Ethylenediamine → Octahydro-6H-6lambda~6~-thieno[3,4-b]pyrazine-6,6-dione

HRID 1162009Notes

Reaction equation

HRID 1162009 reaction equation
Cl[C@H:2]1[C@@H:6](Cl)[CH2:5][S:4](=[O:9])(=[O:8])[CH2:3]1.[CH2:10]([NH2:13])[CH2:11][NH2:12]>O1CCOCC1>[NH:12]1[CH2:11][CH2:10][NH:13][CH:2]2[CH2:3][S:4](=[O:9])(=[O:8])[CH2:5][CH:6]12

Participants

4

Reactant 2

HCID 3301EthylenediamineHCID 12091293737-42-6

Product 1

HCID 16449569Octahydro-6H-6lambda~6~-thieno[3,4-b]pyrazine-6,6-dioneYield 59%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
100 °C

Procedure

cis-3,4-Dichlorotetrahydrothiophene 1,1-dioxide (5.0 g, 26.0 mmol) in dioxane (40 mL) was added dropwise to ethane-1,2-diamine (10.4 g, 173.0 mmol) in dioxane (25 mL) at 0° C. The mixture was heated at 100° C. for 3 h, followed by cooling to room temperature and continued stirring overnight. The two layers were separated and the bottom layer, containing ethylene diamine and amine salt, was washed twice with dioxane. The dioxane layers were combined and the solvent was removed in vacuo. The crude product was recrystallized from toluene to afford 2.7 g (59%) of the title compound as white crystals. HPLC 98%, RT: 0.292 (System B; 10-97% MeCN over 3 min). 1H NMR (270 MHz, methanol-d4) δ ppm 2.67-2.76 (m, 2H) 2.86-2.96 (m, 2H) 3.13-3.20 (m, 2H) 3.33-3.44 (m, 2H) 3.63-3.70 (m, 2H). LC-MS 177 (M+H)+. *Previously described in U.S. Pat. No. 3,882,122.

Workup

  1. temperatureby cooling to room temperature
  2. customThe two layers were separated
  3. additionthe bottom layer, containing ethylene diamine and amine salt
  4. washwas washed twice with dioxane
  5. customthe solvent was removed in vacuo
  6. customThe crude product was recrystallized from toluene

Sources & evidence

ORD record
ord-1d19620b5b0a4015bfdfd4e5ea4f7724
Source dataset
uspto-grants-2010_10
Patent number
US07820675B2

Reaction notes

Loading…