Tetrabutylammonium Fluoride → HCID 86751071, compound

HRID 265320Notes

Reaction equation

HRID 265320 reaction equation
[Si]([O:8][CH2:9][C:10]1[S:11][S:12][C:13]([C:16]2[N:20]([C:21]3[CH:26]=[CH:25][C:24]([OH:27])=[CH:23][CH:22]=3)[N:19]([S:28][CH3:29])[NH:18][N:17]=2)=[CH:14][CH:15]=1)(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1.C(O)(=O)C>[OH:8][CH2:9][C:10]1[S:11][S:12][C:13]([C:16]2[N:20]([C:21]3[CH:26]=[CH:25][C:24]([OH:27])=[CH:23][CH:22]=3)[N:19]([S:28][CH3:29])[NH:18][N:17]=2)=[CH:14][CH:15]=1

Participants

5

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 86751072HCID 86751072, compound

Product 1

HCID 86751071HCID 86751071, compoundYield 79.8%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a stirred solution of the 3-[(tert-butyldimethylsilyloxy)methyl]-6-[methylthio-[1-(4-hydroxyphenyl)-tetrazol-5-yl]]-1,2-dithiin obtained above (440 mg, 0.94 mmol) in 4 mL of THF was added a solution of 7 mL of 1M tetrabutylammonium fluoride in THF and 4 mL of acetic acid. The reaction mixture was stirred for 1 h at 0° C. until TLC analysis showed the reaction to be complete, then concentrated in vacuo. The residue was partitioned between 60 mL of water and 90 mL ethyl acetate. The organic phase was washed with dilute aqueous sodium bicarbonate, water, dried over sodium sulfate, and then concentrated to a small volume. The residue was purified by flash chromatography (ethyl acetate-hexane, 1:3) to yield 265 mg (79.8%) of the title compound as yellow crystals, mp 130°-131° C.; 1H-NMR (CD3OD) δ7.36 (d, J=9.2, 2 H), 6.97 (d, J=9.2, 2 H), 6.47 (d, J=6.0, 1 H), 6.34 (d, J=6.4, 1 H) 4.24 (s 2 H), 4.15 (s, 2 H); 1H-NMR (DMSO-d6):10.26 (s, 1 H, phenol OH), 7.41 (d, 2 H, J=8.8), 6.97 (d, 2 H, J=8.8), 6.52 (d, 1 H, J=6.0), 6.35 (d, 1 H, J=6.0), 5.39 (t, 1 H, J=5.2), 4.30 (s, 2 H), 4.06 (d, 2 H, J=5.2); 13C--NMR (CD3OD) δ160.99, 154.90, 138.09, 130.34, 129.49 127.42, 126.05, 125.77, 117.29, 64.67, 40.01; 1H-NMR NOESY showed an interaction between aromatic and dithiin rings protons. MS (+FAB) 353.5 (MH+); IR (KBr) 3378.7 (OH); 3135 (OH)cm-1. HMBC (DMSO-d6) shows a long range correlation between the protons at 4.30 ppm and the carbon at 154.90 ppm. Anal. calcd for C13H12N4O2S3 :C, 44.30; H, 3.43; N, 15.90; S, 27.29. Found:C, 44.68; H, 3.37; N, 16.24; S, 27.23.

Workup

  1. customthe reaction
  2. concentrationconcentrated in vacuo
  3. customThe residue was partitioned between 60 mL of water and 90 mL ethyl acetate
  4. washThe organic phase was washed with dilute aqueous sodium bicarbonate, water
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated to a small volume
  7. customThe residue was purified by flash chromatography (ethyl acetate-hexane, 1:3)

Sources & evidence

ORD record
ord-d56af8b693c54eba890ddb896ca1ec20
Source dataset
uspto-grants-1997_07
Patent number
US05648354

Reaction notes

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