Triethylamine → Methyl 5-(dipropylamino)-4-((2-(1,3-dithiol-2-ylidene)-3-methoxy-3-oxopropanoyl)amino)-5-oxopentanoate

HRID 1737939Notes

Reaction equation

HRID 1737939 reaction equation
[S:1]1[CH:5]=[CH:4][S:3][C:2]1=[C:6]([C:20]([O:22][CH3:23])=[O:21])[C:7]([NH:9][CH:10]([CH2:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])[C:11]([OH:13])=O)=[O:8].C(N(CC)CC)C.C(Cl)(=O)OCC.[CH2:37]([NH:40][CH2:41][CH2:42][CH3:43])[CH2:38][CH3:39]>ClCCl>[CH2:37]([N:40]([CH2:41][CH2:42][CH3:43])[C:11](=[O:13])[CH:10]([NH:9][C:7](=[O:8])[C:6](=[C:2]1[S:1][CH:5]=[CH:4][S:3]1)[C:20]([O:22][CH3:23])=[O:21])[CH2:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])[CH2:38][CH3:39]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 8902DipropylamineHCID 10928Ethyl chloroformateHCID 154321262-((2-(1,3-Dithiol-2-ylidene)-3-methoxy-3-oxopropanoyl)amino)-5-methoxy-5-oxopentanoic acid

Product 1

HCID 15432127Methyl 5-(dipropylamino)-4-((2-(1,3-dithiol-2-ylidene)-3-methoxy-3-oxopropanoyl)amino)-5-oxopentanoateYield 57%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-((2-(1,3-Dithiol-2-ylidene)-3-methoxy-3-oxopropanoyl)amino)-5-methoxy-5-oxopentanoic acid (4) (239 g) was dissolved in dichloromethane (1.5 l), followed by the addition of 70.7 g of triethylamine. To the resulting solution, 71.8 g of ethyl chlorocarbonate were added dropwise at 5-10° C. under stirring over 30 minutes. Subsequent to further stirring at 15-20° C. for 3 hours, di-n-propylamine (70.7 g) was added dropwise at 5-10° C., followed by stirring at room temperature for 12 hours. The solvent was removed under reduced pressure, and ethyl acetate (2 l) was then added to the residue. The resulting precipitate was filtered off. After the ethyl acetate layer was washed with 0.5 N hydrochloric acid and then with water, the solvent was removed under reduced pressure. Diethyl ether (800 ml) was added to the residue and the resulting precipitate was collected by filtration, whereby methyl 5-(dipropylamino)-4-((2-(1,3-dithiol-2-ylidene)-3-methoxy-3-oxopropanoyl)amino)-5-oxopentanoate (5) (113 g, yield: 57%) was obtained as pale yellow crystals.

Workup

  1. stirringSubsequent to further stirring at 15-20° C. for 3 hours
  2. stirringby stirring at room temperature for 12 hours
  3. customThe solvent was removed under reduced pressure, and ethyl acetate (2 l)
  4. additionwas then added to the residue
  5. filtrationThe resulting precipitate was filtered off
  6. washAfter the ethyl acetate layer was washed with 0.5 N hydrochloric acid
  7. customwith water, the solvent was removed under reduced pressure
  8. additionDiethyl ether (800 ml) was added to the residue
  9. filtrationthe resulting precipitate was collected by filtration

Sources & evidence

ORD record
ord-ec450706ddcf45e8a78a5d30044bc27d
Source dataset
uspto-grants-1999_10
Patent number
US05962509

Reaction notes

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