StartseiteMCPWorkbenchSkills
StartseiteWorkbenchBenachrichtigungenMein Bereich
llms.txt · MCP-AnleitungDatenschutz · Nutzungsbedingungen · Supportv1.8.0
  1. Startseite
  2. /Reaktion

Cesium carbonate → 2-(3-{3-[4-(3,5-Dimethylisoxazol-4-yl)-2-ethyl-5-hydroxyphenoxy]propoxy}-2-propylphenoxy)benzoic acid sodium salt

HRID 1008311
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1008311
C[O:2][C:3](=[O:50])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[O:10][C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([O:17][CH2:18][CH2:19][CH2:20][O:21][C:22]2[CH:27]=[C:26]([O:28]CC3C=CC=CC=3)[C:25](B3OC(C)(C)C(C)(C)O3)=[CH:24][C:23]=2[CH2:45][CH3:46])[C:12]=1[CH2:47][CH2:48][CH3:49].[CH3:51][C:52]1[C:56](I)=[C:55]([CH3:58])[O:54][N:53]=1.C(=O)([O-])[O-].[Cs+].[Cs+].I[Si](C)(C)C.S([O-])([O-])(=O)=S.[Na+:75].[Na+].[OH-].[Na+]>CCOCC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Na+:75].[CH3:51][C:52]1[C:56]([C:25]2[C:26]([OH:28])=[CH:27][C:22]([O:21][CH2:20][CH2:19][CH2:18][O:17][C:13]3[C:12]([CH2:47][CH2:48][CH3:49])=[C:11]([CH:16]=[CH:15][CH:14]=3)[O:10][C:5]3[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=3[C:3]([O-:50])=[O:2])=[C:23]([CH2:45][CH3:46])[CH:24]=2)=[C:55]([CH3:58])[O:54][N:53]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

9

Edukt 6

HCID 10796Cesium carbonate2×HCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 85247Trimethylsilyl iodide2×HCID 6138834-Iodo-3,5-dimethyl-1,2-oxazole2×HCID 60116371
2-(3-{3-[5-Benzyloxy-2-ethyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenoxy]propoxy}-2-propylphenoxy)benzoic acid methyl ester

Produkt 1

HCID 236661022-(3-{3-[4-(3,5-Dimethylisoxazol-4-yl)-2-ethyl-5-hydroxyphenoxy]propoxy}-2-propylphenoxy)benzoic acid sodium saltAusbeute 23 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Katalysator2×HCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
95 °C

Versuchsvorschrift

A mixture of 2-(3-{3-[5-benzyloxy-2-ethyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenoxy]propoxy}-2-propylphenoxy)benzoic acid methyl ester (305 mg, 0.448 mmol), 3,5-dimethyl-4-iodoisoxazole (110 mg, 0.493 mmol), cesium carbonate (293 mg, 0.899 mmol), and PdCl2(dppf) (15 mg, 0.018 mmol) in de-oxygenated toluene (10 mL) was heated at 95° C. for 10 h. Additional portions of 3,5-dimethyl-4-iodoisoxazole (110 mg), cesium carbonate (260 mg), and PdCl2(dppf) (˜15 mg) were added and heating continued at 110° C. for 20 h. The mixture was cooled to room temperature, concentrated in vacuo, diluted with methylene chloride, and filtered down a short plug of silica gel with 20% ethyl acetate/80% hexane. The filtrate was concentrated in vacuo. The resulting colorless oil was dissolved in methylene chloride (4 mL), cooled to 0° C., and treated with iodotrimethylsilane (0.40 mL, 2.7 mmol). The resulting mixture was allowed to warm to room temperature and stirred for 18 h. An additional portion of iodotrimethylsilane (0.70 mL) was added and stirring continued for 72 h. The mixture was poured into dilute sodium thiosulfate solution. The organic layer was separated, washed with water, dried (sodium sulfate), filtered, and concentrated in vacuo. The resulting foam was dissolved in a 1:1 mixture of tetrahydrofuran/l N hydrochloric acid (5 mL) and stirred at room temperature for 18 h. The mixture was concentrated in vacuo and treated with 1 equivalent 1 N sodium hydroxide solution in ether. The resulting mixture was concentrated in vacuo to provide 59 mg (23%) of the title compound as an off-white solid. 1H NMR (DMSO-d6) δ 7.40 (dd, J=9, 2 Hz, 1H), 7.13 (dt, J=8, 2 Hz, 1H), 6.97 (m, 2H), 6.79 (s, 1H), 6.68 (d, J=9 Hz, 1H), 6.65 (d, J=9 Hz, 1H), 6.60 (s, 1H), 6.21 (d, J=8 Hz, 1H), 4.19 (t, J=6 Hz, 2H), 4.01 (t, J=6 Hz, 2H), 2.66 (t, J=8 Hz, 2H), 2.48 (q, J=8 Hz, 2H), 2.24 (s, 3H), 2.17 (quintet, J=6 Hz, 2H), 2.07 (s, 3 H), 1.49 (hextet, J=8 Hz, 2H), 1.07 (t, J=7 Hz, 3H), 0.85 (t, J=7 Hz, 3H); TOF MS ES+ exact mass calculated for C32H36NO7 (p+1): m/z=546.2492. Found: 546.2514; IR (KBr, cm−1) 3400, 1605, 1460.

Aufarbeitung

  1. temperatureheating
  2. temperatureThe mixture was cooled to room temperature
  3. concentrationconcentrated in vacuo
  4. additiondiluted with methylene chloride
  5. filtrationfiltered down a short plug of silica gel with 20% ethyl acetate/80% hexane
  6. concentrationThe filtrate was concentrated in vacuo
  7. dissolutionThe resulting colorless oil was dissolved in methylene chloride (4 mL)
  8. temperaturecooled to 0° C.
  9. temperatureto warm to room temperature
  10. stirringstirring
  11. waitcontinued for 72 h
  12. customThe organic layer was separated
  13. washwashed with water
  14. dry with materialdried (sodium sulfate)
  15. filtrationfiltered
  16. concentrationconcentrated in vacuo
  17. dissolutionThe resulting foam was dissolved in a 1:1 mixture of tetrahydrofuran/l N hydrochloric acid (5 mL)
  18. stirringstirred at room temperature for 18 h
  19. concentrationThe mixture was concentrated in vacuo
  20. concentrationThe resulting mixture was concentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-d48f6934650f40d5bbf73bd7d715fa83
Quelldatensatz
uspto-grants-2004_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US06797723B1

Notizen zur Reaktion

Wird geladen…

Auf dieser SeiteKomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion