Benzene → 4,6-Diaminonicotinonitrile

HRID 50779

반응식

HRID 50779 반응식
Br[C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH2:10])[CH:5]=[C:4]([NH2:11])[N:3]=1.CC([O-])=O.[K+].[OH-].[Na+].C1C=CC=CC=1>C1COCC1.CO.Cl.O.[Pd]>[C:8]([C:7]1[CH:2]=[N:3][C:4]([NH2:11])=[CH:5][C:6]=1[NH2:10])#[N:9]

참가 물질

9

반응물 4

HCID 241BenzeneHCID 14798Sodium HydroxideHCID 1706684,6-Diamino-2-bromo-3-pyridinecarbonitrileHCID 517044Potassium Acetate

생성물 1

HCID 2958964,6-Diaminonicotinonitrile수율 69%

시약·촉매·용매 4

HCID 23938Palladium촉매HCID 313Hydrochloric Acid용매HCID 962Water용매HCID 21899815MeOH tetrahydrofuran용매

실험 절차

Crude 2-bromo-3-cyano-4,6-diaminopyridine [(W. J. Middleton, U.S. Pat. No. 2,790,806 (Apr. 30, 1957), Du Pont; Chem. Abst. 51:P14829 (1957), see also next experimental] (15.1 g, 0.071 mole) is hydrogenated in THF/MeOH (200 mL, 2:1) containing KOAc (7.0 g, 0.071 mole) and 5% Pd/C (4 g) at 55 p.s.i. and 20° C. for 7 days. Filtration over celite, washing with THF/MeOH and removal of the solvent gives a solid, which is dissolved in dilute HCl and water. Adjustment of the solution pH to 10 (conc. NaOH) and cooling gives 3-cyano-4,6-diaminopyridine (6.58 g, 69%) as a yellow solid, mp 197-198° C. [Metzger, R.; Oberdorfer, J.; Schwager, C.; Thielecke, W.; Boldt, P. Liebigs Ann. Chem. 1980, 946-953 record mp (benzene) 205° C.]. Extraction of the remaining liquor with EtOAc (4×200 mL) gives further product (2.12 g, 22%). 1H NMR (DMSO) δ 7.91 (1H, s), 6.26, 6.24 (2H, 2H, brs), 5.63 (1H, s)

후처리

  1. filtrationFiltration over celite
  2. washwashing with THF/MeOH and removal of the solvent
  3. customgives a solid, which

출처 및 근거

ORD 기록
ord-292716e2e63e477b8d6077358cc4055b
출처 데이터셋
uspto-grants-2004_03
특허 번호
US06713484B2

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