3-Chloro-2-chloromethyl-1-propene → HCID 465407, compound

HRID 1251310Notes

Reaction equation

HRID 1251310 reaction equation
[H-].[Na+].[CH2:3]([N:10]([CH2:24][CH2:25][CH2:26][NH:27][S:28]([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)(=[O:30])=[O:29])[CH2:11][CH2:12][CH2:13][NH:14][S:15]([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)(=[O:17])=[O:16])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.Cl[CH2:38][C:39]([CH2:41]Cl)=[CH2:40]>CN(C=O)C.C(OCC)(=O)C.CCCCCC>[CH2:3]([N:10]1[CH2:24][CH2:25][CH2:26][N:27]([S:28]([C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)(=[O:29])=[O:30])[CH2:41][C:39](=[CH2:38])[CH2:40][N:14]([S:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)(=[O:17])=[O:16])[CH2:13][CH2:12][CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 3

HCID 158593-Chloro-2-chloromethyl-1-propeneHCID 24758Sodium hydride2×HCID 11584206HCID 11584206, compound

Product 1

HCID 465407HCID 465407, compoundYield 77.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 21226206Ethyl acetate hexaneSolvent

Procedure

In a 500 mL three-necked round-bottomed flask equipped with a rubber septum and a gas inlet, 0.92 g of a 60% (w/w) dispersion of sodium hydride in mineral oil (0.55 g NaH, 23 mmol) was washed with hexane (3×15 mL) under N2. A solution of 5.78 g (11.5 mmol) of N-benzylbis(3-benzenesulfonamidopropyl)amine in 220 mL of DMF was added slowly with stirring. The resulting clear solution was stirred under N2 while a solution of 1.44 g (11.5 mmol) of 3-chloro-2-chloromethyl-l-propene in 8 mL of DMF was added dropwise over 10 h. Stirring at room temperature under N2 was continued for an additional 24 h. The solvent was removed by rotary evaporation evaporation using a hot water bath. A solution of the residue in 50 mL of CHCl3 was washed with water (3×30 mL) and saturated aq. NaCl (2×30 mL) then dried (MgSO4). Removal of the drying agent by filtration and concentration of the filtrate by rotary evaporation gave the crude product as a thick yellow oil. The oil was dissolved in 100 mL of 1:1 (v/v) ethyl acetate/hexane and filtered through a pad of 16 g of basic alumina (Act 1, 80-200 mesh) washing with an additional 50 mL of 1:1 ethyl acetate/hexane. Concentration of the combined filtrates under vacuum afforded 4.93 g (77 %) of 9-benzyl-3-methylene-1,5-dibenzenesulfonyl-1,5,9-triazacyclododecane as a bubbly film that was converted to the hydrochloride salt.

Workup

  1. washwas washed with hexane (3×15 mL) under N2
  2. additionwas added dropwise over 10 h
  3. stirringStirring at room temperature under N2
  4. customThe solvent was removed by rotary evaporation evaporation
  5. washA solution of the residue in 50 mL of CHCl3 was washed with water (3×30 mL) and saturated aq. NaCl (2×30 mL)
  6. dry with materialthen dried (MgSO4)
  7. customRemoval of the drying agent
  8. filtrationby filtration and concentration of the filtrate
  9. customby rotary evaporation
  10. customgave the crude product as a thick yellow oil
  11. filtrationfiltered through a pad of 16 g of basic alumina (Act 1, 80-200 mesh)
  12. washwashing with an additional 50 mL of 1:1 ethyl acetate/hexane

Sources & evidence

ORD record
ord-f9889fd68abf4f66b5bde2f68b482918
Source dataset
uspto-grants-2002_01
Patent number
US06342492B1

Reaction notes

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