Hydrazine → HCID 4987319, compound

HRID 326445Notes

Reaction equation

HRID 326445 reaction equation
[CH3:1][O:2][C:3]1[CH:20]=[CH:19][C:6]([CH2:7][CH2:8][N:9]2[CH2:16][CH:15]3[C:17](=O)[CH:11]([CH2:12][Se:13][CH2:14]3)[CH2:10]2)=[CH:5][CH:4]=1.NN.[OH-].[K+].C([O-])([O-])=O.[K+].[K+].Cl(O)(=O)(=O)=O>C(O)COCCOCCO.CCOCC.C1(C)C(C)=CC=CC=1>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([CH2:7][CH2:8][N:9]2[CH2:10][CH:11]3[CH2:17][CH:15]([CH2:14][Se:13][CH2:12]3)[CH2:16]2)=[CH:19][CH:20]=1

Participants

9

Reactant 5

HCID 9321HydrazineHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 24247Perchloric AcidHCID 14257725HCID 14257725, compound

Product 1

HCID 4987319HCID 4987319, compoundYield 93.1%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 7237O-XyleneSolventHCID 8172Triethylene GlycolSolvent

Procedure

A jacketed flask equipped for simple distillation was charged with a suspension of 7-p-methoxyphenethyl-3-selena-7-azabicyclo[3.3.1]nonan-9-one (0.65 g, 1.92 mmol), hydrazine (95%, 1.00 g, 29.7 mmol), and potassium hydroxide (85%, 3.0 g, 45.5 mmol) in triethylene glycol (25 mL). Under a rapid stream of nitrogen, the suspension was heated to 140°-145° C. by boiling xylene in the jacket of the flask. Stirring was continued at this temperature for 3 hours during which time a small amount of water and excess hydrazine distilled from the reaction mixture. After cooling to room temperature, the resulting solution was diluted with water (100 mL) and was extracted with ether (5×40 mL). The combined ether extracts were dried (K2CO3) overnight and 60% perchloric acid (0.5 g, 3.0 mmol) was added very slowly. This precipitated an orange solid. The ether was decanted and the solid was recrystallized (absolute ethanol) with the aid of decolorizing carbon to give 0.58 g (71%) of 7-p-methoxyphenethyl-3-selena-7-azabicyclo[3.3.1]nonane hydroperchlorate as white needles: mp 208.5°-209.0° C.; IR (KBr) cm-1 3425, 1085; 1H NMR (DMSO-d6) δ1.73 [br d, 1H, H(9), J=14 Hz], 1.90 [br d, 1H, H(9), J=14 Hz], 2.42 [br s, 2H, H(1,5)], 2.65 [d, 2H, H(2,4)ax, J=12 Hz], 3.02 [t, 2H, H(11-ArCH2) J=7 Hz], 3.22 [d, 2H, H(2,4), J=14 Hz], 3.30 [m, 2H, H(10-NCH2)], 3.36 [d, 2H, H(6,8)ax, J=12 Hz], 3.76 [s, 3H, OCH3 ], 3.86 [d, 2H, H(6,8)eq, J=12 Hz], 6.97 [d, 2H, H(3',5'), J=9 Hz], 7.32 [d, 2H, H(2',6'), J=9 Hz], 8.92 [br s, 1H, H(7)]; 13C NMR (DMSO-d6) ppm 21.9 [t, C(2,4)], 25.3 [d, C(1,5)], 28.5 [t, C(9) or C(11)], 28.9 [t, C(11-ArCH2) or C(9)], 55.0 [q, OCH3 ], 56.7 [t, C(6,8)], 58.9 [t, C(10-NCH2)], 114.0 [d, C(3',5')], 127.7 [s, C(1')], 129.6 [d, C(2',6')], 158.1 [s, C(4')]; 15N NMR (DMSO-d6) ppm 48.10 [N(7)]; 77Se NMR (DMSO-d6) ppm 88.64 [Se(3)]. Analysis calculated for C16H24ClNO5Se: C, 45.24; H, 5.69; N, 3.30; Se, 18.59. Found: C. 45.42; H, 5,80; N, 3.30; Se, 18.46. ##STR26##

Workup

  1. customA jacketed flask equipped for simple distillation
  2. temperatureUnder a rapid stream of nitrogen, the suspension was heated to 140°-145° C.
  3. distillationa small amount of water and excess hydrazine distilled from the reaction mixture
  4. additionthe resulting solution was diluted with water (100 mL)
  5. extractionwas extracted with ether (5×40 mL)
  6. additionwas added very slowly
  7. customThis precipitated an orange solid
  8. customThe ether was decanted
  9. customthe solid was recrystallized (absolute ethanol) with the aid of decolorizing carbon

Sources & evidence

ORD record
ord-067aff42163244f48e8671c9f4407637
Source dataset
uspto-grants-1993_12
Patent number
US05268481

Reaction notes

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