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Chloroform → N-methoxy-N-methyl-4-nitro-2'-methoxymethoxy-6'-methoxy-biphenyl-2-carboxamide

HRID 1358113
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1358113
C([Li])CCC.[CH3:6][O:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([O:14][CH2:15][O:16][CH3:17])[CH:9]=1.[CH3:18][O:19][N:20]([CH3:33])[C:21](=[O:32])[C:22]1[CH:27]=[C:26]([N+:28]([O-:30])=[O:29])[CH:25]=[CH:24][C:23]=1Br.C(Cl)(Cl)Cl>C1COCC1.[Cl-].[Zn+2].[Cl-].[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:18][O:19][N:20]([CH3:33])[C:21]([C:22]1[C:23]([C:9]2[C:8]([O:7][CH3:6])=[CH:13][CH:12]=[CH:11][C:10]=2[O:14][CH2:15][O:16][CH3:17])=[CH:24][CH:25]=[C:26]([N+:28]([O-:30])=[O:29])[CH:27]=1)=[O:32]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 4

HCID 6212ChloroformHCID 5426211-Methoxy-3-(methoxymethoxy)benzeneHCID 18188772N-methoxy-N-methyl-2-bromo-5-nitrobenzamideHCID 178418339Butyllithium

Produkt 1

HCID 18189308N-methoxy-N-methyl-4-nitro-2'-methoxymethoxy-6'-methoxy-biphenyl-2-carboxamideAusbeute 88 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3007855ZincchlorideKatalysator
HCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysator
HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

Butyllithium (8.28 ml. of 2.5M in hexane, 20.69 mmole) was added to a solution of 1-methoxy-3 methoxymethoxy benzene (3.62 g., 21.55 mmole, (T. Kaufman, R. Srivastava, R. Sindelar, J. Med. Chem. 1995, 38, 1437-1445) in. THF (15 mL) at −30° C. The solution was stirred at ambient temperature for 1 hour, cooled to at 0° C. and anhydrous zinc chloride beads (3.5 g, 25.67 mmole) added. The mixture was stirred for 2 hours at 25°. Then a solution of N-methoxy-N-methyl-2-bromo-5-nitrobenzamide (5.00 g, 17.24 mmole) dissolved in THF (20 mL) was added. Bis (triphenylphosphine) palladium dichloride (600 mg.) was added and the solution was stirred at 65° C. for 15 hours. After cooling, chloroform was added and the solution stirred with aqueous KHCO3. The precipitated zinc salts were filtered, the water layer removed and the organic layer dried (Na2SO4), filtered concentrated under reduced pressure and the residuepurified on silica gel eluting with 8% ethyl acetate in CH2Cl2 to provide the titled compound (5.68 g, 88% yield).

Aufarbeitung

  1. customat −30° C
  2. additionadded
  3. stirringThe mixture was stirred for 2 hours at 25°
  4. additionwas added
  5. stirringthe solution was stirred at 65° C. for 15 hours
  6. temperatureAfter cooling
  7. filtrationThe precipitated zinc salts were filtered
  8. customthe water layer removed
  9. dry with materialthe organic layer dried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-648bf1047d70405d923fd46975cfcfba
Quelldatensatz
uspto-grants-2003_07
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US06593480B2

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