o-Bis(bromomethyl)benzene → 1-Tricyclo[8.2.1.03,8]trideca-3(8),4,6-trien-13-ylidene-pyrrolidinium bromide

HRID 902434Notes

Reaction equation

HRID 902434 reaction equation
[Br:1][CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[CH2:9]Br.[C:11]1([N:16]2[CH2:20][CH2:19][CH2:18][CH2:17]2)[CH2:15][CH2:14][CH2:13][CH:12]=1.CCN(C(C)C)C(C)C>CC#N>[Br-:1].[CH:12]12[C:11](=[N+:16]3[CH2:20][CH2:19][CH2:18][CH2:17]3)[CH:15]([CH2:14][CH2:13]1)[CH2:9][C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[CH2:2]2

Participants

5

Reactant 3

HCID 66665o-Bis(bromomethyl)benzeneHCID 81531DiisopropylethylamineHCID 81570Pyrrolidine, 1-(1-cyclopenten-1-yl)-

Product 1

HCID 179861911-Tricyclo[8.2.1.03,8]trideca-3(8),4,6-trien-13-ylidene-pyrrolidinium bromideYield 60.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

1,2-Bis-bromomethyl-benzene (66.4 g, 0.25 mol) was added to a mixture of 1-cyclopent-1-enyl-pyrrolidine (29.4 g, 0.25 mol) and Hünig's base (87 mL, 0.50 mol) in MeCN (200 mL) with vigorous stirring. An exothermic reaction ensued, bringing the mixture to reflux. The mixture was refluxed for 16 h, cooled, the product was filtered off and washed with MeCN to give the pure title compound as a white crystalline solid (48.14 g, 60%). 1H NMR (d6-DMSO, 360 MHz) δ 7.29-7.22 (4 H, m, aromatic), 4.16-4.11 (2 H, m, CH—N+), 4.04-3.99 (2 H, m, CH—N+), 3.60 (2 H, bs, bridgehead CH), 3.05 (4 H, d, benzylic), 2.17-2.05 (4 H, m, N+—C—CH2), 1.92-1.88 (2 H, m), 1.25-1.20 (2 H, m). m/z 240 (M+).

Workup

  1. customAn exothermic reaction
  2. temperatureto reflux
  3. temperatureThe mixture was refluxed for 16 h
  4. temperaturecooled
  5. filtrationthe product was filtered off
  6. washwashed with MeCN

Sources & evidence

ORD record
ord-28c584a845e548c1ac042ec78dead550
Source dataset
uspto-grants-2008_04
Patent number
US07365196B2

Reaction notes

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