Ethylenediamine → N,N'-bis(2-methyl-2-triphenylmethylthiopropyl)ethylenediamine

HRID 613213Notes

Reaction equation

HRID 613213 reaction equation
[CH2:1]([NH2:4])[CH2:2]N.[CH3:5][C:6]([S:10][C:11]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([CH3:9])[CH:7]=O.[CH2:30]1[CH2:34]O[CH2:32][CH2:31]1.[C:35]([BH3-])#[N:36].[Na+]>CO.C(O)(=O)C>[CH3:5][C:6]([S:10][C:11]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([CH3:9])[CH2:7][NH:4][CH2:1][CH2:2][NH:36][CH2:35][C:6]([S:10][C:30]([C:34]1[CH:25]=[CH:24][CH:11]=[CH:18][CH:19]=1)([C:16]1[CH:17]=[CH:12][CH:13]=[CH:14][CH:15]=1)[C:31]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:32]=1)([CH3:5])[CH3:7]

Participants

7

Reactant 4

HCID 3301EthylenediamineHCID 8028TetrahydrofuranHCID 5003444Sodium cyanoborohydride3×HCID 211921942-Methyl-2-(triphenylmethylthio)propanal

Product 1

HCID 21192173N,N'-bis(2-methyl-2-triphenylmethylthiopropyl)ethylenediamine

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 887MethanolSolvent

Conditions

Temperature
20 °C

Procedure

Ethylenediamine (1.3 mL, 0.0194 mol, 100 mol %) was added to 2-methyl-2-(triphenylmethylthio)propanal (13.86 g, 0.0401 mol, 206 mol %) dissolved in methanol (40 mL) and anhydrous THF (40 mL) under argon, and the pH was adjusted to pH 6 by dropwise addition of acetic acid. The solution was stirred for 20 min at 20° C. Sodium cyanoborohydride (1.22 g, 0.0194 mol, 100 mol %) was added and the reaction was stirred at room temperature for 3 hours. Additional sodium cyanoborohydride (1.08 g) was added and the reaction was stirred at 20° C. for 17 hours. A final portion of sodium cyanoborohydride (1.02 g) was added and the reaction heated at reflux under argon for 6 hours. The reaction was quenched with 0.5 M HCl (100 mL) and extracted with ethyl acetate (2×100 mL). The organic extracts were combined, sequentially washed with 2 M NaOH (60 mL), saturated NaCl solution (60 mL), dried (Na2SO4), and filtered. The solvent was removed under reduced pressure to give 16.67 g of crude product which was crystallized from toluene/hexanes to afford 10.20 g (73% yield) of white crystals of the title compound. The melting point of the resulting compound was determined to be 83-86° C. FABMS analysis yielded an m/z of 721 (MH+). Nuclear magnetic resonance characterization experiments yielded the following molecular signature:

Workup

  1. stirringthe reaction was stirred at room temperature for 3 hours
  2. stirringthe reaction was stirred at 20° C. for 17 hours
  3. temperaturethe reaction heated
  4. temperatureat reflux under argon for 6 hours
  5. customThe reaction was quenched with 0.5 M HCl (100 mL)
  6. extractionextracted with ethyl acetate (2×100 mL)
  7. washsequentially washed with 2 M NaOH (60 mL), saturated NaCl solution (60 mL)
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. customThe solvent was removed under reduced pressure
  11. customto give 16.67 g of crude product which
  12. customwas crystallized from toluene/hexanes

Sources & evidence

ORD record
ord-70f2476bdf7f4e98afaf922b889655bb
Source dataset
uspto-grants-1999_12
Patent number
US06007792

Reaction notes

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