Triethylamine → 4-(3,6-Dimethyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-2-methyl-benzonitrile

HRID 220957ノート

反応式

HRID 220957 の反応式
CC1[O:11][C:10]2[C:9]3[CH:12]=[CH:13][CH:14]=[CH:15][C:8]=3NCCC=2N=1.S(Cl)(Cl)=O.[CH3:20][N:21]1[C:30]2[NH:29][C:28]3[CH:31]=[C:32]([CH3:35])[CH:33]=[CH:34][C:27]=3[NH:26][CH2:25][C:24]=2[CH:23]=[N:22]1.C([N:38]([CH2:41][CH3:42])CC)C>C1(C)C=CC=CC=1.ClCCl>[CH3:20][N:21]1[C:30]2[NH:29][C:28]3[CH:31]=[C:32]([CH3:35])[CH:33]=[CH:34][C:27]=3[N:26]([C:10]([C:9]3[CH:12]=[CH:13][C:42]([C:41]#[N:38])=[C:15]([CH3:14])[CH:8]=3)=[O:11])[CH2:25][C:24]=2[CH:23]=[N:22]1

参加物

7

反応物 4

HCID 8471TriethylamineHCID 24386Thionyl ChlorideHCID 231123652-methyl-5,6-dihydro-4H-benzo[b]oxazolo[5,4-d]azepineHCID 1357360353,6-Dimethyl-3,4,9,10-tetrahydro-2,3,4,9-tetraaza-benzo[f]azulene

生成物 1

HCID 1357360404-(3,6-Dimethyl-4,10-dihydro-3H-2,3,4,9-tetraaza-benzo[f]azulene-9-carbonyl)-2-methyl-benzonitrile収率 85%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 6344Dichloromethane溶媒

実験手順

A mixture of 4-cyano-3-methyl-benzoic acid from Example E6 (753 mg, 4.7 mmol) and thionyl chloride (1.02 ml, 14.0 mmol) in toluene (50 ml) was heated at reflux for 2 h. After cooling at room temperature, solvents were re-moved in vacuo and azeotroped with toluene. The residue was redissolved in dichloromethane (45 ml) and a solution of 3,6-dimethyl-3,4,9,10-tetrahydro-2,3,4,9-tetraaza-benzo[f]azulene from Example E2 (11.0 g, 4.7 mmol) in dichloromethane (5 ml) and triethylamine (1.3 ml, 9.3 mmol) was added slowly. The mixture was stirred at room temperature for 20 h, washed with brine, dried and concentrated in vacuo. The residue was purified by flash chromatography on silica gel through an isolute (eluant; EtOAc) to yield the title compound (1.42 g, 85%).

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 2 h
  3. customazeotroped with toluene
  4. dissolutionThe residue was redissolved in dichloromethane (45 ml)
  5. washwashed with brine
  6. customdried
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by flash chromatography on silica gel through an isolute (eluant; EtOAc)

出典と根拠

ORDレコード
ord-3ca72dc839004bcdba630ed3dd0dc1a2
出典データセット
uspto-grants-2012_06
特許番号
US08202858B2

反応ノート

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