Cesium carbonate → N-benzhydrylidene-N'-[2-(benzhydrylidene-hydrazonomethyl)-thiophen-3-yl]-hydrazine

HRID 246054Notes

Reaction equation

HRID 246054 reaction equation
[C:1](=[N:14]/[N:15]=[CH:16]/[C:17]1[S:18][CH:19]=[CH:20][C:21]=1Br)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:23]1([C:29](=[N:36][NH2:37])[C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.CCOC(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:29](=[N:36][NH:37][C:21]1[CH:20]=[CH:19][S:18][C:17]=1[CH:16]=[N:15][N:14]=[C:1]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)([C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 79304DiphenylmethylidenehydrazineHCID 89330312(E)-N-[(E)-(3-bromothiophen-2-yl)methylideneamino]-1,1-diphenylmethanimine

Product 1

HCID 131731220N-benzhydrylidene-N'-[2-(benzhydrylidene-hydrazonomethyl)-thiophen-3-yl]-hydrazineYield 90.5%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of N-benzhydrylidene-N′-[1-(3-bromo-thiophen-2-yl)-meth-(E)-ylidene]-hydrazine (10.8 g, 29.2 mmol) in toluene (200 mL) was added (diphenylmethylene)hydrazine (6.9 g, 35.1 mmol), cesium carbonate (16.2 g, 49.7 mmol), Pd(OAc)2 (1.31 g, 5.85 mol), and 1,1′-bis(diphenylphosphino)ferrocene (2.43 g, 4.4 mmol). The reaction mixture was heated at 100° C. for 8.5 h then cooled to room temperature, diluted with EtOAc and filtered over Celite, rinsing with EtOAc. The filtrate was concentrated and the residue was purified by silica gel chromatography with 10% to 20% EtOAc/heptane to give 12.8 g of N-benzhydrylidene-N′-[2-(benzhydrylidene-hydrazonomethyl)-thiophen-3-yl]-hydrazine as a viscous brown oil.

Workup

  1. temperaturethen cooled to room temperature
  2. filtrationfiltered over Celite
  3. washrinsing with EtOAc
  4. concentrationThe filtrate was concentrated
  5. customthe residue was purified by silica gel chromatography with 10% to 20% EtOAc/heptane

Sources & evidence

ORD record
ord-f41e36512905488da3d6b4fa040c2f10
Source dataset
uspto-grants-2014_02
Patent number
US08658646B2

Reaction notes

Loading…