 1.24 (s, 4H), 0.64 (m, 4H).

Workup

  1. customA 2-neck 1-Liter round bottom flask was equipped with a condenser, a magnetic stir bar and an addition funnel
  2. additionadded to the addition funnel
  3. washThe addition funnel was rinsed with additional portions of anhydrous ether
  4. washto rinse all of the diester into the reaction flask
  5. temperatureThe reaction mixture was then refluxed for several hours
  6. customThe rapidly stirred reaction mixture
  7. filtrationthe ether solution was filtered from the aluminum salts
  8. washThe salts were rinsed with additional portions of diethyl ether
  9. concentrationThe combined organic portions were concentrated under reduced pressure
  10. customto give a white solid
  11. washwashed with 1N HCl solution, water, and brine
  12. dry with materialThe organic layer was dried over Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated under reduced pressure
  15. customThe resulting white solid was crystallized from hot toluene

Sources & evidence

ORD record
ord-7dd5f9f75938410fa0bac9458f56292e
Source dataset
uspto-grants-2014_10
Patent number
US08854730B2

Reaction notes

Loading…