Chloroform → HCID 16104627, compound

HRID 599524Notes

Reaction equation

HRID 599524 reaction equation
[I:1][CH2:2][CH2:3][CH2:4][CH2:5][C:6]12[O:13][CH2:12][C:9]([CH3:14])([CH2:10][O:11]1)[CH2:8][O:7]2.[C:15]1([P:21]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.S1(CCCC1)(=O)=O.C(Cl)(Cl)Cl>CO.CCOC(C)=O.CCOCC.N1C=CC=CC=1>[I-:1].[CH3:14][C:9]12[CH2:12][O:13][C:6]([CH2:5][CH2:4][CH2:3][CH2:2][P+:21]([C:22]3[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=3)([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=3)([O:11][CH2:10]1)[O:7][CH2:8]2

Participants

9

Reactant 4

HCID 6212ChloroformHCID 11776TriphenylphosphineHCID 31347SulfolaneHCID 15337132HCID 15337132, compound

Product 1

HCID 16104627HCID 16104627, compound

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 1049PyridineSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
80 °C

Procedure

In a 250 mL flask, 1-(4-iodobutyl)-4-methyl-2,6,7-trioxabicyclo[2.2.2]octane prepared according to process described in U.S. Pat. No. 5,538,995 (15.8 g, 50.6 mM), triphenylphosphine (14.6 g, 55.66 mM), sulfolane (20 mL) and C5H5N (0.10 mL) were placed under argon. The content of the flask was stirred and heated under argon at 80° C. After 70 minutes, the mixture was cooled to 40° C. and CHCl3 containing 0.3% of pyridine (70 mL) was added. This solution was added dropwise over 10 minutes to the mixture of Et2O (1.5 L) and EtOAc (0.6 L) and vigorously stirred under argon. The reaction mixture was vigorously stirred (600 r.p.m.) for 15 minutes at room temperature, then it was stirred more slowly (150 r.p.m.) for 15 minutes, and the solution was decanted. The thus obtained precipitate was dissolved in CHCl3 containing 0.2% of C5H5N (75 mL). This solution was added dropwise to vigorously stirred mixture of Et2O (1.2 L) and EtOAc (0.5 L). It was stirred under argon at room temperature. After 20 minutes, stirring was stopped. After 10 minutes, the solution was decanted, the precipitate was washed with Et2O (100 mL) and Et2O layer was decanted again. The obtained precipitate was dried under vacuum (1 mm Hg, 25° C., 1.5 h). The crude product (28.95 g, 100%) was obtained. This sample was dissolved in MeOH containing 0.04% of C5H5N (35 mL), EtOAc containing 0.04% of C5H5N (65 mL) was added and it was allowed for crystallization at +4° C. After 1.5 h, the precipitate was filtered and dried (1 mm Hg, 25° C., 1 h). [4-(4-methyl-2,6,7-trioxabicyclo[2.2.2]oct-1-yl)butyl]triphenylphosphonium iodide was obtained (14.01 g, 48.3%) as colourless, thick prisms, t.t.=130-134° C.; 1H-NMR (CDCl3; 200 MHz) 6; 0.78 (3H, s), 1.58-1.80 (6H, m), 3.45 (2H, m), 3.79 (6H, s), 7.70-7.88 (15H, m); 13C-NMR (CDCl3; 50 MHz) δ 14.5, 21.7 (d: 4.0 Hz), 22.7 (d: 50.8 Hz), 24.0 (d: 16.8 Hz), 30.2, 34.7, 72.3 (3×C), 108.5, 117.8 (3×C, d: 86 Hz), 130.5 (6×C, d: 12.4 Hz), 133.5 (6×C, d: 10.0 Hz), 135.1 (3×C, d: 2.8 Hz).

Workup

  1. temperaturethe mixture was cooled to 40° C.
  2. stirringvigorously stirred under argon
  3. stirringThe reaction mixture was vigorously stirred (600 r.p.m.) for 15 minutes at room temperature
  4. stirringit was stirred more slowly (150 r.p.m.) for 15 minutes
  5. customthe solution was decanted
  6. dissolutionThe thus obtained precipitate was dissolved in CHCl3 containing 0.2% of C5H5N (75 mL)
  7. additionThis solution was added dropwise to vigorously stirred mixture of Et2O (1.2 L) and EtOAc (0.5 L)
  8. stirringIt was stirred under argon at room temperature
  9. waitAfter 20 minutes
  10. stirringstirring
  11. waitAfter 10 minutes
  12. customthe solution was decanted
  13. washthe precipitate was washed with Et2O (100 mL) and Et2O layer
  14. customwas decanted again
  15. customThe obtained precipitate was dried under vacuum (1 mm Hg, 25° C., 1.5 h)
  16. customThe crude product (28.95 g, 100%) was obtained
  17. additionwas added
  18. customit was allowed for crystallization at +4° C
  19. waitAfter 1.5 h
  20. filtrationthe precipitate was filtered
  21. customdried (1 mm Hg, 25° C., 1 h)

Sources & evidence

ORD record
ord-18e454bfd6e048bbad5348ffdde6df2d
Source dataset
uspto-grants-2011_03
Patent number
US07897793B2

Reaction notes

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