m-Toluidine → HCID 67106648, compound

HRID 239206Notes

Reaction equation

HRID 239206 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2([C:21]3[CH:26]=[CH:25][CH:24]=[C:23]([CH3:27])[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.CC(C)([O-])C.[Na+].[NH2:34][C:35]1[CH:40]=[CH:39][CH:38]=[C:37]([CH3:41])[CH:36]=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>[CH3:41][C:37]1[CH:36]=[C:35]([NH:34][C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([C:8]3([C:21]4[CH:26]=[CH:25][CH:24]=[C:23]([CH3:27])[CH:22]=4)[C:9]4[CH:10]=[CH:11][CH:12]=[CH:13][C:14]=4[C:15]4[C:20]3=[CH:19][CH:18]=[CH:17][CH:16]=4)[CH:3]=2)[CH:40]=[CH:39][CH:38]=1

Participants

8

Reactant 4

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

Product 1

HCID 67106648HCID 67106648, compoundYield 98%

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 and 2.1 g (22.0 mmol) of sodium tert-butoxide. The air in the flask was replaced with nitrogen. To this mixture were added 37.0 mL of toluene, 0.8 mL (7.4 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 85° C., and 29.8 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). Accordingly, 3.1 g of a compound was obtained in 98% yield, which was the substance to be produced. The synthesis scheme of this Step 1 is shown in the following (E14-1).

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

Sources & evidence

ORD record
ord-fece9975bd984d6cb4143e022249927a
Source dataset
uspto-grants-2014_02
Patent number
US08642190B2

Reaction notes

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