m-Toluidine → HCID 58233521, compound

HRID 239210Notes

Reaction equation

HRID 239210 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2[CH:9]=[C:10]([C:14]3([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[C:26]4[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=4[C:20]4[C:15]3=[CH:16][CH:17]=[CH:18][CH:19]=4)[CH:11]=[CH:12][CH:13]=2)[CH:5]=[CH:6][CH:7]=1.CC(C)([O-])C.[Na+].[NH2:39][C:40]1[CH:45]=[CH:44][CH:43]=[C:42]([CH3:46])[CH:41]=1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>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].CCCCCC.C1(C)C=CC=CC=1>[CH3:46][C:42]1[CH:41]=[C:40]([NH:39][C:6]2[CH:7]=[CH:2][CH:3]=[C:4]([C:8]3[CH:13]=[CH:12][CH:11]=[C:10]([C:14]4([C:27]5[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=5)[C:15]5[CH:16]=[CH:17][CH:18]=[CH:19][C:20]=5[C:21]5[C:26]4=[CH:25][CH:24]=[CH:23][CH:22]=5)[CH:9]=3)[CH:5]=2)[CH:45]=[CH:44][CH:43]=1

Participants

8

Reactant 4

HCID 7934m-ToluidineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 58233563HCID 58233563, compound

Product 1

HCID 58233521HCID 58233521, compoundYield 91%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolventHCID 8058HexaneSolvent

Conditions

Temperature
80 °C

Procedure

In a 50 mL three-neck flask were put 1.2 g (2.5 mmol) of 9-[3-(3-bromophenyl)phenyl]-9-phenylfluorene and 0.7 g (7.4 mmol) of sodium tert-butoxide. The air in the flask was replaced with nitrogen. To this mixture were added 12.5 mL of toluene, 0.3 mL (2.5 mmol) of m-toluidine, and 0.2 mL of a 10% hexane solution of tri(tert-butyl)phosphine. The temperature of this mixture was set to 60° C., and 20.0 mg (0.03 mmol) of bis(dibenzylideneacetone)palladium(0) was added to the mixture. The temperature of the mixture was raised to 80° C., followed by stirring for 2.5 hours. After the stirring, the mixture was suction-filtered through Florisil, Celite, and alumina to give a filtrate. The filtrate was concentrated to give a solid, which was then purified by silica gel column chromatography (the developing solvent has a 2:3 ratio of hexane to toluene). Accordingly, 1.1 g of a solid was obtained in 91% yield, which was the substance to be produced. The synthesis scheme of this Step 3 is shown in the following (E18-3).

Workup

  1. customIn a 50 mL three-neck flask were put
  2. customwas set to 60° C.
  3. filtrationAfter the stirring, the mixture was suction-filtered through Florisil, Celite, and alumina
  4. customto give a filtrate
  5. concentrationThe filtrate was concentrated
  6. customto give a solid, which
  7. customwas then purified by silica gel column chromatography (the developing solvent

Sources & evidence

ORD record
ord-a370ad2bdc6842379c7cf2e066bde688
Source dataset
uspto-grants-2014_02
Patent number
US08642190B2

Reaction notes

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