Methanol → {8-Fluoro-1,4-dioxaspiro[4.5]decan-8-yl}methanol

HRID 75723Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 75723
[F:1][C:2]1([C:12](OCC)=[O:13])[CH2:11][CH2:10][C:5]2([O:9][CH2:8][CH2:7][O:6]2)[CH2:4][CH2:3]1.[Li+].[BH4-].CO.C([O-])(O)=O.[Na+]>C1COCC1>[F:1][C:2]1([CH2:12][OH:13])[CH2:11][CH2:10][C:5]2([O:6][CH2:7][CH2:8][O:9]2)[CH2:4][CH2:3]1

Komponenten

6

Edukt 4

HCID 887Methanol2×HCID 516892Sodium BicarbonateHCID 4148881Lithium borohydrideHCID 67960160Ethyl 8-fluoro-1,4-dioxaspiro[4.5]decane-8-carboxylate

Produkt 1

HCID 67225989{8-Fluoro-1,4-dioxaspiro[4.5]decan-8-yl}methanolAusbeute 56 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To a solution of crude ethyl 8-fluoro-1,4-dioxaspiro[4.5]decane-8-carboxylate, Intermediate 30, (16.26 g, 70 mmol calculated based on previous reaction, 1 equiv) in THF (100 mL) was added LiBH4 (45.5 mL of a 2 M solution in THF, 91 mmol, 1.3 equiv) followed by MeOH (3.68 mL, 91 mmol, 1.3 equiv). Significant warming was observed following MeOH addition. The reaction was stirred 30 min at which time TLC showed no ester remaining. The reaction was poured into a saturated aqueous solution of NaHCO3 and the aqueous solution was extracted with ether (×3). The combined ether layers were dried (MgSO4) and concentrated in vacuo. The crude product was purified by silica gel chromatography (30-90% ethyl acetate/hexane) to provide the title compound (7.50 g, 56% yield for 2 steps) as a pale yellow oil. 1H NMR (400 MHz, CDCl3) δ ppm 3.90-4.03 (m, 4H), 3.64 (d, J=6.78 Hz, 1H), 3.59 (d, J=6.78 Hz, 1H), 1.97-2.09 (m, 2H), 1.84-1.95 (m, 2H), 1.62-1.80 (m, 4H); 19F NMR (376 MHz, CDCl3) δ ppm −171.25 (br. s., 1F).

Aufarbeitung

  1. temperatureSignificant warming
  2. extractionthe aqueous solution was extracted with ether (×3)
  3. dry with materialThe combined ether layers were dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customThe crude product was purified by silica gel chromatography (30-90% ethyl acetate/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-5a876810e4d94988af54b4bb03411aa1
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08835411B2

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