Butyl nitrite → 3-(Dipropylcarbamoyl)benzoic acid

HRID 1014866

Reaktionsgleichung

Reaktionsgleichung von HRID 1014866
C(O[C@H:5]1[CH2:9][N:8](C(OC(C)(C)C)=O)[C@@H:7]([C:17](O)=O)[CH2:6]1)C=C.Br[C:21]1[CH:22]=[C:23]([CH:27]=[C:28]([C:30]([O:32]C)=O)[CH:29]=1)[C:24]([OH:26])=[O:25].N(O[CH2:37]CCC)=O.C(OC(N1C[C@H](O)C[C@@H]1C(O)=O)=O)(C)(C)C>[Cu](Br)Br.O.C(#N)C>[CH2:7]([N:8]([CH2:9][CH2:5][CH3:6])[C:30]([C:28]1[CH:27]=[C:23]([CH:22]=[CH:21][CH:29]=1)[C:24]([OH:26])=[O:25])=[O:32])[CH2:17][CH3:37]

Komponenten

8

Edukt 4

HCID 10996Butyl nitriteHCID 688616N-Boc-cis-4-hydroxy-D-prolineHCID 225936413-Bromo-5-(methoxycarbonyl)benzoic acidHCID 67315699(4R)-1-Boc-4-(2-propen-1-yloxy)-D-proline

Produkt 1

HCID 1827693-(Dipropylcarbamoyl)benzoic acidAusbeute 97 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24611Copper bromide (CuBr2)KatalysatorHCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

Step G (2): 3-bromo-5-(methoxycarbonyl)benzoic acid. To a mixture of copper (II) bromide (5.5 g, 24.6 mmol), n-butyl nitrite (3.17 g, 30.75 mmol) and acetonitrile (300 mL) was added 3-amino-5-(methoxycarbonyl)benzoic acid (Step G (1), 4.0 g, 20.5 mmol) in aceonitrile (300 mL) over 30 min at 0° C. and the mixture was warmed up and stirred at rt for 3 h. H2O was added and acetonitrile was removed. Ethyl acetate (600 mL) was added and the mixture was washed with 3N HCl, H2O, dried over Na2SO4, and concentrated in vacuo to give the title compound (97% yield): 1H NMR (CDCl3, 500 MHz) δ ppm 3.96 (3H, s), 8.41 (1H, s), 8.41 (1H, s), 8.67 (1H, m). MS (ESI) (M−H)− 259.02.

Aufarbeitung

  1. temperaturethe mixture was warmed up
  2. customacetonitrile was removed
  3. additionEthyl acetate (600 mL) was added
  4. washthe mixture was washed with 3N HCl, H2O
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-7e4cf51a9ccc4cd58d94b5cebc37a06a
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07981913B2

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