Nitrogen → HCID 20195687, compound

HRID 653167Notes

Reaction equation

HRID 653167 reaction equation
N#N.[CH:3]1[C:6]2[CH:7]=[CH:8][C:9]([N:11]3[C:15](=[O:16])[C:14]4=[CH:17][C:18](Br)=[CH:19][CH:20]=[C:13]4[C:12]3=[O:22])=[CH:10][C:5]=2[CH:4]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:42][Si:43]([C:46]#[CH:47])([CH3:45])[CH3:44]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CCN(CC)CC>[CH:3]1[C:6]2[CH:7]=[CH:8][C:9]([N:11]3[C:15](=[O:16])[C:14]4=[CH:17][C:18]([C:47]#[C:46][Si:43]([CH3:45])([CH3:44])[CH3:42])=[CH:19][CH:20]=[C:13]4[C:12]3=[O:22])=[CH:10][C:5]=2[CH:4]=1

Participants

7

Reactant 4

HCID 947NitrogenHCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 20195685HCID 20195685, compound

Product 1

HCID 20195687HCID 20195687, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolvent

Procedure

In a 100 ml 3 necked round-bottomed flask, equipped with a thermometer, reflux condensor and N2 -adaptor, were placed N-4-benzocyclobutenyl 4-bromophthalimide (4.00 g, 12.2 mmol), palladium acetate (24 mg), triphenylphosphine (48 mg) and 60 ml of dry NEt3. The resultant reaction mixture was refluxed under N2 for about 15 minutes. Then, it was allowed to cool slowly to room temperature under N2. Trimethylsilylacetylene (2.50g, 25.4 mmol) was introduced into the reaction mixture via the reflux condensor. Immediately, the quantitative amount of white solids precipitated. The reaction mixture was then heated at 100° C. for about 3 hrs and stirred at room temperature overnight under N2. The brown heterogeneous mixture was poured into about 300 ml of H2O and extracted with CH2Cl2 (2×100 ml+2×50 ml). The CH2Cl2 extract was then washed with 200 ml H2O and dried over MgSO 4. Upon removal of the solvent, a mixture of white and brown solids was obtained. The mixture was washed with approximately 250 ml of H2O and air dried for an hour. It was then dissolved in 50 ml CH2Cl2 and the resultant solution was passed through a short column containing 25 g of silica gel saturated with hexane. Elution with 1:1 CH2Cl2 /hexane led to the isolation of microcrystalline tan solid from the first fraction. Yield=4.0 g (95%) mp=192-193° C. Calc. for C21H19NO2Si: 73.01% C; 5.54% H; 4.05% N. Found: 72.95% C; 5.45% H; 4.01% N. Mass Spectroscopy: 345 (M+, 100%). Proton NMR (CDCl3) 0.30 (Singlet, Me3Si--); 3.24 (Singlet, alicyclic protons); 7.10-7.29, 7.92-8.06 (complex, aromatic protons). IR(KBr): 2960 m, 2930 m (aliphatic and alicyclic C--H stretches); 2175 w (C≡C stretch); 1712, 1772 (symmetric and asymmetric stretches of imide group).

Workup

  1. customThe resultant reaction mixture
  2. temperaturewas refluxed under N2 for about 15 minutes
  3. customImmediately, the quantitative amount of white solids precipitated
  4. temperatureThe reaction mixture was then heated at 100° C. for about 3 hrs
  5. additionThe brown heterogeneous mixture was poured into about 300 ml of H2O
  6. extractionextracted with CH2Cl2 (2×100 ml+2×50 ml)
  7. extractionThe CH2Cl2 extract
  8. washwas then washed with 200 ml H2O
  9. dry with materialdried over MgSO 4
  10. customUpon removal of the solvent
  11. additiona mixture of white and brown solids
  12. customwas obtained
  13. washThe mixture was washed with approximately 250 ml of H2O and air
  14. customdried for an hour
  15. dissolutionIt was then dissolved in 50 ml CH2Cl2
  16. additioncontaining 25 g of silica gel saturated with hexane
  17. washElution with 1:1 CH2Cl2 /hexane

Sources & evidence

ORD record
ord-3d6d132e29df459a87eac8a7149d9cd5
Source dataset
uspto-grants-1987_06
Patent number
US04675370

Reaction notes

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