Trimethylsilylacetylene → HCID 639597, compound

HRID 411301Notes

Reaction equation

HRID 411301 reaction equation
[CH3:1][O:2][C:3]1[C:16]2[C:7](=[N:8][C:9]3[C:14]([C:15]=2OS(C(F)(F)F)(=O)=O)=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:6]([O:25][CH3:26])=[CH:5][CH:4]=1.C(N(CC)C(C)C)(C)C.[CH3:36][Si:37]([C:40]#[CH:41])([CH3:39])[CH3:38]>O1CCCC1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][O:2][C:3]1[C:16]2[C:7](=[N:8][C:9]3[C:14]([C:15]=2[C:41]#[C:40][Si:37]([CH3:39])([CH3:38])[CH3:36])=[CH:13][CH:12]=[CH:11][CH:10]=3)[C:6]([O:25][CH3:26])=[CH:5][CH:4]=1

Participants

6

Reactant 3

HCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 10500406HCID 10500406, compound

Product 1

HCID 639597HCID 639597, compoundYield 98%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 1,4-dimethoxy-9-trifluoromethylsulfonyloxyacridine (prepared as described in Preparation 1 above) (1.2 g, 3.1 mmol) in dry tetrahydrofuran (10 ml) under N2 were successively added tetrakis(triphenylphosphine) palladium (0), (0.3 g, 0.3 mmol), N,N-diisopropylethylamine (1.6 ml, 9.3 mmol) and trimethylsilylacetylene (1.3 ml, 9.3 mmol). The mixture was stirred at reflux for 5 h. After this time the solvent was evaporated and the residue was dissolved in CH2Cl2 and washed with water. The organic solution was dried an evaporated affording a residue which was purified by column chromatography. Elution with hexane/CH2Cl2 (1:1) gave the title compound (1.0 g, 98%) as a red solid; m.p. 110-111° C. (CH2Cl2). IR (film): ν/cm−1=2810 (w, C≡C), 1608 (s, Ar), 1527 (m, Ar), 1468 (s, Ar); 1H NMR (200 MHz, CDCl3): δH/ppm=0.41 (s, 9H, 3×CH3), 3.99 (s, 3H, OCH3), 4.11 (s, 3H, OCH3), 6.75 (d, J=8.4 Hz, 1H, H-2), 6.93 (d, J=8.4 Hz, 1H, H-3), 7.63 (dd, J=8.0 and 7.2 Hz, 1H, H-7), 7.78 (dd, J=8.4 and 7.2 Hz, 1H, H-6), 8.35 (d, J=8.4 Hz, 1H, H-5), 8.64 (d, J=8.0 Hz, 1H, H-8); 13C NMR (50.3 MHz, CDCl3): δC=0.0 (q, CH3), 55.8 (q, OCH3), 56.1 (q, OCH3), 101.5 (s, ≡C—Si), 103.9 (d, C-2), 105.7 (d, C-3), 111.8 (s, ≡C), 120.5 (s, C-9a), 126.4 (d, C-7), 126.9 (d, C-6), 127.5 (s, C-9), 129.9 (d, C-5), 130.0 (s, C-8a), 130.3 (d, C-8), 142.1 (s, C-4a), 147.0 (s, C-1), 149.4 (s, C-4 and C-10a); MS (EI); m/z (%)=336 [M+1] (10), 335 [M+] (36), 320 (100), 306 (13), 290 (10), 262 (14); HRMS: calcd. for C20H21NO2Si 335.1341; found 335.1336; Elemental analysis: C20H21NO2Si.0.125CH2Cl2 (346.10): calcd. C 69.84, H, 6.19, N, 4.05; found C 69.70, H 6.42, N 4.09.

Workup

  1. temperatureat reflux for 5 h
  2. customAfter this time the solvent was evaporated
  3. dissolutionthe residue was dissolved in CH2Cl2
  4. washwashed with water
  5. customThe organic solution was dried an evaporated
  6. customaffording a residue which
  7. customwas purified by column chromatography
  8. washElution with hexane/CH2Cl2 (1:1)

Sources & evidence

ORD record
ord-9fa39418311e455c9dc01d89b8d2b2b0
Source dataset
uspto-grants-2003_05
Patent number
US06559161B1

Reaction notes

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