Sodium Carbonate → HCID 68278472, Verbindung

HRID 931432

Reaktionsgleichung

Reaktionsgleichung von HRID 931432
[O-]S([O-])=O.[Na+].[Na+].C([O-])([O-])=O.[Na+].[Na+].[CH3:13][C:14]1[CH:15]=[C:16]([S:21](Cl)(=[O:23])=[O:22])[CH:17]=[C:18]([CH3:20])[CH:19]=1.Cl[CH2:26][C:27]1[N:28]=[C:29]([C:33]2[CH:42]=[CH:41][C:36]([C:37]([O:39][CH3:40])=[O:38])=[CH:35][CH:34]=2)[O:30][C:31]=1[CH3:32]>O.CN(C=O)C>[CH3:13][C:14]1[CH:15]=[C:16]([S:21]([CH2:26][C:27]2[N:28]=[C:29]([C:33]3[CH:42]=[CH:41][C:36]([C:37]([O:39][CH3:40])=[O:38])=[CH:35][CH:34]=3)[O:30][C:31]=2[CH3:32])(=[O:23])=[O:22])[CH:17]=[C:18]([CH3:20])[CH:19]=1

Komponenten

7

Edukt 4

HCID 10340Sodium CarbonateHCID 24437Sodium SulfiteHCID 27362353,5-Dimethylbenzenesulfonyl chlorideHCID 23076573Methyl 4-(4-(chloromethyl)-5-methyloxazol-2-yl)benzoate

Produkt 1

HCID 68278472HCID 68278472, VerbindungAusbeute 90 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittel2×HCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A solution of Na2SO3 (308 mg, 2.4 mmol) and Na2CO3 (259 mg, 2.4 mmol) in water (5 mL) was added to a suspension of 3,5-dimethylbenzenesulfonyl chloride (500 mg, 2.4 mmol) in water (5 mL) and the mixture was stirred at 100° C. for 2 h. The mixture was cooled, filtered, and the filtrate was made acidic with 1 M HCl and chilled at 0° C. for 2 h. The precipitate was filtered, washed with water (1 mL) and dried. A mixture of chloride 2 (289 mg, 1.08 mmol) and crude sulfinic acid (184 mg, 1.08 mmol) in dry DMF (10 mL) was stirred at 100° C. for 16 h. The mixture was cooled and diluted with ice/water (50 mL) and stirred for 15 min. The precipitate was filtered, washed with water (5 mL). The residue purified by column chromatography, eluting with a gradient (50-100%) of EtOAc/pet. ether, to give benzoate 25 (388 mg, 90%) as a white powder: mp (EtOAc) 141-143° C.; 1H NMR (CDCl3) δ 8.03 (ddd, J=8.6, 1.8, 1.5 Hz, 2H, H-2, H-6), 7.94 (ddd, J=8.6, 1.8, 1.5 Hz, 2H, H-3, H-5), 7.42 (br s, 2H, H-2′, H-6′), 7.25 (br s, 1H, H-4′), 4.28 (s, 2H, CH2SO2), 3.94 (s, 3H, OCH3), 2.35 (s, 3H, CH3), 2.33 (s, 6H, 2×CH3); MS m/z 400.5 (MH+, 100%). Anal. calcd for C21H21NO5S: C, 63.14; H, 5.30; N, 3.51. Found: C, 63.23; H, 5.28; N, 3.46%.

Aufarbeitung

  1. temperatureThe mixture was cooled
  2. filtrationfiltered
  3. temperaturechilled at 0° C. for 2 h
  4. filtrationThe precipitate was filtered
  5. washwashed with water (1 mL)
  6. customdried
  7. stirringwas stirred at 100° C. for 16 h
  8. temperatureThe mixture was cooled
  9. stirringstirred for 15 min
  10. filtrationThe precipitate was filtered
  11. washwashed with water (5 mL)
  12. customThe residue purified by column chromatography
  13. washeluting with a gradient (50-100%) of EtOAc/pet. ether

Quellen und Nachweise

ORD-Eintrag
ord-e263f87422964412b78dfc3f51cf052b
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09296732B2

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