m-Toluidine → HCID 67105540, compound

HRID 239207Notes

Reaction equation

HRID 239207 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2([C:21]3[CH:26]=[CH:25][CH:24]=[C:23](C)[CH:22]=3)[C:20]3[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=3[C:14]3[C:9]2=[CH:10][CH:11]=[CH:12][CH:13]=3)[CH:5]=[CH:6][CH:7]=1.[NH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[C:31]([CH3:35])[CH:30]=1.[CH3:36]C(C)([O-])C.[Na+].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>[CH3:35][C:31]1[CH:30]=[C:29]([NH:28][C:6]2[CH:7]=[CH:2][CH:3]=[C:4]([C:8]3([C:21]4[CH:22]=[CH:23][C:24]([CH3:36])=[CH:25][CH:26]=4)[C:20]4[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=4[C:14]4[C:9]3=[CH:10][CH:11]=[CH:12][CH:13]=4)[CH:5]=2)[CH:34]=[CH:33][CH:32]=1

Participants

8

Reactant 4

HCID 7934m-ToluidineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 58233546HCID 58233546, compound

Product 1

HCID 67105540HCID 67105540, compoundYield 91%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
90 °C

Procedure

In a 200 mL three-neck flask were put 3.0 g (7.3 mmol) of 9-(3-bromophenyl)-9-(3-methylphenyl)-fluorene, 0.8 mL (7.3 mmol) of m-toluidine, and 2.1 g (21.9 mmol) of sodium tert-butoxide. The air in the flask was replaced with nitrogen. To this mixture were added 37.0 mL of toluene and 0.2 mL of a 10% hexane solution of tri(tert-butyl)phosphine. The temperature of this mixture was set to 85° C., and 36.0 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0) was added to the mixture. The temperature of the mixture was raised to 90° C., followed by stirring for 4.0 hours. After the stirring, the mixture was suction-filtered through Florisil, Celite, and alumina to give a filtrate. The filtrate was concentrated to give an oily substance, which was then purified by silica gel column chromatography (the developing solvent has a 2:1 ratio of hexane to toluene). The obtained fractions were concentrated to give 2.9 g of a white solid in 91% yield, which was the substance to be produced. The synthesis scheme of this Step 1 is shown in (E15-1) given below.

Workup

  1. customIn a 200 mL three-neck flask were put
  2. customwas set to 85° 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 an oily substance, which
  7. customwas then purified by silica gel column chromatography (the developing solvent
  8. concentrationThe obtained fractions were concentrated

Sources & evidence

ORD record
ord-ed09fc1f9f664326a7d2a45caf753f65
Source dataset
uspto-grants-2014_02
Patent number
US08642190B2

Reaction notes

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