N-Methylethylamine → 2-Chloro-3-fluoro-4-[4-(N-methyl-N-ethylcarbamoyl)phenylsulphanyl]nitrobenzene

HRID 2120377Notes

Reaction equation

HRID 2120377 reaction equation
[Cl:1][C:2]1[C:7]([F:8])=[C:6]([S:9][C:10]2[CH:15]=[CH:14][C:13]([C:16]([OH:18])=O)=[CH:12][CH:11]=2)[CH:5]=[CH:4][C:3]=1[N+:19]([O-:21])=[O:20].C(Cl)(=O)C(Cl)=O.[CH2:28]([NH:30][CH3:31])[CH3:29]>C(Cl)Cl.CN(C=O)C>[Cl:1][C:2]1[C:7]([F:8])=[C:6]([S:9][C:10]2[CH:11]=[CH:12][C:13]([C:16](=[O:18])[N:30]([CH3:31])[CH2:28][CH3:29])=[CH:14][CH:15]=2)[CH:5]=[CH:4][C:3]=1[N+:19]([O-:21])=[O:20]

Participants

6

Reactant 3

HCID 12219N-MethylethylamineHCID 65578Oxalyl chlorideHCID 234394562-Chloro-3-fluoro-4-(4-carboxyphenylsulphanyl)nitrobenzene

Product 1

HCID 234394082-Chloro-3-fluoro-4-[4-(N-methyl-N-ethylcarbamoyl)phenylsulphanyl]nitrobenzeneYield 34.9%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

2-Chloro-3-fluoro-4-(4-carboxyphenylsulphanyl)nitrobenzene (Method 24; 5.5 g, 16.8 mmol) was suspended with stirring in DCM (100 ml) and oxalyl chloride (3.22 ml) was added. A couple of drops of DMF were added to initiate the reaction and it was left to stir overnight. The mixture was evaporated to dryness and then redissolved in DCM (20 ml). N-ethyl-N-methylamine (0.46 ml, 5.28 mmol) was dissolved in DCM (1 ml) and to this with stirring was added some of the above acid chloride solution (2.4 mmol). The solution was left to stir overnight and then washed with water, brine and dried by pouring onto a Chem Elut column eluting with EtOAc. The resulting solution was evaporated down to dryness and then purified by chromatography on a Mega Bond Elut column eluting with a graduated solvent of hexane/EtOAc to yield the title compound (680 mg). NMR: 1.1 (s, 3H), 2.9 (d, 3H), 3.2 (s, 1H), 3.4 (s, 1H), 7.2 (m, 1H), 7.5 (d, 2H), 7.6 (d, 2H), 8.0 (m, 1H); m/z 369.

Workup

  1. customthe reaction and it
  2. waitwas left
  3. customThe mixture was evaporated to dryness
  4. dissolutionredissolved in DCM (20 ml)
  5. stirringto this with stirring
  6. waitThe solution was left
  7. stirringto stir overnight
  8. washwashed with water, brine
  9. customdried
  10. additionby pouring onto a Chem Elut column
  11. washeluting with EtOAc
  12. customThe resulting solution was evaporated down to dryness
  13. custompurified by chromatography on a Mega Bond Elut column
  14. washeluting with a graduated solvent of hexane/EtOAc

Sources & evidence

ORD record
ord-8f657f4e85b94bbb9f2f5c3e502b4d40
Source dataset
uspto-grants-2004_02
Patent number
US06689909B1

Reaction notes

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