Triphenylphosphine → HCID 49851937, compound

HRID 1496926Notes

Reaction equation

HRID 1496926 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH:13]=[CH:12][C:11]([CH2:14]O)=[CH:10][CH:9]=2)=[N:6][CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:35]N1C(=O)CCC1=O>C(Cl)Cl>[Br:35][CH2:14][C:11]1[CH:12]=[CH:13][C:8]([C:5]2[CH:4]=[CH:3][C:2]([F:1])=[CH:7][N:6]=2)=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 67184N-bromobutanimideHCID 56604654HCID 56604654, compound

Product 1

HCID 49851937HCID 49851937, compoundYield 87.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of alcohol 111 (305 mg, 1.50 mmol) and triphenylphosphine (474 mg, 1.81 mmol) in anhydrous CH2Cl2 (12 mL) was carefully treated with recrystallized N-bromosuccinimide (322 mg, 1.81 mmol) (water bath cooling), and the mixture was stirred at room temperature for 3 h. The resulting solution was concentrated, and then added to excess pentane at the top of a silica gel column (20 g in pentane), rinsing on with minimal extra CH2Cl2. Elution with pentane firstly gave foreruns, and then further elution with 20-50% Et2O/pentane gave 2-[4-(bromomethyl)phenyl]-5-fluoropyridine (112) (348 mg, 87%) as a white solid that was used directly in the next step; 1H NMR (CDCl3) δ 8.54 (d, J=2.9 Hz, 1H), 7.92 (dt, J=8.4, 1.9 Hz, 2H), 7.72 (ddd, J=8.7, 4.3, 0.4 Hz, 1H), 7.52-7.43 (m, 3H), 4.54 (s, 2H); HRESIMS calcd for C12H10BrFN m/z [M+H]+ 267.9955, 265.9975, found 267.9959, 265.9979.

Workup

  1. concentrationThe resulting solution was concentrated
  2. additionadded to excess pentane at the top of a silica gel column (20 g in pentane)
  3. washrinsing on with minimal extra CH2Cl2
  4. washElution with pentane firstly gave foreruns
  5. washfurther elution with 20-50% Et2O/pentane

Sources & evidence

ORD record
ord-d326a9f7d8fa4f4fbdd6e4fa0ad1b231
Source dataset
uspto-grants-2015_12
Patent number
US09198913B2

Reaction notes

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