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

HRID 1393209Notes

Reaction equation

HRID 1393209 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:22][N:23](C)C)[C:14](=O)[CH:15]3[CH3:20])(=[O:10])=[O:9])=[CH:4][CH:3]=1.O.[NH2:27]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:22]=[N:23][NH:27][C:14]=2[CH:15]3[CH3:20])(=[O:9])=[O:10])=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 66842262HCID 66842262, compound

Product 1

HCID 1604539212-(4-Chloro-benzenesulfonyl)-7-methyl-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-methyl-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-methyl-4,5,12-triaza-tricyclo[6.3.1.02,6]dodeca-2(6),3-diene as a white solid. Retention time (min)=1.72, Method [1], MS (ESI) 352.0 (M+H); 1H-NMR (300 MHz, CDCl3) δ 7.81-7.78 (m, 2H), 7.47-7.43 (m, 2H), 7.27 (s, 1H), 5.2 (b s, 1H), 4.09 (d, J=4.94 Hz, 1H), 2.89 (q, J=7.14 Hz, 1H), 1.82-1.60 (m, 3H), 1.42-1.34 (m, 3H), 1.19 (d, J=7.14 Hz, 3H); 13C-NMR (75 MHz, CDCl3) δ 149.9, 140.7, 139.0, 129.6, 128.7, 126.4, 115.6, 55.83, 48.6, 34.1, 31.1, 30.9, 21.8, 15.6 ppm.

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-a98c9d9c1447493c9f26e3a067d12aa5
Source dataset
uspto-grants-2008_03
Patent number
US07345056B2

Reaction notes

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