Nitrogen → N-[3-(2,2-dipyridin-3-ylethyl)pyridin-2-yl]benzene-1,2-diamine

HRID 1686070Notes

Reaction equation

HRID 1686070 reaction equation
Cl[C:2]1[C:7]([CH2:8][CH:9]([C:16]2[CH:17]=[N:18][CH:19]=[CH:20][CH:21]=2)[C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)=[CH:6][CH:5]=[CH:4][N:3]=1.[C:22]1([NH2:29])[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[NH2:28].CC(C)([O-])C.[Na+].N#N>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[Fe+2]>[N:12]1[CH:13]=[CH:14][CH:15]=[C:10]([CH:9]([C:16]2[CH:17]=[N:18][CH:19]=[CH:20][CH:21]=2)[CH2:8][C:7]2[C:2]([NH:28][C:23]3[C:22]([NH2:29])=[CH:27][CH:26]=[CH:25][CH:24]=3)=[N:3][CH:4]=[CH:5][CH:6]=2)[CH:11]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 7243O-PhenylenediamineHCID 23676156Sodium t-butoxideHCID 866343192-Chloro-3-(2,2-dipyridin-3-ylethyl)pyridine

Product 1

HCID 67264573N-[3-(2,2-dipyridin-3-ylethyl)pyridin-2-yl]benzene-1,2-diamine

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 152416121,1`-Bis(diphenylphosphino)ferroceneCatalystHCID 1140TolueneSolvent

Procedure

To a solution of 2-chloro-3-(2,2-dipyridin-3-ylethyl)pyridine in 160 mL toluene was added phenylenediamine (8.41 g), tris(dibenzylideneacetone)-dipalladium(0) (356 mg), 1,1-bis(diphenylphosphino)ferrocene (431 mg), and sodium tert-butoxide (2.24 g) under N2. The reaction was heated at 100 C under a stream of N2 for 14 h, then partitioned between saturated aqueous sodium bicarbonate and CH2Cl2. The aqueous solution was extracted with CH2Cl2 (3×), and the combined organic solutions were dried (Na2SO4) and concentrated. To the resulting black residue were added CH2Cl2 and hexane, and the precipitated solid was filtered off (washing with 1:1 CH2Cl2:hexane, followed by toluene). The filtrate was concentrated and purified by flash chromatography to give 4.1 g of N-[3-(2,2-dipyridin-3-ylethyl)pyridin-2-yl]benzene-1,2-diamine as a grey solid.

Workup

  1. custompartitioned between saturated aqueous sodium bicarbonate and CH2Cl2
  2. extractionThe aqueous solution was extracted with CH2Cl2 (3×)
  3. dry with materialthe combined organic solutions were dried (Na2SO4)
  4. concentrationconcentrated
  5. additionTo the resulting black residue were added CH2Cl2 and hexane
  6. filtrationthe precipitated solid was filtered off
  7. wash(washing with 1:1 CH2Cl2:hexane, followed by toluene)
  8. concentrationThe filtrate was concentrated
  9. custompurified by flash chromatography

Sources & evidence

ORD record
ord-1dae641de9d940a6b0110b16ef91b239
Source dataset
uspto-grants-2012_04
Patent number
US08148535B2

Reaction notes

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