Potassium Carbonate → 2'-Hydroxymethyl-3-methylamino-4-nitro-biphenyl-2-carbonitrile

HRID 2246896Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2246896
Cl[C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH:10][CH3:11])[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1.[OH:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1B(O)O.C(=O)([O-])[O-].[K+].[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2N(C)C)CCCCC1>CC(N(C)C)=O.CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[OH:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH:10][CH3:11])[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1

Komponenten

8

Edukt 4

HCID 11430Potassium CarbonateHCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 43742622-(Hydroxymethyl)phenylboronic AcidHCID 112180896-Chloro-2-(methylamino)-3-nitrobenzonitrile

Produkt 1

HCID 592186742'-Hydroxymethyl-3-methylamino-4-nitro-biphenyl-2-carbonitrileAusbeute 82 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 8857Ethyl AcetateLösungsmittelHCID 31374DimethylacetamideLösungsmittel

Reaktionsbedingungen

Temperatur
68 °C

Versuchsvorschrift

6-Chloro-2-methylamino-3-nitro-benzonitrile (500 mg, 2.4 mmol), 2-hydroxymethyl-phenylboronic acid (466 mg, 3.1 mmol), and potassium carbonate (1.30 g, 6.1 mmol) were combined in DMA (10 mL) in a flask purged with nitrogen. Tris(dibenzylideneacetone)dipalladium(0) (108 mg, 0.12 mmol) and 2-dicyclohexylphosphino-2′-(N,N-dimethyl-amino)biphenyl (93 mg, 0.24 mmol) were added, and the reaction stirred at 68° C. under nitrogen for 16 h. The solution was diluted with EtOAc (50 mL), and washed with 1N HCl and brine. Organics were dried (MgSO4) and concentrated in vacuo. Purification by silica gel chromatography (2:1:1 hexanes/CHCl3/EtOAc) gave 550 mg (82%) of the title compound as an orange solid. 1H NMR (400 MHz, CDCl3): δ 8.49 (br s, 1H), 8.35 (d, 1H, J=8.8 Hz), 7.59 (d, 1H, J=7.6 Hz), 7.46 (td, 1H, J=7.6, 1.2 Hz), 7.40 (td, 1H, J=7.6, 1.2 Hz), 7.20 (dd, 1H, J=7.6, 1.2 Hz), 6.60 (d, 1H, J=8.8 Hz), 4.52 (qAB, 2H, J=31.6, 12.8 Hz), 3.46 (s, 3H). MS (ES) [m+H] calc'd for C15H13N3O3, 284; found 284.

Aufarbeitung

  1. custompurged with nitrogen
  2. washwashed with 1N HCl and brine
  3. dry with materialOrganics were dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customPurification by silica gel chromatography (2:1:1 hexanes/CHCl3/EtOAc)

Quellen und Nachweise

ORD-Eintrag
ord-5d7fcc08241f4d88bd462a222a786760
Quelldatensatz
uspto-grants-2010_03
Patentnummer
US07687638B2

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