N,N'-Diphenyl-P-Phenylenediamine → N,N'-Diphenyl-N,N'-di(m-tolyl)-1,4-phenylenediamine

HRID 394823

Reaction equation

HRID 394823 reaction equation
[C:1]1([NH:7][C:8]2[CH:13]=[CH:12][C:11]([NH:14][C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.I[C:22]1[CH:23]=[C:24]([CH3:28])[CH:25]=[CH:26][CH:27]=1.C(O[Na])(C)(C)C.[CH3:35][C:36]1[CH:41]2C(C)(C)[CH:39]([CH2:40]2)[CH2:38][CH:37]=1>[Cu]Cl.C1(C2C=CC(C3C=CC=CN=3)=NC=2C2C=CC=CC=2)C=CC=CC=1.O.C1(C)C=CC=CC=1>[C:15]1([N:14]([C:38]2[CH:39]=[CH:40][CH:41]=[C:36]([CH3:35])[CH:37]=2)[C:11]2[CH:12]=[CH:13][C:8]([N:7]([C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[C:22]3[CH:27]=[CH:26][CH:25]=[C:24]([CH3:28])[CH:23]=3)=[CH:9][CH:10]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

9

Reactant 4

HCID 6319N,N'-Diphenyl-P-PhenylenediamineHCID 6654(+-)-alpha-PineneHCID 122683-IodotolueneHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 14250518N,N'-Diphenyl-N,N'-di(m-tolyl)-1,4-phenylenediamineYield 90.5%

Reagents, catalysts & solvents 4

HCID 62652Cuprous chlorideCatalystHCID 98614242-(5,6-Diphenyl-2-pyridyl)pyridineCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A mixture of 31.2 g (0.12 mole) of N,N′-diphenyl-N,N′-p-phenylenediamine, 54.5 g (0.25 mole) of m-iodotoluene, 32.6 g (0.34 mole) of t-butoxy sodium, 59.0 mg (0.6 mmole) of copper (I) chloride, 185 mg (0.6 mmole) of 2-(5,6-diphenyl-2-pyridyl)pyridine (A-8) and 87.6 ml of α-pinene was reacted at 125 to 130° C. for 5 hours under a nitrogen gas stream. After completion of the reaction, 66 ml of toluene and 66 ml of water were added to separate the reaction mixture. Toluene was then concentrated under reduced pressure. The residue was crystallized by the addition of 39 ml of ethyl acetate and 253 ml of isopropanol, whereby 47.8 g (yield: 90.5%) of the target compound was obtained as pale yellow crude crystals. The compound was found to have a melting point of 170 to 171° C. and an HPLC content (column: YMC-A-002, UV detector: 310 nm, eluent having a flow rate of 1.1 ml/min) was 99.5%.

Workup

  1. customwas reacted at 125 to 130° C. for 5 hours under a nitrogen gas stream
  2. additionwere added
  3. customto separate the reaction mixture
  4. concentrationToluene was then concentrated under reduced pressure
  5. customThe residue was crystallized by the addition of 39 ml of ethyl acetate and 253 ml of isopropanol

Sources & evidence

ORD record
ord-ec820f4221474c6e9e960e66d32ab375
Source dataset
uspto-grants-2003_08
Patent number
US06603007B1

Linked notes

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