Morpholine → 6-(4-morpholinyl)-3-[3-(trifluoromethyl)phenyl]-1,5(6H)-pyridazindicarboxylic acid diethyl ester

HRID 54645

Reaktionsgleichung

Reaktionsgleichung von HRID 54645
[C:1]([O:5][CH2:6][CH3:7])(=[O:4])[C:2]#[CH:3].[NH:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1.C(N(C(C)C)CC)(C)C.[CH2:23]([O:25][C:26]([NH:28][N:29]=[C:30]([C:34]1[CH:39]=[CH:38][CH:37]=[C:36]([C:40]([F:43])([F:42])[F:41])[CH:35]=1)[CH:31](Cl)Cl)=[O:27])[CH3:24]>C(Cl)Cl>[CH2:23]([O:25][C:26]([N:28]1[CH:3]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)[C:2]([C:1]([O:5][CH2:6][CH3:7])=[O:4])=[CH:31][C:30]([C:34]2[CH:39]=[CH:38][CH:37]=[C:36]([C:40]([F:43])([F:42])[F:41])[CH:35]=2)=[N:29]1)=[O:27])[CH3:24]

Komponenten

6

Edukt 4

HCID 8083MorpholineHCID 12182Ethyl propiolateHCID 81531DiisopropylethylamineHCID 53937192[2,2-Dichloro-1-[3-(trifluoromethyl)phenyl]ethylidene]hydrazinecarboxylic acid ethyl ester

Produkt 1

HCID 117980206-(4-morpholinyl)-3-[3-(trifluoromethyl)phenyl]-1,5(6H)-pyridazindicarboxylic acid diethyl esterAusbeute 55 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

Ethyl propiolate (3.43 g, 0.035 mole) was stirred under N2 in methylene chloride (300 mL) at RT while morpholine (3.05 g, 0.035 mole) was added dropwise over 15 min. The mixture was then refluxed for 30 min. and then cooled to room temperature (RT). Diisopropylethylamine (5.65 g, 0.0437 mole) was then added to the mixture followed by the addition of [2,2-dichloro-1-[3-(trifluoromethyl)phenyl]ethylidene]hydrazinecarboxylic acid ethyl ester (10 g, 0.029 mole) which was added dropwise as a solution in methylene chloride (60 mL) over 30 min. The mixture was then refluxed for 18 h, cooled, and partitioned 2 times with water. The organic layer was dried (MgSO4), filtered and evaporated in vacuo to give a crude solid. This solid was recrystallized from cyclohexane/ethyl acetate to give 6-(4-morpholinyl)-3-[3-(trifluoromethyl)phenyl]-1,5(6H)-pyridazindicarboxylic acid diethyl ester (7.26 g, 55% yield) as a yellow solid, mp=128°-129° C.

Aufarbeitung

  1. additionwas added dropwise over 15 min
  2. temperatureThe mixture was then refluxed for 30 min.
  3. temperatureThe mixture was then refluxed for 18 h
  4. temperaturecooled
  5. custompartitioned 2 times with water
  6. dry with materialThe organic layer was dried (MgSO4)
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customto give a crude solid
  10. customThis solid was recrystallized from cyclohexane/ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-15ff2ce4cecc42499a6575bedd7c8d5e
Quelldatensatz
uspto-grants-1997_04
Patentnummer
US05623072

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