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4-Bromotoluene → Ethyl 4-[(5,6-dihydro-5,5-dimethyl-8-(4-methylphenyl)-2-naphthalenyl)azo]-benzoate

HRID 495948
ノート
印刷プレビュー

反応式

HRID 495948 の反応式
[C:1]([Li:5])([CH3:4])([CH3:3])[CH3:2].Br[C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=1.[CH3:14][C:15]1(C)CC=C(OS(C(F)(F)F)(=O)=O)[C:21]2[CH:20]=[C:19]([N:33]=[N:34][C:35]3[CH:45]=[CH:44][C:38]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:37][CH:36]=3)[CH:18]=[CH:17][C:16]1=2>C1COCC1.[NH4+].[Cl-].[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Li:5][C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=1.[CH3:2][C:1]1([CH3:4])[CH2:14][CH:15]=[C:16]([C:7]2[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=2)[C:17]2[CH:18]=[C:19]([N:33]=[N:34][C:35]3[CH:36]=[CH:37][C:38]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:44][CH:45]=3)[CH:20]=[CH:21][C:3]1=2
参加物実験手順後処理出典と根拠反応ノート

参加物

9

反応物 3

HCID 78054-BromotolueneHCID 22323756Ethyl 4-[(5,6-dihydro-5,5-dimethyl-8-trifluoromethylsulfonyloxy-naphthalen-2-yl)azo]benzoateHCID 178418306HCID 178418306、化合物

生成物 2

HCID 22323724Ethyl 4-[(5,6-dihydro-5,5-dimethyl-8-(4-methylphenyl)-2-naphthalenyl)azo]-benzoateHCID 178506695HCID 178506695、化合物

試薬・触媒・溶媒 4

HCID 3007855
Zincchloride
触媒
HCID 178418397HCID 178418397、化合物触媒
HCID 8028Tetrahydrofuran溶媒3 回
HCID 25517Ammonium Chloride溶媒

実験手順

A solution of 4-lithiotoluene was prepared by the addition of 62.9 mg (0.58 ml 0.98 mmol) of t-butyl lithium (1.7 M solution in pentane) to a cold solution (−78° C.) of 84.0 mg (0.491 mmol) of 4-bromotoluene in 1.0 ml of THF. After stirring for 30 minutes a solution of 107.0 mg (0.785 mmol) of zinc chloride in 2.0 ml of THF was added. The resulting solution was warmed to room temperature, stirred for 30 minutes, and added via cannula to a solution of 94.7 mg (0.196 mmol) of ethyl 4-[(5,6-dihydro-5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-2-naphthalenyl)azo]-benzoate (Compound BB) and 25 mg (0.02 mmol) of tetrakis(triphenylphosphine)palladium(0) in 2.0 ml of THF. The resulting solution was heated at 50° C. for 1.5 hours, cooled to room temperature and diluted with sat. aqueous NH4Cl. The mixture was extracted with EtOAc (40 ml) and the combined organic layers were washed with water and brine. The organic phase was dried over Na2SO4, concentrated in vacuo, and the title compound isolated as a red solid by column chromatography (25% EtOAc-hexanes) 1H NMR (CDCl3): δ 8.21 (2H, d, J=8.6 Hz), 7.96 (2H, d, J=8.6 Hz), 7.94 (2H, m), 7.49 (1H, d, J=8.2 Hz), 6.08 (1H, t, J=2.5 Hz), 4.42 (2H, q, J=7.1 Hz), 2.49 (2H, d, J=4.8 Hz), 1.44 (3H, t, J=7.1 Hz), 1.38 (6H, s).

後処理

  1. additionwas added
  2. temperatureThe resulting solution was heated at 50° C. for 1.5 hours
  3. temperaturecooled to room temperature
  4. extractionThe mixture was extracted with EtOAc (40 ml)
  5. washthe combined organic layers were washed with water and brine
  6. dry with materialThe organic phase was dried over Na2SO4
  7. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-b64a411830054859b42bc5a19a440e41
出典データセット
uspto-grants-2005_09
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06942980B1

反応ノート

読み込み中…

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