Triethylamine → HCID 6455298, compound

HRID 1855775Notes

Reaction equation

HRID 1855775 reaction equation
[CH3:1][C@@H:2]([C@@H:22]([OH:24])[CH3:23])[C@@H:3]1[O:5][C@H:4]1[CH2:6][C@@H:7]1[C@@H:12]([OH:13])[C@@H:11]([OH:14])[C@H:10]([CH2:15]/[C:16](/[CH3:21])=[CH:17]/[C:18]([OH:20])=[O:19])[O:9][CH2:8]1.C(N(CC)CC)C.CCOP(Cl)(OCC)=O>O1CCCC1>[CH3:1][C@@H:2]([CH:22]([OH:24])[CH3:23])[CH:3]1[O:5][CH:4]1[CH2:6][C@H:7]1[C@H:12]([OH:13])[C@H:11]([OH:14])[C@H:10]([CH2:15]/[C:16](/[CH3:21])=[CH:17]/[C:18]([OH:20])=[O:19])[O:9][CH2:8]1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 13139Diethyl chlorophosphateHCID 10246906monic acid A

Product 1

HCID 6455298HCID 6455298, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of monic acid (1.032 g; 3 mM) and triethylamine (0.420 ml; 3 mM) in dry tetrahydrofuran (50 ml) was added diethyl phosphorochloride (0.518 g; 3 mM), at room temperature under an argon atmosphere. The mixture was stirred at room temperature for three hours and precipitated triethylamine hydrochloride was removed by filtration. The solid was washed with tetrahydrofuran and to the combined filtrate and washings was added the sodium salt of N-acetyl-β-mercaptoethylamine (0.423 g; 3 mM). The resulting suspension was stirred at room temperature for three days and then filtered through a celite plug. The solvent was removed at reduced pressure and the residue partitioned between ethyl acetate and sodium bicarbonate solution. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulphate. Removal of the solvent at reduced pressure gave the crude thiol ester as a pale yellow oil. This oil was purified by column chromatography over silica gel (Type 60; 50 g). Elution with 5% methanol/chloroform afforded the pure 2-acetamidoethanethiol ester of monic acid A as a colourless oil, (0.310 g; 23%). [α]D20 -7.04° (c, 1.0 CHCl3)νmax (CHBr3) 3350, 1660 and 1625 cm-1, λmax (EtOH) 240 nm (εm 9,630), 267 nm (εm 8,390), δH (CDCl3) 6.67 (1H, broad resonance, NH); 6.02 (1H, s, CH=C); 2.17 (3H, s, CH3 --15); 1.94 (3H, s, COCH3); 1.19 (3H, d, J=6.0 Hz, CH3 --14); 0.92 (3H, d, J=6.5 Hz, CH3 --17), δc (CDCl3), 189.3, 171.0, 155.7, 124.2, 75.0, 71.1, 70.4, 68.9, 65.5, 61.1, 55.7, 42.8, 39.9, 31.7, 28.5, 23.1, 20.8, 20.3, and 12.6. m/e 327.1799 (3% C17H27O6 requires 327.1808).

Workup

  1. customat room temperature
  2. customprecipitated triethylamine hydrochloride
  3. customwas removed by filtration
  4. washThe solid was washed with tetrahydrofuran and to the combined filtrate and washings
  5. additionwas added the sodium salt of N-acetyl-β-mercaptoethylamine (0.423 g; 3 mM)
  6. stirringThe resulting suspension was stirred at room temperature for three days
  7. filtrationfiltered through a celite plug
  8. customThe solvent was removed at reduced pressure
  9. customthe residue partitioned between ethyl acetate and sodium bicarbonate solution
  10. washThe organic layer was washed with saturated brine
  11. dry with materialdried over anhydrous magnesium sulphate
  12. customRemoval of the solvent at reduced pressure
  13. customgave the crude thiol ester as a pale yellow oil
  14. customThis oil was purified by column chromatography over silica gel (Type 60; 50 g)
  15. washElution with 5% methanol/chloroform

Sources & evidence

ORD record
ord-3d6939893832499fa5fcf5fce5ae886d
Source dataset
uspto-grants-1980_08
Patent number
US04216223

Reaction notes

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