Toluene → 2,2'-Dimethylbiphenyl

HRID 1387704Notes

Reaction equation

HRID 1387704 reaction equation
CC([O-])(C)C.[Na+].Cl[C:8]1[CH:9]=[C:10](C)[CH:11]=[C:12]([CH3:14])[CH:13]=1.[CH2:16](NC)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].C1(C)C=CC=CC=1>CCOCC.[Pd].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]>[CH3:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:13]1[CH:8]=[CH:9][CH:10]=[CH:11][C:12]=1[CH3:14]

Participants

8

Reactant 4

HCID 1140Toluene3×HCID 328873,5-DimethylchlorobenzeneHCID 93190N-MethylheptylamineHCID 23676156Sodium t-butoxide

Product 1

HCID 117972,2'-DimethylbiphenylYield 126.1%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
105 °C

Procedure

This is an example of Pd/ligand 4-catalyzed aryl amination reaction for aryl amine synthesis. A reaction tube containing NaOtBu (120 mg, 1.25 mmol) was thoroughly evacuated and purged with argon. 5-Chloro-m-xylene (0.14 mL, 1.04 mmol), heptylmethylamine (0.21 mL, 1.25 mmol), a toluene solution of Pd(dba)2 (1.2 mL, 1.0 mg/mL, 2.1 μmol) and a toluene solution of ligand 4 (2.5 mL, 1.0 mg/mL, 6.2 ,μmol) and toluene (0.3 mL) were added to the reaction tube and the reaction was heated at 105° C. for 21.5 h. The reaction was taken up in ether (100 mL) and washed with H2O (30 mL) and brine (30 mL). The organic phase was dried over MgSO4, filtered and concentrated under vacuum. The crude product was purified by column chromatography on silica gel using hexanes/ethyl acetate as eluant to afford compound 2 (shown below in Table 1) as a yellowish oil (239 mg, 98%) after drying under vacuum. 1 H NMR (CDCl3): δ6.33 (br, 3H, ArH), 3.25 (t, J=7.6, 2H, —NCH2—), 2.89 (s, 3H, —N—CH3), 2.27 (s, 6H, Ar(CH3)2), 1.54 (br, 2H, —NCH2CH2—), 1.30 (br, 8H, —(CH2)4CH3), 0.89 (br t, J=6.6, 3 H, —CH3).

Workup

  1. customamination reaction
  2. customwas thoroughly evacuated
  3. custompurged with argon
  4. washwashed with H2O (30 mL) and brine (30 mL)
  5. dry with materialThe organic phase was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under vacuum
  8. customThe crude product was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-d754c5f64d364befb0237a6127282d32
Source dataset
uspto-grants-2001_07
Patent number
US06268513B1

Reaction notes

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