Toluene → HCID 11505284, compound

HRID 917801Notes

Reaction equation

HRID 917801 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([NH:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:5]=[CH:6][CH:7]=1.I[C:16]1[CH:21]=[CH:20][C:19]([C:22]2[CH:27]=[CH:26][C:25]([C:28]3[CH:33]=[CH:32][C:31](I)=[CH:30][CH:29]=3)=[CH:24][CH:23]=2)=[CH:18][CH:17]=1.[OH-].[K+].[C:37]1([CH3:43])[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>[Br-].C([P+](CCCC)(CCCC)CCCC)CCC.[Cu]Cl.CCCCCC.O1CCCC1.O>[C:9]1([N:8]([C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([CH3:1])[CH:3]=2)[C:16]2[CH:21]=[CH:20][C:19]([C:22]3[CH:27]=[CH:26][C:25]([C:28]4[CH:33]=[CH:32][C:31]([N:8]([C:4]5[CH:5]=[CH:6][CH:7]=[CH:2][CH:3]=5)[C:39]5[CH:40]=[CH:41][CH:42]=[C:37]([CH3:43])[CH:38]=5)=[CH:30][CH:29]=4)=[CH:24][CH:23]=3)=[CH:18][CH:17]=2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

9

Reactant 4

HCID 1140Toluene2×HCID 14569N-(3-Methylphenyl)anilineHCID 14797Potassium HydroxideHCID 35635834,4''-Diiodo-p-terphenyl

Product 1

HCID 11505284HCID 11505284, compound

Reagents, catalysts & solvents 4

HCID 62652Cuprous chlorideCatalystHCID 76564Tetrabutylphosphonium bromideCatalystHCID 962WaterSolventHCID 21883165Tetrahydrofuran hexaneSolvent

Conditions

Temperature
52.5 °C

Procedure

N-(3-Methylphenyl)-N-phenylamine was mixed in an amount of 18.05 g (98.52 mmol) with 11.87 g (24.63 mmol) of 4,4″-diiodo-1,1′:4′,1″-terphenyl, 11.06 g (197.0 mmol) of potassium hydroxide, 0.4 g (4.0 mmol) of copper-(I) chloride, 1.36 g (4.0 mmol) of tetra-n-butylphosphonium bromide, and 10 mL of toluene. This mixture was reacted at 115-125° C. for 1 hour in a nitrogen stream. After the reaction, 25 mL of toluene and 50 mL of water were added and the resultant mixture was subjected to liquid separation. Thereafter, the organic layer was washed with water and dehydrated and dried with anhydrous sodium sulfate. After the drying agent was removed by filtration, 3.9 g of activated clay was added. The resultant mixture was stirred at 50-55° C. for 1 hour and the clay was removed by filtration. The toluene was distilled off under reduced pressure and 28 mL of ethyl acetate was added to the residue. The resultant solution was cooled for crystallization, and the precipitate was taken out by filtration. Thus, the target compound (I-11) was obtained as white crude crystals in an amount of 13.7 g (yield, 94.0%). The target compound obtained had a melting point of 189-190° C. and a content as determined by HPLC of 99.5% (HPLC conditions: column, YMC-A-002; eluent, hexane/tetrahydrofuran (V/V=97/3); detection UV, 310 nm; flow rate, 0.8 mL/min).

Workup

  1. customThis mixture was reacted at 115-125° C. for 1 hour in a nitrogen stream
  2. additionwere added
  3. customthe resultant mixture was subjected to liquid separation
  4. washThereafter, the organic layer was washed with water
  5. dry with materialdried with anhydrous sodium sulfate
  6. customAfter the drying agent was removed by filtration, 3.9 g of activated clay
  7. additionwas added
  8. customthe clay was removed by filtration
  9. distillationThe toluene was distilled off under reduced pressure and 28 mL of ethyl acetate
  10. additionwas added to the residue
  11. temperatureThe resultant solution was cooled for crystallization
  12. filtrationthe precipitate was taken out by filtration
  13. customThus, the target compound (I-11) was obtained as white crude crystals
  14. customin an amount of 13.7 g (yield, 94.0%)
  15. customThe target compound obtained

Sources & evidence

ORD record
ord-5526819cef1843f698b9a48b11dd41ae
Source dataset
uspto-grants-2007_09
Patent number
US07273953B2

Reaction notes

Loading…