2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 5-(1-Azidoethyl)-2-fluoropyridine

HRID 1640874Notes

Reaction equation

HRID 1640874 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.CCCC[N+](CCCC)(CCCC)CCCC.[N-:51]=[N+:52]=[N-:53].[F:54][C:55]1[N:60]=[CH:59][C:58]([CH:61](O)[CH3:62])=[CH:57][CH:56]=1>C(Cl)Cl>[N:51]([CH:61]([C:58]1[CH:57]=[CH:56][C:55]([F:54])=[N:60][CH:59]=1)[CH3:62])=[N+:52]=[N-:53]

Participants

6

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 11776TriphenylphosphineHCID 57432321-Butanaminium, N,N,N-tributyl-, azideHCID 666001661-(6-Fluoropyridin-3-yl)ethan-1-ol

Product 1

HCID 866404925-(1-Azidoethyl)-2-fluoropyridineYield 65.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a 1-L flask kept cold in an ice bath, add triphenylphosphine (27.9 g, 106.3 mmol), 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile (24.12 g, 106.3 mmol). Add DCM slowly with stirring (150 mL). To the dark solution add tetra-N-butylammonium azide (30.23 g, 106.3 mmol) slowly, followed by 1-(6-fluoro-pyridin-3-yl)-ethanol (10 g, 70.85 mmol) dissolved in DCM (10 mL). Remove the flask from the ice bath and stir at RT for 1 h. Remove the solvent on a rotovap and purify by normal phase chromatography 5% to 20% ethyl acetate in hexanes to obtain the title compound as a colorless oil (7.75 g). GCMS m/z 166 [M]+.

Workup

  1. customTo a 1-L flask kept cold in an ice bath
  2. customRemove the flask from the ice bath
  3. customRemove the solvent on a rotovap
  4. custompurify by normal phase chromatography 5% to 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-d66d02841e7a47da8de26b9c3cd1cbdf
Source dataset
uspto-grants-2012_02
Patent number
US08114872B2

Reaction notes

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