Dimethylformamide → 1-(benzo[d][1,3]dioxol-5-yl)-N-(5-bromopyridin-2-yl)cyclopropanecarboxamide

HRID 17950

Reaktionsgleichung

Reaktionsgleichung von HRID 17950
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3([C:13]([OH:15])=O)[CH2:12][CH2:11]3)=[CH:9][C:4]=2[O:3][CH2:2]1.S(Cl)(Cl)=O.CN(C)C=O.[Br:25][C:26]1[CH:27]=[CH:28][C:29]([NH2:32])=[N:30][CH:31]=1>N1C=CC=CC=1>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3([C:13]([NH:32][C:29]4[CH:28]=[CH:27][C:26]([Br:25])=[CH:31][N:30]=4)=[O:15])[CH2:11][CH2:12]3)=[CH:9][C:4]=2[O:3][CH2:2]1

Komponenten

6

Edukt 4

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 706222-Amino-5-bromopyridineHCID 143496081-(1,3-Dioxaindan-5-yl)cyclopropane-1-carboxylic acid

Produkt 1

HCID 591661631-(benzo[d][1,3]dioxol-5-yl)-N-(5-bromopyridin-2-yl)cyclopropanecarboxamideAusbeute 83,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1049PyridineLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

1-Benzo[1,3]dioxol-5-yl-cyclopropanecarboxylic acid (2.38 g, 11.5 mmol) was placed in an oven-dried flask under nitrogen. Thionyl chloride (2.5 mL) and N,N-dimethylformamide (0.3 mL) were added and the solution was allowed to stir for 30 minutes at 60° C. The excess thionyl chloride was removed under vacuum and the resulting solid was suspended in 7 mL of anhydrous pyridine. This solution was then slowly added to a solution of 5-bromo-pyridin-2-ylamine (2.00 g, 11.6 mmol) suspended in 10 mL of anhydrous pyridine. The resulting mixture was allowed to stir for 15 hours at 110° C. The mixture was then evaporated to dryness, suspended in 100 mL of dichloromethane, and washed with three 25 mL portions of 1N NaOH. The organic layer was dried over sodium sulfate, evaporated to near dryness, and then purified by silica gel column chromatography utilizing dichloromethane as the eluent to yield the pure product (3.46 g, 83%) ESI-MS m/z calc. 361.2. found 362.1 (M+1)+; Retention time 3.40 minutes. 1H NMR (400 MHz, DMSO-d6) δ 1.06-1.21 (m, 2H), 1.44-1.51 (m, 2H), 6.07 (s, 2H), 6.93-7.02 (m, 2H), 7.10 (d, J=1.6 Hz, 1H), 8.02 (d, J=1.6 Hz, 2H), 8.34 (s, 1H), 8.45 (s, 1H).

Aufarbeitung

  1. customThe excess thionyl chloride was removed under vacuum
  2. stirringto stir for 15 hours at 110° C
  3. customThe mixture was then evaporated to dryness
  4. washwashed with three 25 mL portions of 1N NaOH
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. customevaporated
  7. custompurified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-654e0b84ebe44faebe4df5c260b7777d
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07741321B2

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