4,4,4-Trifluoro-3-hydroxy-3-methyl-1-[4-(1-pyrrolidinylsulfonyl)phenyl]but-1-yne → 4,4,4-Trifluoro-3-hydroxy-3-methyl-1-[4-(1-pyrrolidinylsulfonyl)phenyl]-trans-but-1-ene

HRID 1938175Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1938175
[H-].COCCO[Al+]OCCOC.[Na+].[H-].[F:15][C:16]([F:37])([F:36])[C:17]([OH:35])([CH3:34])[C:18]#[C:19][C:20]1[CH:25]=[CH:24][C:23]([S:26]([N:29]2[CH2:33][CH2:32][CH2:31][CH2:30]2)(=[O:28])=[O:27])=[CH:22][CH:21]=1>C1(C)C=CC=CC=1.C(OCC)C>[F:37][C:16]([F:15])([F:36])[C:17]([OH:35])([CH3:34])/[CH:18]=[CH:19]/[C:20]1[CH:25]=[CH:24][C:23]([S:26]([N:29]2[CH2:33][CH2:32][CH2:31][CH2:30]2)(=[O:27])=[O:28])=[CH:22][CH:21]=1

Komponenten

5

Edukt 2

HCID 214691154,4,4-Trifluoro-3-hydroxy-3-methyl-1-[4-(1-pyrrolidinylsulfonyl)phenyl]but-1-yneHCID 21584525Sodium bis(2-methoxyethoxy)aluminiumhydride

Produkt 1

HCID 214691114,4,4-Trifluoro-3-hydroxy-3-methyl-1-[4-(1-pyrrolidinylsulfonyl)phenyl]-trans-but-1-eneAusbeute 88,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1140TolueneLösungsmittelHCID 3283Diethyl EtherLösungsmittel

Versuchsvorschrift

To a solution of sodium bis(methoxyethoxy) aluminum hydride (720 mL of a 3.4M solution in toluene, 2.45 mmol) in anhydrous diethyl ether (6 mL) cooled to -2° C. under a nitrogen atmosphere was added dropwise an ethereal solution (25 mL) of 4,4,4-trifluoro-3-hydroxy-3-methyl-1-[4-(1-pyrrolidinylsulfonyl)phenyl]but-1-yne (500 mg). The rate of addition was adjusted such that the reaction temperature (internal) did not exceed 10° C. Upon complete addiron the reaction was kept near 0° C. After 30 minutes the reaction was quenched by the addition of 3M sulfuric acid (20 mL). The product was extracted into diethyl ether. The combined organic extracts were dried, filtered, and evaporated. The crude product was adsorbed onto silica gel and purified by chromatography (1:8 diethyl ether: chloroform) to yield a white compound (447 mg). This material was further purified by recrystalization employing diethyi ether:hexanes (1:5) to provide the title compound (251 mg); mp 119°-121° C.; MS: m/z=350(M+1); NMR: (CDCl3): 1.59 (s,3), 1.73-1.78 (m,4), 2.45 (s,1), 3.22-3.27 (m,4), 6.41 (d,1, J=16.0), 6.93 (d,1,J=16.0), 7.52-7.55 (m,2), 7.77-7.81 (m,2). Analysis for C15H18F3NO3S: Calculated: C, 51.57; H, 5.19; N, 4.01; Found: C, 51.45; H, 5.19; N, 3.90.

Aufarbeitung

  1. additionThe rate of addition
  2. customdid not exceed 10° C
  3. customwas kept near 0° C
  4. customAfter 30 minutes the reaction was quenched by the addition of 3M sulfuric acid (20 mL)
  5. extractionThe product was extracted into diethyl ether
  6. customThe combined organic extracts were dried
  7. filtrationfiltered
  8. customevaporated
  9. custompurified by chromatography (1:8 diethyl ether: chloroform)

Quellen und Nachweise

ORD-Eintrag
ord-cf30ddbbce174d63b1765a6ea9805909
Quelldatensatz
uspto-grants-1997_12
Patentnummer
US05693639

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