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Citric Acid → 3-Bromo-1-(4-fluorophenyl)-1h-1,2,4-triazole

HRID 1180639
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1180639
[Br:1][C:2]1[N:6]=[CH:5][NH:4][N:3]=1.[C:7]([OH:10])(=[O:9])[CH3:8].[C:11](O)(=O)[CH3:12].[F:15][C:16]1[CH:21]=[CH:20][C:19]([Bi]([C:30]2[CH:35]=[CH:34][C:33](F)=[CH:32]C=2)C2C=CC(F)=CC=2)=[CH:18][CH:17]=1.[CH3:37]N(C)C(N(C)C)=N.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O1CCCC1.C([O-])(=O)C.[Cu+2].C([O-])(=O)C.C(OCC)(=O)C.O>[C:7]([O:10][CH2:11][CH3:12])(=[O:9])[CH3:8].[CH3:30][CH2:35][CH2:34][CH:33]([CH3:32])[CH3:37].[F:15][C:16]1[CH:21]=[CH:20][C:19]([N:4]2[CH:5]=[N:6][C:2]([Br:1])=[N:3]2)=[CH:18][CH:17]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

10

Edukt 4

HCID 311Citric AcidHCID 664601,1,3,3-TetramethylguanidineHCID 11966511Acetic acid;tris(4-fluorophenyl)bismuthaneHCID 178419478HCID 178419478, Verbindung

Produkt 2

HCID 21882781Isohexane ethyl acetateAusbeute 40 %
HCID 23571132
3-Bromo-1-(4-fluorophenyl)-1h-1,2,4-triazole
Ausbeute 45 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 8895Cupric acetateKatalysatorHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

A mixture of 3-bromo-1,2,4-1H-triazole (prepared as described in Chemische Berichte 1967, 100, 2250) (1.0 g, 6.76 mmol), tri(4-fluorophenyl)bismuth diacetate (prepared by the method described in Synthetic Communications 1996, 4569) (4.53 g, 7.4 mmol), copper (II) acetate (0.25 g, 20 mol %) and N,N,N′,N′-tetramethylguanidine (1.7 mL, 13.5 mmol) in dry tetrahydrofuran (30 mL) was stirred at 50° C. under a balloon of air for 16 hr. The suspension was poured into water (100 mL) and 1M citric acid (30 mL) to give a suspension of pH 3-4. Ethyl acetate (100 mL) was added and the mixture was filtered through Celite®, washing the filter cake with ethyl acetate (100 mL). The two phases of the filtrate were separated and the organic layer was dried (Na2SO4) and concentrated. Flash column chromatography on silica gel, eluting with 25% then 40% ethyl acetate—isohexane, gave 1-(4-fluorophenyl)-3-bromo-1,2,4-1H-triazole as an off-white solid (0.74 g, 45%). δ (1H, 400 MHz, CDCl3) 7.18-7.24 (2H, m), 7.60-7.65 (2H, m), 8.37 (1H, s). MS (ES+) 242, 244 ([MH]+). Step 2: [6S,9R,11R] 2′,3′,4′,5,5′,6,7,8,9,10-Decahydro-2-(1-(4-fluorophenyl)-1,2,4-triazol-3-yl)-5′-(2,2,2-trifluoroethyl)-spiro[6,9-methanobenzocyclooctene-11,3′-[1,2,5]thiadiazole] 1′,1′-dioxide

Aufarbeitung

  1. customprepared by the method
  2. customto give
  3. additiona suspension of pH 3-4
  4. filtrationthe mixture was filtered through Celite®
  5. washwashing the filter cake with ethyl acetate (100 mL)
  6. customThe two phases of the filtrate were separated
  7. dry with materialthe organic layer was dried (Na2SO4)
  8. concentrationconcentrated
  9. washFlash column chromatography on silica gel, eluting with 25%

Quellen und Nachweise

ORD-Eintrag
ord-a23892edaaf5417a80a37de2404fb7b0
Quelldatensatz
uspto-grants-2007_10
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07282513B2

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