Diethyl Ether → HCID 22848979, compound

HRID 326208Notes

Reaction equation

HRID 326208 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].CON(C)[C:10](=[O:29])[C@H:11]([CH2:20][C:21]1[CH:26]=[CH:25][C:24]([O:27]C)=[CH:23][CH:22]=1)[NH:12][C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14].OS([O-])(=O)=O.[K+].[CH2:37]([O:39]CC)C>>[C:16]([O:15][C:13]([NH:12][C@H:11]([CH:10]=[O:29])[CH2:20][C:21]1[CH:22]=[CH:23][C:24]([O:27][O:39][CH3:37])=[CH:25][CH:26]=1)=[O:14])([CH3:17])([CH3:18])[CH3:19]

Participants

5

Reactant 4

HCID 3283Diethyl Ether2×HCID 516920Potassium bisulfateHCID 21226445Aluminium lithium hydrideHCID 22848978HCID 22848978, compound

Product 1

HCID 22848979HCID 22848979, compound

Conditions

Temperature
4 °C

Procedure

To 150 ml of anhydrous ethyl ether was added 1.04 g (27.37) mmols) of lithium aluminum hydride and the suspension was gently refluxed for 30 minutes. Upon cooling to 4° C., the reflux condenser was replaced by a pressure equalizing dropping funnel containing 7.4 g (21.9 mmols) of N-(t-butoxycarbonyl)-O-methyl-L-tyrosine N-methoxy-N-methylamide dissolved in 100 ml of anhydrous ethyl ether. The contents of the funnel were added over one hour. The reaction mix was allowed to react for an additional two hours. At the end of this time a cold solution of KHSO4 (5.433 g in 230 ml of H2O) was added to the reaction vessel. The layers were separated and the aqueous layer was extracted three times with 150 mls of ether each time. The ether layers were combined and worked up as follows. Washed three times with 200 mls of 3N HCl. Washed three times with 200 mls of saturated sodium bicarbonate. Washed three times with 200 mls of brine. Dried over magnesium sulfate, filtered, and concentrated in vacuo. There remained 3.78 g (61.6%) of a white solid with a mp of 69°-72° C.: Rf=0.65 in 50/50 ethyl acetate/hexane; IR (cm-1, KBr) 3360, 2840, 1740, 1695, 1530, 1255, 1180: MS m/e 279.3 (M+); 1 H (CDCl3), 300 MHz) δ9.63 (s, 1H), δ7.08 (d, 2H, J=8.5 Hz) δ6.84 (d, 2H, J=8.5), δ5.05 (br s, 1H), δ4.40 (m, 1H), δ3.79 (s, 3H), δ3.06 (d, 2H, J=6.50), δ1.44 (s, 9H); 13C NMR (CDCl3, 75.47 MHz) δ200, 158.79, 130.28, 127.69, 114.27, 61.05, 55.29, 34.70, 28.26; Anal. Calcd: C, 64.51; H, 7.52; N, 5.01. Found: C,64.60, H, 7.86; N, 4.93.

Workup

  1. temperaturethe suspension was gently refluxed for 30 minutes
  2. additionThe contents of the funnel were added over one hour
  3. additionThe reaction mix
  4. customto react for an additional two hours
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted three times with 150 mls of ether each time
  7. washWashed three times with 200 mls of 3N HCl
  8. washWashed three times with 200 mls of saturated sodium bicarbonate
  9. washWashed three times with 200 mls of brine
  10. dry with materialDried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-18c8909db2ee4768b612ef5931ea2568
Source dataset
uspto-grants-1993_12
Patent number
US05268164

Reaction notes

Loading…