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

HRID 903027Notes

Reaction equation

HRID 903027 reaction equation
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]

Participants

6

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-b9b034f10f4441dd8ab00088dcd36ae2
Source dataset
uspto-grants-1980_10
Patent number
US04226777

Reaction notes

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