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

HRID 1739150Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1739150
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]

Komponenten

8

Edukt 4

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

Produkt 1

HCID 195916263-Azido-3'-tert-butoxycarbonylbiphenylAusbeute 89,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 7187Benzoyl PeroxideKatalysatorHCID 962WaterLösungsmittelHCID 5943Carbon TetrachlorideLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

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.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-b813539f185d47ad962582722f08446b
Quelldatensatz
uspto-grants-1999_10
Patentnummer
US05965539

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