Triethylamine → HCID 6455298, compound

HRID 1855774Notes

Reaction equation

HRID 1855774 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.P(Cl)(=O)(OCC)OCC>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 (2.064 g; 6 mM) and triethylamine (0.840 ml; 6 mM) in dry tetrahydrofuran (50 ml) was added diethyl phosphorochloridate (1.035 g; 6 mM), at room temperature under an argon atmosphere. The mixture was stirred at room temperature for three hours and the precipitated triethylamine hydrochloride was removed by filtration. The solid was washed with tetrahydrofuran and to the combined filtrate and washings was added thallium (I) methanethiolate (1.506 g; 6 mM). The resulting suspension was stirred at room temperature for sixteen hours 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 colourless oil. This oil was purified by column chromatography over silica gel (Type 60; 25 g). Elution with 5% methanol/chloroform afforded the pure methanethiol ester of monic acid A as a colourless oil, which crystallised with ether (1.10 g; 49%). M.pt. 74°-75° C. (ether). (Found: C, 58.0; H, 8.1; S, 8.8 C18H30SO6 requires: C, 57.7; H, 8.1; S, 8.6%), [α]D20 -9.25° (c 1.0 CHCl3), λmax (EtOH) 237 nm (εm 12,100), 268 nm (εm 10,300), νmax (CHBr3) 3440, 1660 and 1620 cm-1, δH (CDCl3) 6.01 (1H, s, CH=C); 2.28 (3H, s, --SCH3); 2.17 (3H, s, CH3 --15); 1.20 (3H, d, J=6.5 Hz, CH3 --14); 0.91 (3H, d, J=6.0 Hz, CH3 --17), δc (CDCl3) 190.0, 154.0, 124.4, 75.0, 70.9, 70.4, 68.9, 65.4, 61.1, 55.7, 42.7, 39.7, 31.6, 20.6, 20.1, 12.5, 11.5, m/e 327.1812 (C17H27O6 requires 327.1808; 10%), 227 (20%), 169 (10%), 141 (23%), 111 (100%), no M+.

Workup

  1. customat room temperature
  2. customthe precipitated triethylamine hydrochloride was removed by filtration
  3. washThe solid was washed with tetrahydrofuran and to the combined filtrate and washings
  4. additionwas added thallium (I) methanethiolate (1.506 g; 6 mM)
  5. stirringThe resulting suspension was stirred at room temperature for sixteen hours
  6. filtrationfiltered through a celite plug
  7. customThe solvent was removed at reduced pressure
  8. customthe residue partitioned between ethyl acetate and sodium bicarbonate solution
  9. washThe organic layer was washed with saturated brine
  10. dry with materialdried over anhydrous magnesium sulphate
  11. customRemoval of the solvent at reduced pressure
  12. customgave the crude thiol ester as a colourless oil
  13. customThis oil was purified by column chromatography over silica gel (Type 60; 25 g)
  14. washElution with 5% methanol/chloroform

Sources & evidence

ORD record
ord-7a415acfff044259beda72299d78fb91
Source dataset
uspto-grants-1980_08
Patent number
US04216223

Reaction notes

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