Triphenylphosphine → 5-(1-Azidoethyl)-2-fluoropyridine

HRID 561017

Reaction equation

HRID 561017 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(C#N)CC=CCC=1C#N.CCCC[N+](CCCC)(CCCC)CCCC.[N-:47]=[N+:48]=[N-:49].[F:50][C:51]1[N:56]=[CH:55][C:54]([CH:57](O)[CH3:58])=[CH:53][CH:52]=1>ClCCl>[N:47]([CH:57]([C:54]1[CH:53]=[CH:52][C:51]([F:50])=[N:56][CH:55]=1)[CH3:58])=[N+:48]=[N-:49]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 57432321-Butanaminium, N,N,N-tributyl-, azideHCID 20439962HCID 20439962, compoundHCID 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 a ice bath, add triphenylphosphine (27.9 g, 106.3 mmol), 1,4-cyclohexadiene-1,2-dicarbonitrile, 4,5-dichloro-3,6-dioxo-(24.12 g, 106.3 mmol). Add dichloromethane 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 dichloromethane (10 mL). Remove the flask from the ice bath and stir at room temperature for 1 hour. Remove the solvent on a rotovap and purify by normal phase chromatography 5% to 20% ethyl acetate in hexanes to obtain the product as colorless oil (7.75 g). GCMS (EI) m/z 166 M+.

Workup

  1. customTo a 1-L flask kept cold in a 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-560b8f80d2454092b3134c53b19523fa
Source dataset
uspto-grants-2011_11
Patent number
US08063212B2

Linked notes

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