Hydrazine hydrate (1:1) → 12-(4-Chloro-benzenesulfonyl)-7-ethyl-4,5,12-triaza-tricyclo[6.3.1.02,6]dodeca-2(6),3-diene

HRID 2354876Notes

Reaction equation

HRID 2354876 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]2[CH:16]3[CH2:17][CH2:18][CH2:19][CH:12]2[C:13](=[CH:23][N:24](C)C)[C:14](=O)[CH:15]3[CH2:20][CH3:21])(=[O:10])=[O:9])=[CH:4][CH:3]=1.O.[NH2:28]N>C(O)(=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]2[CH:16]3[CH2:17][CH2:18][CH2:19][CH:12]2[C:13]2[CH:23]=[N:24][NH:28][C:14]=2[CH:15]3[CH2:20][CH3:21])(=[O:10])=[O:9])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 66842034HCID 66842034, compound

Product 1

HCID 1604539612-(4-Chloro-benzenesulfonyl)-7-ethyl-4,5,12-triaza-tricyclo[6.3.1.02,6]dodeca-2(6),3-diene

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 9-(4-chloro-benzenesulfonyl)-2-dimethylaminomethylene-4-ethyl-9-aza-bicyclo[3.3.1]nonan-3-one crude mixture in glacial acetic acid (1 mL) followed by hydrazine monohydrate (0.5 mL). The reaction mixture was stirred at 100° C. for 1 h after which the solution was cooled to room temperature and quenched by the addition of a saturated aqueous NaHCO3 solution (until pH>7). The resulting solution was extracted with EtOAc (3×20 mL), the organic extracts were combined, dried (Na2SO4), filtered, concentrated and purified by silica gel column chromatography and preparative HPLC to give 12-(4-chloro-benzenesulfonyl)-7-ethyl-4,5,12-triaza-tricyclo[6.3.1.02,6]dodeca-2(6),3-diene as a white solid. Retention time (min)=1.896, Method [1], MS (ESI) 366.1 (M+H); 1H-NMR (300 MHz, CDCl3) δ 7.81-7.78 (m, 2H), 7.47-7.43 (m, 2H), 7.25 (s, 1H), 5.15 (b s, 1H), 4.27 (d, J=4.95 Hz, 1H), 2.56 (dd, J=9.34, 5.49 Hz, 1H), 2.10-1.22 (m, 8H), 1.02 (t, J=7.14 Hz, 3H) (major diastereomer); 1H-NMR (300 MHz, CDCl3) δ 7.68-7.66 (m, 2H), 7.35-7.32 (m, 2H), 7.22 (s, 1H), 5.28 (b s, 1H), 4.31 (d, J=5.5 Hz, 1H), 2.80-2.73 (m, 1H), 2.05-1.21 (m, 8H), 1.06 (t, J=7.69 Hz, 3H) (minor diastereomer).

Workup

  1. temperaturewas cooled to room temperature
  2. customquenched by the addition of a saturated aqueous NaHCO3 solution (until pH>7)
  3. extractionThe resulting solution was extracted with EtOAc (3×20 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. custompurified by silica gel column chromatography and preparative HPLC

Sources & evidence

ORD record
ord-d50c65d777c0449abdbee25dbd648a05
Source dataset
uspto-grants-2010_07
Patent number
US07754712B2

Reaction notes

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