Tetrabutylammonium Fluoride → HCID 66809409, compound

HRID 876351Notes

Reaction equation

HRID 876351 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:15][CH:14]([O:16][Si](C(C)(C)C)(C)C)[CH2:13][CH:12]1[C:24]([C:26]1[C:34]2[C:29](=[CH:30][C:31]([F:35])=[CH:32][CH:33]=2)[NH:28][CH:27]=1)=[O:25])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-].CCCC[N+](CCCC)(CCCC)CCCC.[F-].C1COCC1>C1COCC1>[CH2:1]([O:8][C:9]([N:11]1[CH2:15][CH:14]([OH:16])[CH2:13][CH:12]1[C:24]([C:26]1[C:34]2[C:29](=[CH:30][C:31]([F:35])=[CH:32][CH:33]=2)[NH:28][CH:27]=1)=[O:25])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 2724141Tetrabutylammonium FluorideHCID 11078149TBAF tetrahydrofuranHCID 66809681HCID 66809681, compound

Product 1

HCID 66809409HCID 66809409, compoundYield 24.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution containing 3 (227 g) in THF (600 mL) was added 1 M TBAF in THF (160 mL) at ambient temperature. After 9 h, another 20 mL of the 1 M TBAF/THF solution was added. After ca. 48 h, the reaction mixture was concentrated in vacuo and then redissolved in EtOAc (600 mL). The organic solution was washed with water (310 mL) and the product precipitated to form a thick suspension which was filtered (slow). The solids were washed with EtOAc (165 mL in portions) and dried to provide 43 g of 4. The combined filtrate was concentrated in vacuo to precipitate an additional 4.8 g of 4 after drying. 1H NMR (300 MHz, d6-DMSO), mixture of rotomers: δ12.08 (br s, 1H), 8.43 (d, J=10.5 Hz, 1H), 8.16 (ddd, J=5.4, 8.7, 14.1 Hz, 1H), 7.36-7.31 (m, 2H), 7.27 (app. d, J=10.2 Hz, 1H), 7.09-6.93 (m, 4H), 5.24 (dt, J=8.1, 15.6 Hz, 1H), 5.14 (br s, 1H), 5.04 (app. d, J=6.4 Hz, 1H), 4.90 (app. dd, J=13.4, 28.4 Hz, 1H), 4.30 (br s, 1H), 3.58-3.43 (m, 2H), 2.27 (m, 1H), 1.93 (m, 1H) ppm; 13C NMR (75 MHz, d6-DMSO), mixture of rotomers: δ194.0, 193.6, 159.9 (d, JCF=235.2 Hz), 154.6 (d, JCF=9.6 Hz), 138.1, 137.5 (d, JCF=26.9 Hz), 136.0, 129.0, 128.5, 128.1 (d, JCF=40.0 Hz), 123.4, 123.3, 123.0, 122.9, 114.4 (d, JCF=11.7 Hz), 110.6 (d, JCF=23.7 Hz), 99.3 (d, JCF=25.2 Hz), 69.5, 68.8, 66.4, 66.3, 61.4, 61.1, 56.2, 55.7 ppm. Mass spectrum (ESI), m/z 382.6 [(M)+; calcd for C21H19FN2O4: 382.3].

Workup

  1. waitAfter ca. 48 h
  2. concentrationthe reaction mixture was concentrated in vacuo
  3. dissolutionredissolved in EtOAc (600 mL)
  4. washThe organic solution was washed with water (310 mL)
  5. customthe product precipitated
  6. customto form a thick suspension which
  7. filtrationwas filtered (slow)
  8. washThe solids were washed with EtOAc (165 mL in portions)
  9. customdried

Sources & evidence

ORD record
ord-ea5e6628b78f4e1784f07946c74522f5
Source dataset
uspto-grants-2015_03
Patent number
US08986993B2

Reaction notes

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