Azobisisobutyronitrile → HCID 23507935, compound

HRID 381608Notes

Reaction equation

HRID 381608 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([N:9]([C:16]2[C:25]3[CH2:24][CH2:23][CH2:22][CH2:21][C:20]=3[CH:19]=[CH:18][CH:17]=2)[C:10](=[O:15])[C:11]([F:14])([F:13])[F:12])=[CH:5][CH:4]=1)#[N:2].BrN1C(=O)CCC1=O.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)(Cl)(Cl)Cl.CN(C=O)C>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([N:9]([C:16]2[C:25]3[CH2:24][CH2:23][CH:22]=[CH:21][C:20]=3[CH:19]=[CH:18][CH:17]=2)[C:10](=[O:15])[C:11]([F:14])([F:13])[F:12])=[CH:5][CH:4]=1)#[N:2]

Participants

6

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 23507966HCID 23507966, compound

Product 1

HCID 23507935HCID 23507935, compound

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of N-(4-cyanophenyl)-N-(5,6,7,8-tetrahydro-1-naphthyl)-2,2,2-trifluoro acetamide (10.7 g, 31.1 mmol), N-bromosuccinimide (6.6 g, 37 mmol), and AIBN (200 mg, 1.2 mmol) in CCl4 (300 ml) was stirred at reflux under nitrogen for 1 hour. After cooling the solution was filtered, concentrated in vacuo to a volume of ˜25 ml, and applied to a column of silica gel. Elution with ethyl acetate:hexane (1:10) gave a mixture of benzylic bromides (10.7 g). A solution of the bromides and Li2CO3 (5.0 g, 68 mmol) in DMF (50 ml) was stirred at 110-120° C. under nitrogen for 3 hours and then overnight at room temperature. The solution was concentrated in vacuo and the residue taken up in methylene chloride (150 ml) and washed with water (50 ml). The aqueous phase was separated, extracted with more methylene chloride (100 ml), and the combined organic solutions were then washed with a small volume of water, dried (K2CO3) and concentrated in vacuo. The residue was purified by chromatography on silica gel eluting with ethyl acetate:hexane (1:13) to give N-(4-cyanophenyl)-N-(7,8-dihydro-1-naphthyl)-2,2,2-trifluoroacetamide and the corresponding 5,6,-dihydro isomer in a 3:1 ratio as determined by NMR. (4.3 g). 1H NMR (DMSO-d6, 200 MHz) δ: 2.10-2.46 (m, 3H, CH2), 2.63-2.89 (m, 1H, CH2), 6.03-6.22 (m, 1H, CH), 6.41 (dt, J=10,2 Hz, 0.25H, CH), 6.48 (dt, J=10,2 Hz, 0.75H, CH), 7.08-7.33 (m, 3H, Ar), 7.41 (d, J=9 Hz, 2H, Ar), 7.64 (d, J=9 Hz, 2H, Ar). Anal. Calculated for C19H13F3N2O: C, 66.67; H, 3.83; N, 8.18. Found: C, 66.55; H. 3.86; N, 8.10.

Workup

  1. temperatureat reflux under nitrogen for 1 hour
  2. temperatureAfter cooling the solution
  3. filtrationwas filtered
  4. concentrationconcentrated in vacuo to a volume of ˜25 ml
  5. washElution with ethyl acetate:hexane (1:10)
  6. customgave
  7. customovernight
  8. customat room temperature
  9. concentrationThe solution was concentrated in vacuo
  10. washwashed with water (50 ml)
  11. customThe aqueous phase was separated
  12. extractionextracted with more methylene chloride (100 ml)
  13. washthe combined organic solutions were then washed with a small volume of water
  14. dry with materialdried (K2CO3)
  15. concentrationconcentrated in vacuo
  16. customThe residue was purified by chromatography on silica gel eluting with ethyl acetate:hexane (1:13)

Sources & evidence

ORD record
ord-025a66987f5d4592ad270bcc8617f5ed
Source dataset
uspto-grants-2001_10
Patent number
US06306865B1

Reaction notes

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