Thionyl Chloride → HCID 178436086, compound

HRID 1577155Notes

Reaction equation

HRID 1577155 reaction equation
S([N:11]1[CH2:15][CH2:14][NH:13][C:12]1=[N:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[CH2:23][CH2:24]O)(C1C=CC(C)=CC=1)(=O)=O.S(Cl)(Cl)=O.[Na].[Cl-].[NH4+]>N1C=CC=CC=1.ClCCl.CO>[CH:23]([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=1[N:16]=[C:12]1[NH:11][CH2:15][CH2:14][NH:13]1)=[CH2:24]

Participants

7

Reactant 4

HCID 24386Thionyl ChlorideHCID 25517Ammonium ChlorideHCID 5360545SodiumHCID 178427379HCID 178427379, compound

Product 1

HCID 178436086HCID 178436086, compound

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

N'-Tosyl-2-[2-(2-hydroxyethyl)phenylimino]imidazolidine from Example 17, Step B (1.8 g) is dissolved in pyridine (25 ml) containing thionyl chloride (3 ml). The mixture is heated at reflux until thin layer chromatography shows starting material to be gone [silica gel=dichloromethane:methanol (19:1)], about three hours. The volatiles are evaporated in vacuo and the residue is partitioned between water and ether. The aqueous layer is extracted (3×50 ml) with ether and the combined extracts are washed with brine, dried over sodium sulfate and evaporated to off white crystals which can be purified by recrystallization from ethyl acetate (1.23 g, 72%). Ammonia (50 ml) is condensed in a cooled flask fitted with a dry ice condenser. The N-tosyl derivative (0.5 g) is added and when solution occurs, small pieces of freshly cut metallic sodium are added one at a time until a blue color persists. Solid ammonium chloride is added to remove the blue color and the ammonia is evaporated in a stream of nitrogen. The solid residue is partitioned between water and ether. The aqueous layer is basified to pH 14 and reextracted with dichloromethane (2×50 ml). The organic extracts are pooled, extracted with 2 N acetic acid (3×50 ml) and these extracts are combined, back-extracted with dichloromethane, and neutralized with dilute hydrochloric acid.

Workup

  1. temperatureThe mixture is heated
  2. temperatureat reflux until thin layer chromatography
  3. customThe volatiles are evaporated in vacuo
  4. customthe residue is partitioned between water and ether
  5. extractionThe aqueous layer is extracted (3×50 ml) with ether
  6. washthe combined extracts are washed with brine
  7. dry with materialdried over sodium sulfate
  8. customevaporated to off white crystals which
  9. customcan be purified by recrystallization from ethyl acetate (1.23 g, 72%)
  10. customcondensed in a cooled flask
  11. customfitted with a dry ice condenser
  12. customto remove the blue color
  13. customthe ammonia is evaporated in a stream of nitrogen
  14. customThe solid residue is partitioned between water and ether
  15. extractionextracted with 2 N acetic acid (3×50 ml)
  16. extractionback-extracted with dichloromethane

Sources & evidence

ORD record
ord-33f06580361a4f23a7731bdbec017f79
Source dataset
uspto-grants-1981_09
Patent number
US04287201

Reaction notes

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