Benzoyl Peroxide → 4-(4-Trifluoromethylbenzoyl)-3-chloro-5-methylbenzyl azide

HRID 280677Notes

Reaction equation

HRID 280677 reaction equation
[F:1][C:2]([F:21])([F:20])[C:3]1[CH:19]=[CH:18][C:6]([C:7]([C:9]2[C:14]([CH3:15])=[CH:13][C:12]([CH3:16])=[CH:11][C:10]=2[Cl:17])=[O:8])=[CH:5][CH:4]=1.BrN1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[N-:48]=[N+:49]=[N-:50].CN(C)C(=[NH2+])N(C)C>C(Cl)(Cl)(Cl)Cl>[F:21][C:2]([F:20])([F:1])[C:3]1[CH:4]=[CH:5][C:6]([C:7]([C:9]2[C:14]([CH3:15])=[CH:13][C:12]([CH2:16][N:48]=[N+:49]=[N-:50])=[CH:11][C:10]=2[Cl:17])=[O:8])=[CH:18][CH:19]=1.[F:21][C:2]([F:20])([F:1])[C:3]1[CH:4]=[CH:5][C:6]([C:7]([C:9]2[C:10]([Cl:17])=[CH:11][C:12]([CH3:16])=[CH:13][C:14]=2[CH2:15][N:48]=[N+:49]=[N-:50])=[O:8])=[CH:18][CH:19]=1

Participants

7

Reactant 4

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimide2×HCID 23320953HCID 23320953, compoundHCID 178484365HCID 178484365, compound

Product 2

HCID 233209604-(4-Trifluoromethylbenzoyl)-3-chloro-5-methylbenzyl azideYield 22%HCID 23320968HCID 23320968, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
0 °C

Procedure

A stirred mixture of 1-(4-trifluoromethylbenzoyl)-2-chloro-4,6-dimethylbenzene (6.90 g, 22.1 mmol), N-bromosuccinimide (3.94 g, 22.1 mmol), and dibenzoyl peroxide (224 mg, 0.925 mmol) in dry carbon tetrachloride (180 ml) was refluxed 44 hours. Additional N-bromosuccinimide (1.97 g, 11.1 mmol) was added and the mixture was refluxed 24 hours. The mixture was cooled to 0° C., filtered, and washed with carbon tetrachloride. The combined filtrate and washes were evaporated to dryness under vacuum, and the residue was dissolved in dichloromethane (135 ml), treated with tetramethylguanidinium azide (7.25 g, 45.8 mmol), and stirred 40 minutes at ambient temperature. Solvent was removed under vacuum and the residue was stirred with diethyl ether (180 ml). The mixture was filtered and the precipitate was washed with diethyl ether. The combined filtrate and washes were washed twice with water and once with brine, dried over anhydrous magnesium sulfate, and evaporated to dryness under vacuum. The residue was dissolved in hexane (300 ml) and decanted, and the residual gum was washed with hexane. The combined hexane layers were evaporated to dryness under vacuum. The residue was chromatographed on silica gel (500 g) eluted with 93:7 (v/v) hexane-ethyl acetate using a preparative high-performance liquid chromatograph to provide 1.71 g (22%) oily 4-(4-trifluoromethylbenzoyl)-3-chloro-5-methylbenzyl azide (A), 1.30 g (17%) 2-(4-trifluoromethylbenzoyl)-3-chloro-5-methylbenzyl azide (B), and 0.48 g of a mixture of A and B.

Workup

  1. temperaturewas refluxed 44 hours
  2. temperaturethe mixture was refluxed 24 hours
  3. filtrationfiltered
  4. washwashed with carbon tetrachloride
  5. customThe combined filtrate and washes were evaporated to dryness under vacuum
  6. dissolutionthe residue was dissolved in dichloromethane (135 ml)
  7. customSolvent was removed under vacuum
  8. stirringthe residue was stirred with diethyl ether (180 ml)
  9. filtrationThe mixture was filtered
  10. washthe precipitate was washed with diethyl ether
  11. washThe combined filtrate and washes were washed twice with water and once with brine
  12. dry with materialdried over anhydrous magnesium sulfate
  13. customevaporated to dryness under vacuum
  14. dissolutionThe residue was dissolved in hexane (300 ml)
  15. customdecanted
  16. washthe residual gum was washed with hexane
  17. customThe combined hexane layers were evaporated to dryness under vacuum
  18. customThe residue was chromatographed on silica gel (500 g)
  19. washeluted with 93:7 (v/v) hexane-ethyl acetate using a preparative high-performance liquid chromatograph

Sources & evidence

ORD record
ord-673d8b57282445f39d3f2ed7606f1fb0
Source dataset
uspto-grants-1986_05
Patent number
US04590201

Reaction notes

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