Triethylamine → HCID 6455298, compound

HRID 2050175Notes

Reaction equation

HRID 2050175 reaction equation
P(Cl)(OCC)(OCC)=O.[CH3:10][C@@H:11]([CH:31]([OH:33])[CH3:32])[CH:12]1[O:14][CH:13]1[CH2:15][C@H:16]1[C@H:21]([OH:22])[C@H:20]([OH:23])[C@H:19]([CH2:24]/[C:25](/[CH3:30])=[CH:26]/[C:27]([OH:29])=[O:28])[O:18][CH2:17]1.C(N(CC)CC)C.[Cl-].[CH3:42][O:43][C:44]([CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][NH3+:54])=[O:45]>O1CCCC1>[CH3:42][O:43][C:44]([CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][NH-:54])=[O:45].[CH3:10][C@@H:11]([CH:31]([OH:33])[CH3:32])[CH:12]1[O:14][CH:13]1[CH2:15][C@H:16]1[C@H:21]([OH:22])[C@H:20]([OH:23])[C@H:19]([CH2:24]/[C:25](/[CH3:30])=[CH:26]/[C:27]([OH:29])=[O:28])[O:18][CH2:17]1

Participants

7

Reactant 4

HCID 8471Triethylamine2×HCID 13139Diethyl chlorophosphateHCID 6455298HCID 6455298, compoundHCID 10656735HCID 10656735, compound

Product 2

HCID 6455298HCID 6455298, compoundHCID 131711747HCID 131711747, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Diethyl chlorophosphate (0.507 g; 2.94 mM) was added to a solution of monic acid A (0.982 g; 2.94 mM) and triethylamine (0.412 ml; 2.94 mM) in dry tetrahydrofuran (50 ml). This solution was stirred at room temperature for three hours, under a nitrogen atmosphere. A solution of 8-methoxycarbonyloctylammonium chloride (0.65 g; 2.94 mM) and triethylamine (0.412 ml; 2.94 mM) in aqueous tetrahydrofuran (10 ml) was then added and the reaction mixture stirred for a further sixteen hours at room temperature. The solvent was then removed at reduced pressure and the residue partitioned between ethyl acetate and saturated sodium bicarbonate solution. The organic layer was washed with brine, dried over anhydrous magnesium sulphate and the solvent removed to yield the crude amide as a yellow oil. The product was purified by preparative thin layer chromatography on four 20×20×20×0.2 cm silica plates, eluting with 12% methanol/chloroform. The major band afforded the pure 8-methoxycarbonyloctylamide of monic acid A as a colourless oil. (0.610 g; 40%), [α]D20 -0.74° (c, 1.0 CHCl3), λmax (EtOH) 223 nm (εm 14,130); νmax (CHBr3) 3350, 1780, 1660 and 1630 cm-1 ; δH (CDCl3) 5.93 (1H, broad t, (NH), 5.62 (1H, s, CH=C), 3.65 (3H, s, CO2CH3), 2.13 (3H, s, CH3 -15), 1.30 (s, methylene envelope), 1.20 (3H, d, J 6.0 Hz, CH3 -14), 0.92 (3H, d, J 7.0 Hz, CH3 -17); δC (CDCl3) 174.4, 167.6, 150.3, 120.4, 75.1, 70.8, 70.5, 68.9, 65.5, 61.0, 55.7, 51.5, 42.7, 39.8, 39.4, 34.1, 31.8, 29.6, 29.1, 27.0, 24.9, 20.8, 18.7, 12.6, m/e 513 (M+) 482, 366, 269, 227, 188, 172, 156, 11, 83.

Workup

  1. stirringthe reaction mixture stirred for a further sixteen hours at room temperature
  2. customThe solvent was then removed at reduced pressure
  3. customthe residue partitioned between ethyl acetate and saturated sodium bicarbonate solution
  4. washThe organic layer was washed with brine
  5. dry with materialdried over anhydrous magnesium sulphate
  6. customthe solvent removed
  7. customto yield the crude amide as a yellow oil
  8. customThe product was purified by preparative thin layer chromatography on four 20×20×20×0.2 cm silica plates
  9. washeluting with 12% methanol/chloroform

Sources & evidence

ORD record
ord-47221a716cce4a6088841783df08c898
Source dataset
uspto-grants-1980_04
Patent number
US04200635

Reaction notes

Loading…