Aluminium lithium hydride → HCID 69305970, compound

To a flame dried 1 L RBF containing a stir bar, lithium aluminum hydride (2.166 g, 57.0 mmol) was added. The RBF was placed in an ice bath and the reaction was capped with a septum containing a nitrogen gas line and an out-vent. Dry ether (10 mL) was added through the septum while the mixture was stirring. Methyl 3,5-dinonyloxybenzoate (20 g, 47.5 mmol) was added and dissolved in 60 mL dry ether, drop-wise through the septum. After this addition, the reaction mixture became clumpy and would not stir so about 150 mL more of dry ether was added to dilute the mixture. After 1 hour, the nitrogen line and the out-vent were removed and the septum was changed. The mixture was stirred overnight. The RBF was then placed in an ice bath. Distilled water (150 mL) was added drop-wise through the septum until the mixture turned a white-grey color. The reaction mixture was allowed to stir at room temperature for 10 minutes and then 100 mL 1M hydrochloric acid was added until the pH reached less than 2. The mixture was then extracted with ether 4 time (200 mL) and the ether layers were combined and then washed with 200 mL distilled water, then with 200 mL aqueous sodium carbonate (5%), then with 200 mL distilled water, then with 200 mL brine, and then dried with magnesium sulfate and gravity filtered. The solvent was removed under reduced pressure, producing a waxy white solid. The solid was air dried overnight. The solid was purified by silica gel flash chromatography using a solvent system of 1 L 20% ether and hexanes and 2 L 40% ether and hexanes. The product was collected and the solvent was removed under reduced pressure. The resulting oil was covered with the septum and allowed to stand over night where it is partially solidified. There was a 13.22 g yield or a 71.8% yield of the derivative. The NMR characterization data for this derivative is as follows. 1H NMR (300 MHz, CDCl3): 0.88 (t, J=6.3, 6H, CH2CH3), 1.1-1.55 (m, 28H, CH2(CH2)6), 1.76 (p, J=6.6, 4H, OCH2CH2), 3.92 (t, J=7.0, 4H, OCH2CH2), 4.62 (d, J=6.1, 2H, CHCH2CH), 5.29 (s, 1H, CH2OH), 6.63 (t, J=2.2, 1H, ArH), 7.15 (d, J=2.2, 2H, ArH). 13C (75 MHz, CDCl3): 160.54, 143.33, 105.07, 100.54, 68.12, 31.98, 29.65, 29.50, 29.37, 29.35, 26.14, 22.78, 14.21.

1. customTo a flame dried 1 L RBF
2. additioncontaining a stir bar
3. customThe RBF was placed in an ice bath
4. customthe reaction was capped with a septum
5. additioncontaining a nitrogen gas line
6. additionAfter this addition
7. additionwas added
8. additionto dilute the mixture
9. customthe nitrogen line and the out-vent were removed
10. stirringThe mixture was stirred overnight
11. customThe RBF was then placed in an ice bath
12. additionDistilled water (150 mL) was added drop-wise through the septum until the mixture
13. stirringto stir at room temperature for 10 minutes
14. addition100 mL 1M hydrochloric acid was added until the pH
15. extractionThe mixture was then extracted with ether 4 time (200 mL)
16. washwashed with 200 mL
17. distillationdistilled water
18. distillationwith 200 mL aqueous sodium carbonate (5%), then with 200 mL distilled water
19. dry with materialwith 200 mL brine, and then dried with magnesium sulfate and gravity
20. filtrationfiltered
21. customThe solvent was removed under reduced pressure
22. customproducing a waxy white solid
23. customdried overnight
24. customThe solid was purified by silica gel flash chromatography
25. customThe product was collected
26. customthe solvent was removed under reduced pressure
27. waitto stand over night
28. customyield

ORD record

ord-044db7a76baa476db5e306932831dab7

Source dataset

uspto-grants-2008_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07332529B2