Benzyl Bromide → HCID 18552237, compound

HRID 1264450Notes

Reaction equation

HRID 1264450 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][C:7]([CH2:8]Br)=[CH:6][CH:5]=1)([O-:3])=[O:2].[CH2:12]([SH:28])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27].[O-]CC.[Na+].C(Br)C1C=CC=CC=1>C(O)C>[CH2:12]([S:28][CH2:8][C:7]1[CH:10]=[CH:11][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

Participants

6

Reactant 4

HCID 7498Benzyl BromideHCID 18015HexadecanethiolHCID 660114-Nitrobenzyl bromideHCID 2723922Sodium ethoxide

Product 1

HCID 18552237HCID 18552237, compoundYield 89.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

A solution of 4-nitrobenzyl bromide in ethanol (150.0 g, 0.694 mol in 1.5 L) was brought to reflux. Separately, a solution of 1-hexadecanethiol in ethanol (231 mL, 0.691 mol in 1.5 L) was treated with sodium ethoxide in ethanol (258 mL, 0.691 mol of a 21% solution) over ten minutes, stirred at room temperature for 15 minutes, then warmed to dissolve the precipitate. This was then added to the benzyl bromide solution over twenty minutes, stirred at room temperature for two hours, then allowed to sit undisturbed overnight. The crystallized thioether was collected and combined with the product from a 230 mmol run. This light yellow solid was dissolved in CH2Cl2 (3 L), washed with water (1 L), then dried (Na2SO4), filtered, and spin-evaporated to give 324.5 g of 1 (89.5% yield). The material was a single spot by TLC (19:1 hexanes/EtOAc), and was suitable for further transformation.

Workup

  1. temperatureto reflux
  2. temperaturewarmed
  3. dissolutionto dissolve the precipitate
  4. stirringstirred at room temperature for two hours
  5. waitto sit undisturbed overnight
  6. customThe crystallized thioether was collected
  7. dissolutionThis light yellow solid was dissolved in CH2Cl2 (3 L)
  8. washwashed with water (1 L)
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. customspin-evaporated

Sources & evidence

ORD record
ord-9707b6a1d8494279a08a46c3f2a9bc35
Source dataset
uspto-grants-2003_04
Patent number
US06544499B1

Reaction notes

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