Triphenylphosphine → 2-(Bromomethyl)-4-chloro-1-nitrobenzene

HRID 1504913Notes

Reaction equation

HRID 1504913 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=1)[CH2:7]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:32]N1C(=O)CCC1=O>ClCCl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([N+:10]([O-:12])=[O:11])=[C:6]([CH:9]=1)[CH2:7][Br:32]

Participants

5

Reactant 3

HCID 11776Triphenylphosphine2×HCID 67184N-bromobutanimide2×HCID 5560665-Chloro-2-nitrobenzyl alcohol

Product 1

HCID 124231272-(Bromomethyl)-4-chloro-1-nitrobenzeneYield 32.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

5.61 g of 5-chloro-2-nitrobenzyl alcohol is mixed with 9.1 g of triphenylphosphine in 100 ml of dichloromethane. To this solution 6.1 g of N-bromosuccinimide is added portionwise over 5 minutes (to avoid foaming as the reaction warms to ca. 50° C.). After stirring 30 minutes 10 wt % of both triphenylphosphine (900 mg) and N-bromosuccinimide (600 mg) are added. After an additional 30 minutes stirring the reaction mixture is concentrated to approximately 10 ml, poured on a bed of Celite®, and then rinsed through with 0.1% methanol in dichloromethane. Evaporation of the filtrate provides 2.43 g of 5-chloro-2-nitrobenzyl bromide as a light yellow oil. 1H-NMR (500 MHz, CDCl3) δ (ppm) 4.806 (s, 2H), 7.457-7.479 (dd, 1H), 7.589-7.593 (s, 1H), 8.033-8.051 (d, 1H).

Workup

  1. customwarms to ca. 50° C.
  2. additionare added
  3. concentrationis concentrated to approximately 10 ml
  4. additionpoured on a bed of Celite®
  5. washrinsed through with 0.1% methanol in dichloromethane
  6. customEvaporation of the filtrate

Sources & evidence

ORD record
ord-2707c46ac0c04af6a52c9b3839d2e51d
Source dataset
uspto-grants-2015_12
Patent number
US09216945B2

Reaction notes

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