Oxalyl chloride → HCID 178447227, Verbindung

HRID 2236776Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2236776
[C:1]([OH:7])(=O)/[C:2](=[CH:4]/[CH3:5])/[CH3:3].C(Cl)(=O)C(Cl)=O.[NH2:14][C:15]1[CH:36]=[CH:35][C:18]([CH2:19][NH:20]/[CH:21]=[C:22]2\[C:23](=[O:34])[NH:24][C:25](=[O:33])[C:26]3[C:31]\2=[CH:30][C:29]([I:32])=[CH:28][CH:27]=3)=[CH:17][C:16]=1[O:37][Si](C(C)C)(C(C)C)C(C)C.C(N(C(C)C)CC)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C(#N)C.O1CCCC1>[OH:37][C:16]1[CH:17]=[C:18]([CH2:19][NH:20]/[CH:21]=[C:22]2\[C:23](=[O:34])[NH:24][C:25](=[O:33])[C:26]3[C:31]\2=[CH:30][C:29]([I:32])=[CH:28][CH:27]=3)[CH:35]=[CH:36][C:15]=1[NH:14][C:1](=[O:7])/[C:2](/[CH3:3])=[CH:4]/[CH3:5]

Komponenten

8

Edukt 5

HCID 65578Oxalyl chlorideHCID 81531DiisopropylethylamineHCID 125468Tiglic acidHCID 2724141Tetrabutylammonium FluorideHCID 178460972HCID 178460972, Verbindung

Produkt 1

HCID 178447227HCID 178447227, VerbindungAusbeute 21,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6342AcetonitrileLösungsmittel2×HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
65 °C

Versuchsvorschrift

To a suspension or solution of carboxylic acid, in this case tiglic acid (0.11 g, 1.1 mmol) in anhydrous acetonitrile (3 mL) is added oxalyl chloride (neat, 100 μL, 1.1 mmol). The mixture is shaken at 65° C. for 30 minutes and then reduced to half volume under reduced pressure. The resulting acetonitrile solution is then added to a solution of (4Z)-4-[({4-amino-3-[(triisopropylsilyl)oxy]benzyl}amino)methylene]-6-iodoisoquinoline-1,3(2H,4H)-dione (65 mg, 0.11 mmol) and diisopropylethylamine (380 μL, 2.2 mmol) in tetrahydrofuran (3 mL) After stirring overnight at room temperature, the reaction mixture is concentrated to dryness under reduced pressure. Tetrabutylammonium fluoride solution (1.0 M, 2.0 mL, 2.0 mmol) is added and the mixture is shaken at 55° C. for 2 hours and then allowed to cool to room temperature. Following concentration, the residue is triturated with water and the resulting solid collected by filtration, washed with acetonitrile, and dried under house vacuum to give (2E)-N-[2-hydroxy-4-({[(Z)-(6-iodo-1,3-dioxo-2,3-dihydroisoquinolin-4(1H)-ylidene)methyl]amino}methyl)phenyl]-2-methylbut-2-enamide (12 mg, 21%).

Aufarbeitung

  1. stirringAfter stirring overnight at room temperature
  2. concentrationthe reaction mixture is concentrated to dryness under reduced pressure
  3. stirringthe mixture is shaken at 55° C. for 2 hours
  4. temperatureto cool to room temperature
  5. concentrationconcentration
  6. customthe residue is triturated with water
  7. filtrationthe resulting solid collected by filtration
  8. washwashed with acetonitrile
  9. customdried under house vacuum

Quellen und Nachweise

ORD-Eintrag
ord-f56c9379fc0748eb87252d459144182a
Quelldatensatz
uspto-grants-2010_05
Patentnummer
US07713994B2

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