Ethyl 3-chloro-3-oxopropionate → (1,1-Dioxo-1,4-dihydro-1lambda6-thia-2,4,8-triaza-naphthalen-3-yl)-acetic acid ethyl ester

HRID 548383

Reaktionsgleichung

Reaktionsgleichung von HRID 548383
[NH2:1][C:2]1[C:3]([S:8]([NH2:11])(=[O:10])=[O:9])=[N:4][CH:5]=[CH:6][CH:7]=1.[CH2:12]([O:14][C:15](=[O:20])[CH2:16][C:17](Cl)=O)[CH3:13]>O1CCOCC1.C(OCC)(=O)C>[CH2:12]([O:14][C:15](=[O:20])[CH2:16][C:17]1[NH:1][C:2]2[C:3](=[N:4][CH:5]=[CH:6][CH:7]=2)[S:8](=[O:10])(=[O:9])[N:11]=1)[CH3:13]

Komponenten

5

Edukt 2

HCID 118931Ethyl 3-chloro-3-oxopropionateHCID 149437023-Aminopyridine-2-sulfonamide

Produkt 1

HCID 59184502(1,1-Dioxo-1,4-dihydro-1lambda6-thia-2,4,8-triaza-naphthalen-3-yl)-acetic acid ethyl esterAusbeute 11 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8857Ethyl AcetateLösungsmittel2×HCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

3-Amino-pyridine-2-sulfonic acid amide (1.8 g, 10.4 mmol) was dissolved in 1,4-dioxane (45 mL). Chlorocarbonyl-acetic acid ethyl ester (1.57 mL, 12.48 mmol) was added. The mixture was stirred at 90° C. for 1.5 h. Upon cooling, the mixture was diluted with ethyl acetate (300 mL) and washed with half-saturated aqueous sodium bicarbonate solution (100 mL) followed by saturated aqueous brine solution (100 mL). The organic layer was dried over magnesium sulfate, filtered and concentrated in vacuo. The resulting oily residue was treated with toluene (36 mL) and triethylamine (9 mL). The mixture was stirred at 110° C. in a sealed tube for 1.5 h. The residue never completely dissolved. Upon cooling, the mixture was concentrated in vacuo to afford a thick oil. Trituration with a minimal amount of ethyl acetate (˜5 mL) solidified the product. The solids were collected by vacuum filtration and dried in vacuo for 16 h to afford the desired product, (1,1-dioxo-1,4-dihydro-1λ6-thia-2,4,8-triaza-naphthalen-3-yl)-acetic acid ethyl ester (0.3 g, 1.11 mmol, 11%), as a white solid. 1H NMR (400 MHz, DMSO-d6) δ: 1.21 (3H, t, J=7.0 Hz), 3.71 (2H, s), 4.16 (2H, quartet, J=7.1 Hz), 7.70-7.76 (2H, m), 8.62 (1H, dd, J1−4.0 Hz, J2=1.5 Hz), 12.29 (1H, bs). LC-MS (ESI) calcd for C10H11N3O4S 269.05, found 270.1 [M+H+].

Aufarbeitung

  1. temperatureUpon cooling
  2. washwashed with half-saturated aqueous sodium bicarbonate solution (100 mL)
  3. dry with materialThe organic layer was dried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. additionThe resulting oily residue was treated with toluene (36 mL) and triethylamine (9 mL)
  7. stirringThe mixture was stirred at 110° C. in a sealed tube for 1.5 h
  8. dissolutionThe residue never completely dissolved
  9. temperatureUpon cooling
  10. concentrationthe mixture was concentrated in vacuo
  11. customto afford a thick oil
  12. filtrationThe solids were collected by vacuum filtration
  13. customdried in vacuo for 16 h

Quellen und Nachweise

ORD-Eintrag
ord-6105bf1f330a4e12aa1073b512d27950
Quelldatensatz
uspto-grants-2011_05
Patentnummer
US07939524B2

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