Chlorine monoxide → 4-(Isocyano(tosyl)methyl)benzonitrile

HRID 2202100Notes

Reaction equation

HRID 2202100 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([CH:9]([S:13]([C:16]2[CH:22]=[CH:21][C:19]([CH3:20])=[CH:18][CH:17]=2)(=[O:15])=[O:14])[NH:10][CH:11]=O)=[CH:5][CH:4]=1)#[N:2].O(Cl)Cl>O1CCCC1>[N+:10]([CH:9]([S:13]([C:16]1[CH:17]=[CH:18][C:19]([CH3:20])=[CH:21][CH:22]=1)(=[O:15])=[O:14])[C:6]1[CH:5]=[CH:4][C:3]([C:1]#[N:2])=[CH:8][CH:7]=1)#[C-:11]

Participants

4

Reactant 2

HCID 24646Chlorine monoxideHCID 11438410HCID 11438410, compound

Product 1

HCID 1317357244-(Isocyano(tosyl)methyl)benzonitrileYield 53.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of N-((4-cyanophenyl)(tosyl)methyl)formamide (3 g, 9.54 mmol, 1.00 equiv) in tetrahydrofuran (30 mL) at −10° C. was added dropwise phorphorus oxychloride (4.4 g, 28.70 mmol, 3.00 equiv) and TEA (4.8 g, 47.44 mmol, 5.00 equiv). The reaction mixture was stirred at room temperature for 3 h and then concentrated under vacuum. The residue was diluted with 100 mL of dichloromethane then washed with 3×50 mL of water and 2×50 mL of brine. The organic layer was dried over anhydrous sodium sulfate and concentrated under vacuum. The residue was purified on a silica gel column eluted with 0-30% of ethyl acetate in petroleum ether to give 1.5 g (53%) of 4-(isocyano(tosyl)methyl)benzonitrile as an off-white solid. 1H-NMR (300 MHz, DMSO-d6): δ 8.00-7.90 (m, 3H), 7.80-7.70 (m, 4H), 7.50-7.44 (m, 2H), 2.42 (s, 3H) ppm.

Workup

  1. concentrationconcentrated under vacuum
  2. additionThe residue was diluted with 100 mL of dichloromethane
  3. washthen washed with 3×50 mL of water and 2×50 mL of brine
  4. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  5. concentrationconcentrated under vacuum
  6. customThe residue was purified on a silica gel column
  7. washeluted with 0-30% of ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-6fe5723bb70843f3a0d7e93a7dfbf5af
Source dataset
uspto-grants-2016_06
Patent number
US09365527B2

Reaction notes

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