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

반응식

HRID 548383 반응식
[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]

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 8857Ethyl Acetate용매2회HCID 312751,4-Dioxane용매

반응 조건

온도
90 °C

실험 절차

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+].

후처리

  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

출처 및 근거

ORD 기록
ord-6105bf1f330a4e12aa1073b512d27950
출처 데이터셋
uspto-grants-2011_05
특허 번호
US07939524B2

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