Dichloromethane → 3-Azido-3'-tert-butoxycarbonylbiphenyl

HRID 1739150ノート

反応式

HRID 1739150 の反応式
C[C:2]1[CH:3]=[C:4]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH:9]=2)[CH:5]=[CH:6][CH:7]=1.BrN1C(=O)CCC1=O.[N-:29]=[N+:30]=[N-:31].[Na+].C(Cl)Cl>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.O>[N:29]([C:2]1[CH:3]=[C:4]([C:8]2[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH:9]=2)[CH:5]=[CH:6][CH:7]=1)=[N+:30]=[N-:31]

参加物

8

反応物 4

HCID 6344DichloromethaneHCID 33557Sodium AzideHCID 67184N-bromobutanimideHCID 108018643-Methyl-3'-tert-butoxycarbonylbiphenyl

生成物 1

HCID 195916263-Azido-3'-tert-butoxycarbonylbiphenyl収率 89.1%

試薬・触媒・溶媒 3

HCID 7187Benzoyl Peroxide触媒HCID 962Water溶媒HCID 5943Carbon Tetrachloride溶媒

反応条件

温度
80 °C

実験手順

Compound 19 (2.18 g, 8.13 mmol) and N-bromosuccinimide (1.70 g, 9.50 mmol) was suspended in 60 mL of CCl4. Dibenzoyl peroxide (20 mg) was added and the mixture was refluxed for 1.5 hr. After removing the solid, the filtrate was washed with concentrated sodium bicarbonate and dried over sodium sulfate. 1H NMR showed the crude material contained 70% of monobrominated and 30% of dibrominated product. This material was dissolved in 20 mL of DMSO and sodium azide (3.70 g, 57 mmol) was added. The mixture was heated to 80° C. for 4 hr before being poured into a mixture of methylene chloride and water. The organic layer was dried and evaporated. The residue was purified by flash column chromatography (5% of ethyl acetate in hexane) to give 20 (2.14 g, 78%, two steps) as colorless oil. 1H NMR (CDCl3) δ 8.22 (s, 1H), 8.00 (d, 7.7 Hz, 1H), 7.76 (d, 8.2 Hz, 1H), 7.58 (m, 2H), 7.50 (m, 2H), 7.33 (d, 7.6 Hz, 1H), 4.43 (s, 2H), 1.62 (s, 9H). 13C NMR (CDCl3) δ 165.2, 140.5, 140.3, 135.8, 132.3, 130.7, 129.1, 128.5, 128.2, 127.8, 127.1, 126.7, 126.6, 80.9, 54.3, 27.8.

後処理

  1. temperaturethe mixture was refluxed for 1.5 hr
  2. customAfter removing the solid
  3. washthe filtrate was washed with concentrated sodium bicarbonate
  4. dry with materialdried over sodium sulfate
  5. dissolutionThis material was dissolved in 20 mL of DMSO
  6. customThe organic layer was dried
  7. customevaporated
  8. customThe residue was purified by flash column chromatography (5% of ethyl acetate in hexane)

出典と根拠

ORDレコード
ord-b813539f185d47ad962582722f08446b
出典データセット
uspto-grants-1999_10
特許番号
US05965539

反応ノート

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