Pyridine → 2-Fluoro-2-nitro-1,3-propanediol monotriflate

HRID 903027ノート

反応式

HRID 903027 の反応式
S([O:8][S:9]([C:12]([F:15])([F:14])[F:13])(=[O:11])=[O:10])(C(F)(F)F)(=O)=O.[F:16][C:17]([N+:22]([O-:24])=[O:23])([CH2:20]O)[CH2:18][OH:19].N1C=CC=CC=1.C(Cl)Cl.C(OCC)(=O)C>CCOCC>[S:9]([O:8][CH2:20][C:17]([F:16])([N+:22]([O-:24])=[O:23])[CH2:18][OH:19])([C:12]([F:13])([F:14])[F:15])(=[O:10])=[O:11]

参加物

6

反応物 4

HCID 1049PyridineHCID 67749Trifluoromethanesulfonic anhydrideHCID 126832742-Fluoro-2-nitropropane-1,3-diolHCID 21226138Dichloromethane ethylacetate

生成物 1

HCID 126832752-Fluoro-2-nitro-1,3-propanediol monotriflate収率 88%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

実験手順

A solution of 10.9 ml (0.65 mol) of triflic anhydride in 210 ml of ether was added dropwise over 25 minutes to a solution of 17.4 g (0.124 mol) of 2-fluoro-2-nitro-1,3-propanediol and 6.0 ml (0.074 mol) of pyridine in 210 ml of ether, at a temperature just below 26° C. After 16 hours, the resulting precipitate was filtered and washed with ether. The filtrate was stripped of solvent and the residue was partitioned between 300 ml of methylene chloride and 60 ml of water. The methylene chloride layer was washed with 30 ml of water, dried over sodium sulfate and chromatographed on a 125 g silica gel column. Elution with 500 ml of methylene chloride and with 1100 ml of 9:1 methylene chloride-ethyl acetate gave 15.5 g (88% yield) of 2-fluoro-2-nitro-1,3-propanediol monotriflate, which was recrystallized from methylene chloride. Skelly F: mp 29°-30°; proton NMR (CDCl3) δ2.65 (broad s, 1H,OH), 4.10 (d,J=14 Hz, 2H, CH2OH), 5.07 (m, J=14 Hz, 2 H CH2OSO2CF3); fluorine NMR (CDCl3) φ72.0 (s, 3F, CF3), 139.4 (quint, J=14 Hz, 1F, O2NCF): IR (CH2Cl2) 3625 (OH), 1580, 1350 (NO2), 1420, 1220, 1140, 900 (OSO2CF2), 1000 cm-1 (CF).

後処理

  1. filtrationthe resulting precipitate was filtered
  2. washwashed with ether
  3. customthe residue was partitioned between 300 ml of methylene chloride and 60 ml of water
  4. washThe methylene chloride layer was washed with 30 ml of water
  5. dry with materialdried over sodium sulfate
  6. customchromatographed on a 125 g silica gel column
  7. washElution with 500 ml of methylene chloride

出典と根拠

ORDレコード
ord-b9b034f10f4441dd8ab00088dcd36ae2
出典データセット
uspto-grants-1980_10
特許番号
US04226777

反応ノート

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