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

HRID 849303Notes

Reaction equation

HRID 849303 reaction equation
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]

Participants

8

Reactant 4

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

Product 1

HCID 195916263-Azido-3'-tert-butoxycarbonylbiphenylYield 89.1%

Reagents, catalysts & solvents 3

HCID 7187Benzoyl PeroxideCatalystHCID 962WaterSolventHCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
80 °C

Procedure

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.

Workup

  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)

Sources & evidence

ORD record
ord-6e07863a183f493e82ed4fe83a44ecb6
Source dataset
uspto-grants-2000_01
Patent number
US06011175

Reaction notes

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