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 1938175ノート

反応式

HRID 1938175 の反応式
[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

参加物

5

反応物 2

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

生成物 1

HCID 214691114,4,4-Trifluoro-3-hydroxy-3-methyl-1-[4-(1-pyrrolidinylsulfonyl)phenyl]-trans-but-1-ene収率 88.9%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-cf30ddbbce174d63b1765a6ea9805909
出典データセット
uspto-grants-1997_12
特許番号
US05693639

反応ノート

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