2-Bromobenzonitrile → 2-(10,11-Dihydro-dibenzo[a,d]cyclohepten-5-ylidenemethyl)-benzonitrile

HRID 2218639Notes

Reaction equation

HRID 2218639 reaction equation
[CH2:1]=[C:2]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[CH2:6][CH2:5][C:4]2[CH:13]=[CH:14][CH:15]=[CH:16][C:3]1=2.Br[C:18]1[CH:25]=[CH:24][CH:23]=[CH:22][C:19]=1[C:20]#[N:21].CC([O-])=O.[Na+]>CC(N(C)C)=O>[CH:12]1[C:7]2[CH2:6][CH2:5][C:4]3[CH:13]=[CH:14][CH:15]=[CH:16][C:3]=3[C:2](=[CH:1][C:18]3[CH:25]=[CH:24][CH:23]=[CH:22][C:19]=3[C:20]#[N:21])[C:8]=2[CH:9]=[CH:10][CH:11]=1

Participants

5

Reactant 3

HCID 162722-BromobenzonitrileHCID 517045Sodium AcetateHCID 46413975-Methylene-10,11-dihydro-5H-dibenzo[a,d][7]annulene

Product 1

HCID 689329272-(10,11-Dihydro-dibenzo[a,d]cyclohepten-5-ylidenemethyl)-benzonitrile

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Procedure

Sparge a mixture of 5-methylene-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2.0 g, 9.7 mmol) (prepared as described in Journal of Organic Chemistry, 53 (8) 1768-1774 (1988)), 2-bromobenzonitrile ((1.77 g, 9.7 mmol), NaOAc (1 g, 12 mmol) and dimethylacetamide (100 mL) with nitrogen for 15 minutes. Add Hermann catalyst (320 mg, 0.46 mmol)(Chem. Eur. J. 1357-1364 (1997)) and heat at 150° C. for 6 days. Cool the reaction and partition between water (1 L) and EtOAc (500 mL). Wash the organic layer with water (3×1L). Dry (MgSO4) and concentrate under reduced pressure to give 3.3 g brown oil. Purify on silica gel using EtOAc/hexane 500 mg nitrile that is 81% pure by glc. Recrystallize (EtOH) to give 213 mg (7%) pale yellow plates, mp 185.4° C. 1H NMR (CDCl3) δ 3.04 (br d, 2H), 3.47 (br s, 2H), 6.82-7.34 (m, 11H), 7.62 (m, 2H); MS (ES) 308 (M+1). HPLC shows 98% purity.

Workup

  1. customSparge
  2. temperatureCool
  3. customthe reaction
  4. custompartition between water (1 L) and EtOAc (500 mL)
  5. washWash the organic layer with water (3×1L)
  6. dry with materialDry (MgSO4)
  7. concentrationconcentrate under reduced pressure

Sources & evidence

ORD record
ord-966b685e339b4be3ab1d10b72ba3dbde
Source dataset
uspto-grants-2008_08
Patent number
US07411072B2

Reaction notes

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