Propylamine → 5-Chloro-2-nitro-N,N'-dipropylbenzamidine

HRID 1167134Notes

Reaction equation

HRID 1167134 reaction equation
[CH2:1]([NH:4][C:5](=O)[C:6]1[CH:11]=[C:10]([Cl:12])[CH:9]=[CH:8][C:7]=1[N+:13]([O-:15])=[O:14])[CH2:2][CH3:3].O=S(Cl)Cl.[NH2:21][CH2:22][CH2:23][CH3:24]>C1COCC1>[Cl:12][C:10]1[CH:9]=[CH:8][C:7]([N+:13]([O-:15])=[O:14])=[C:6]([CH:11]=1)[C:5]([NH:21][CH2:22][CH2:23][CH3:24])=[N:4][CH2:1][CH2:2][CH3:3]

Participants

5

Reactant 3

HCID 7852PropylamineHCID 24386Thionyl ChlorideHCID 45328165-Chloro-2-nitrobenzoic acid propylamide

Product 1

HCID 229958345-Chloro-2-nitro-N,N'-dipropylbenzamidine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

In a sulfonation flask 32.8 g (0.125 mol) 5-chloro-2-nitrobenzoic acid propylamide are dissolved in 74.4 g (0.625 mol) SOCl2 and heated at reflux temperature for 4 hours. Then the excess SOCl2 is removed in a water jet vacuum and the crude imidoylchloride is dissolved in 30 ml of absolute THF. The resulting solution was added dropwise to a stirred solution of 15.4 g (0.26 mol) 1-aminopropane in 30 ml THF. The mixture is stirred for 5 hours at reflux temperature and then the solvent is removed in a water jet vacuum. The residue is taken up in ethylacetate and the organic phase is washed twice with water and saturated sodiumcarbonate solution. After drying of the organic phase, the solvent is removed in a water jet vacuum and the raw material purified by column chromatography over silica gel (eluant: hexane/THF=3:1). Yield: 27.8 g 5-chloro-2-nitro-N,N′-dipropylbenzamidine in the form of brown crystals; m.p. 63-64° C.

Workup

  1. temperatureheated
  2. temperatureat reflux temperature for 4 hours
  3. customThen the excess SOCl2 is removed in a water jet vacuum
  4. dissolutionthe crude imidoylchloride is dissolved in 30 ml of absolute THF
  5. temperatureat reflux temperature
  6. customthe solvent is removed in a water jet vacuum
  7. washthe organic phase is washed twice with water and saturated sodiumcarbonate solution
  8. customAfter drying of the organic phase
  9. customthe solvent is removed in a water jet vacuum
  10. customthe raw material purified by column chromatography over silica gel (eluant: hexane/THF=3:1)

Sources & evidence

ORD record
ord-eb78539e44a14073b3abc2128bd6e320
Source dataset
uspto-grants-2003_09
Patent number
US06617330B2

Reaction notes

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