Terpinolene → N,N,N',N'-Tetra(3-methylphenyl)-9,10-diaminophenanthrene

HRID 917802

反応式

HRID 917802 の反応式
[CH3:1][C:2]1[CH:3]=[C:4]([CH:28]=[CH:29][CH:30]=1)[NH:5][C:6]1[C:7]2[C:12]([C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][C:18]=3[C:19]=1[NH:20][C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([CH3:27])[CH:22]=1)=[CH:11][CH:10]=[CH:9][CH:8]=2.I[C:32]1[CH:33]=[C:34]([CH3:38])[CH:35]=[CH:36][CH:37]=1.[OH-].[K+].[CH3:41][C:42]1[CH2:50][CH2:49][C:45](=C(C)C)[CH2:44][CH:43]=1>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.[Cu]Br.CO.O1CCCC1>[CH3:1][C:2]1[CH:3]=[C:4]([N:5]([C:44]2[CH:45]=[CH:49][CH:50]=[C:42]([CH3:41])[CH:43]=2)[C:6]2[C:7]3[C:12]([C:13]4[CH:14]=[CH:15][CH:16]=[CH:17][C:18]=4[C:19]=2[N:20]([C:36]2[CH:37]=[CH:32][CH:33]=[C:34]([CH3:38])[CH:35]=2)[C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([CH3:27])[CH:22]=2)=[CH:11][CH:10]=[CH:9][CH:8]=3)[CH:28]=[CH:29][CH:30]=1

参加物

8

反応物 4

HCID 11463TerpinoleneHCID 122683-IodotolueneHCID 14797Potassium HydroxideHCID 19347451N~9~,N~10~-Bis(3-methylphenyl)phenanthrene-9,10-diamine

生成物 1

HCID 20734448N,N,N',N'-Tetra(3-methylphenyl)-9,10-diaminophenanthrene

試薬・触媒・溶媒 3

HCID 24593copper(I) bromide触媒HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)触媒HCID 21899815MeOH tetrahydrofuran溶媒

実験手順

9,10-Bis(3-methylanilino)phenanthrene was mixed in an amount of 6.6 g (17.0 mmol) with 14.8 g (68.0 mmol) of m-iodotoluene, 3.82 g (68 mmol) of potassium hydroxide, 0.98 g (6.8 mmol) of copper-(I) bromide, 2.52 g (6.8 mmol) of ethyltriphenylphosphonium bromide, and 10 mL of terpinolene. This mixture was reacted at 115-125° C. for 2 hours in a nitrogen stream. After the reaction, the reaction solvent was distilled off by vacuum concentration. To the residue were added 5 mL of toluene, 67 mL of ethyl acetate, and 22 mL of water. The resultant mixture was subjected to liquid separation. To the organic layer was added 71 mL of methanol. The resultant solution was cooled for crystallization. Thus, the target compound (I-22) was obtained as light-yellow crude crystals in an amount of 9.0 g (yield, 93.0%). The target compound obtained had a melting point of 223-224° C. and a content as determined by HPLC of 99.6% (HPLC conditions: column, YMC-A-312; eluent, methanol/tetrahydrofuran (V/V=99/1); detection UV, 254 nm; flow rate, 1.0 mL/min).

後処理

  1. customThis mixture was reacted at 115-125° C. for 2 hours in a nitrogen stream
  2. customAfter the reaction
  3. distillationthe reaction solvent was distilled off by vacuum concentration
  4. additionTo the residue were added 5 mL of toluene, 67 mL of ethyl acetate, and 22 mL of water
  5. customThe resultant mixture was subjected to liquid separation
  6. additionTo the organic layer was added 71 mL of methanol
  7. temperatureThe resultant solution was cooled for crystallization
  8. customThus, the target compound (I-22) was obtained as light-yellow crude crystals
  9. customin an amount of 9.0 g (yield, 93.0%)
  10. customThe target compound obtained

出典と根拠

ORDレコード
ord-3f91ae5a596443c381e3e84785efddf8
出典データセット
uspto-grants-2007_09
特許番号
US07273953B2

関連ノート

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