Carbazole → HCID 66780455、化合物

HRID 572955ノート

反応式

HRID 572955 の反応式
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[C:14](Br)([CH2:17][C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:16])[CH3:15]>[N+](C)([O-])=O.C1(C)C=CC=CC=1.[Cl-].[Cl-].[Zn+2]>[CH3:19][C:18]([CH3:21])([CH2:17][CH:14]([CH3:16])[CH3:15])[CH2:20][C:3]1[CH:2]=[CH:1][C:13]2[NH:12][C:11]3[C:6]([C:5]=2[CH:4]=1)=[CH:7][C:8]([CH2:19][C:18]([CH3:21])([CH3:20])[CH2:17][CH:14]([CH3:16])[CH3:15])=[CH:9][CH:10]=3

参加物

6

反応物 2

HCID 6854CarbazoleHCID 11435470Pentane, 2-bromo-2,4,4-trimethyl-

生成物 1

HCID 66780455HCID 66780455、化合物

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 1140Toluene溶媒HCID 6375Nitromethane溶媒

実験手順

ZnCl2 (36.8 g, 276 mmol) and carbazole (21.0 g, 126 mmol) are suspended in 600 mL nitromethane in a 1 qt jar in a glove-box. The t-octyl bromide (53.4 g, 276 mmol) is added dropwise to the gray-green suspension via addition funnel. The mixture turns into a black solution during the addition. The solution is allowed to stir at room temperature for two hours and then poured into 500 mL ice water. The product is extracted out of the mixture with 500 mL and 250 mL CH2Cl2. The combined organic portions are dried with MgSO4, filtered and rotovapped to yield a dark residue. This residue is taken up in 200 mL toluene, passed through a plug of silica, and washed through with 150 mL toluene. The yellow solution is reduced to a solid on the rotovap. This material is recrystallized from 100 mL hexane at −13° C. 27 g (55%) of white crystals are collected. The crystallization only moderately improved the purity of the product. 1H NMR (CDCl3): δ 8.02 (d, JH-H=1.6 Hz, 2H), 7.80 (br s, 1H, NH), 7.42 (dd, JH-H=8.6, 1.8 Hz, 2H), 7.29 (d, JH-H=8.5 Hz, 2H), 1.83 (s, 4H, CH2), 1.49 (s, 12H, CMe2), 0.72 (s, 18H, CMe3).

後処理

  1. additionThe mixture turns into a black solution during the addition
  2. extractionThe product is extracted out of the mixture with 500 mL and 250 mL CH2Cl2
  3. dry with materialThe combined organic portions are dried with MgSO4
  4. filtrationfiltered
  5. customto yield a dark residue
  6. washwashed through with 150 mL toluene
  7. customThis material is recrystallized from 100 mL hexane at −13° C
  8. custom27 g (55%) of white crystals are collected
  9. customThe crystallization

出典と根拠

ORDレコード
ord-d6d47f43c6664eb0b1819f204c75ad96
出典データセット
uspto-grants-2015_05
特許番号
US09029487B2

反応ノート

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