4-Nitrobenzyl bromide → HCID 10050982, compound

HRID 1742108Notes

Reaction equation

HRID 1742108 reaction equation
[CH2:1]([C:5]1[N:6]([CH2:11][C:12]2[CH:17]=[CH:16][C:15]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[C:24]#[N:25])=[CH:14][CH:13]=2)[C:7](=[S:10])[NH:8][N:9]=1)[CH2:2][CH2:3][CH3:4].C(N(CC)C(C)C)(C)C.[N+:35]([C:38]1[CH:45]=[CH:44][C:41]([CH2:42]Br)=[CH:40][CH:39]=1)([O-:37])=[O:36]>COCCO>[CH2:1]([C:5]1[N:6]([CH2:11][C:12]2[CH:17]=[CH:16][C:15]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[C:24]#[N:25])=[CH:14][CH:13]=2)[C:7]([S:10][CH2:42][C:41]2[CH:44]=[CH:45][C:38]([N+:35]([O-:37])=[O:36])=[CH:39][CH:40]=2)=[N:8][N:9]=1)[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 3

HCID 660114-Nitrobenzyl bromideHCID 81531DiisopropylethylamineHCID 10066359HCID 10066359, compound

Product 1

HCID 10050982HCID 10050982, compoundYield 86.9%

Reagents, catalysts & solvents 1

HCID 80192-MethoxyethanolSolvent

Procedure

A mixture of 209 mg (0.6 mmole) of 5-n-butyl-4-[(2'cyanobiphenyl-4-yl)methyl]-2,4-dihydro-3H-1,2,4-triazole-3-thione (from Example 15, Step C), 209 μl (155 mg, 1.2 mmole) of N,N-diisopropylethylamine, 259 mg (1.2 mmole) of 4-nitrobenzyl bromide, and 2 ml of 2-methoxyethanol was stirred under N2 at room temperature for 2 hours. The solution was then concentrated in vacuo at 30° C. to small volume and then partitioned between a mixture of 25 ml of ether, 5 ml of ethyl acetate, and 25 ml of 0.2 N HCl. The organic phase was washed with an additional portion of 0.2 N HCl and then with saturated NaCl solution. The organic solution was dried (MgSO4), filtered, and concentrated. The residue was purified by column chromatography on silica gel (gradient elution with 0-1.6% methanol in CH2Cl2). Concentration of the combined product fractions yielded 252 mg (84%) of the title compound as a sticky foam, homogeneous by TLC in 19:1 CH2Cl2 --MeOH; mass spectrum (FAB) m/e 484 (M+1)+.

Workup

  1. concentrationThe solution was then concentrated in vacuo at 30° C. to small volume
  2. custompartitioned between a mixture of 25 ml of ether, 5 ml of ethyl acetate, and 25 ml of 0.2 N HCl
  3. washThe organic phase was washed with an additional portion of 0.2 N HCl
  4. dry with materialThe organic solution was dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by column chromatography on silica gel (gradient elution with 0-1.6% methanol in CH2Cl2)

Sources & evidence

ORD record
ord-caca7a2949b24045b7b0914e19240197
Source dataset
uspto-grants-1994_08
Patent number
US05336778

Reaction notes

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