O-Xylene → HCID 14257741, compound

HRID 326444Notes

Reaction equation

HRID 326444 reaction equation
[CH2:1]([N:9]1[CH2:16][CH:15]2[C:17](=O)[CH:11]([CH2:12][Se:13][CH2:14]2)[CH2:10]1)[CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[OH-].[K+].C1(C)C(C)=CC=CC=1>C(O)COCCOCCO>[CH2:1]([N:9]1[CH2:16][CH:15]2[CH2:17][CH:11]([CH2:12][Se:13][CH2:14]2)[CH2:10]1)[CH2:2][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1

Participants

5

Reactant 3

HCID 7237O-XyleneHCID 14797Potassium HydroxideHCID 14257723HCID 14257723, compound

Product 1

HCID 14257741HCID 14257741, compoundYield 54.2%

Reagents, catalysts & solvents 1

HCID 8172Triethylene GlycolSolvent

Procedure

A jacketed flask was charged with a mixture of 7-phenethyl-3-selena-7-azabicyclo[3.3.1]nonan-9-one (1.3 g, 4.2 mmol) N2H4 (95%, 2.0 g, 59 mmol), and KOH (85%, 6.0 g, 91 mmol) in triethylene glycol (40 mL). The flask was equipped for simple distillation under a rapid stream of nitrogen. The reaction mixture was heated to 140°-145° C. by boiling xylene contained in the jacket. Heating was continued under a nitrogen stream for 5 hours. During this time, a small amount of water and hydrazine distilled out. The resulting clear, light brown solution was cooled in a water bath to room temperature and was then poured into ice-water (200 mL). The white suspension which formed was extracted with ether (5×40 mL). The combined ether extracts were washed with brine (30 mL) and dried (K2CO3) overnight. After filtering out the desiccant, this ether solution was cooled to 0°-5° C. in an ice bath and 60% HClO4 (1.0 g, 6.0 mmol) was added dropwise, very slowly. After stirring overnight, the resulting orange precipitate was filtered and recrystallized (methanol, decolorizing carbon) to give 0.67 g (40%) of 7-phenethyl-3-selena-7-azabicyclo[3.3.1]nonane hydroperchlorate as white plates: mp 249°-250° C. (dec): IR (KBr) cm-1 3400, 1140; 1H NMR (DMSO-d6) δ1.73 [br d, 1H, H(9), J=14.0 Hz], 1.89 [br d, 1H, H(9), J=13.8 Hz], 2.41 [br s, 2H, H(1,5)], 2.64 [d, 2H, H(2,4)ax, J=12.1 Hz], 3.07 [t, 2H, H(11-ArCH2), J=7.9 Hz], 3.20 [d, 2H, H(2,4)eq, J=12.2 Hz], 3.33 [m, 4H, H(10-NCH2), (6,8)ax ], 3.86 [d, 2H, H(6,8)eq, J=12.3 Hz], 7.28-7.50 [m, 5H, Ar-H], 8.89 [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-ArCH2)], 29.9 [t, C(11-ArCH2) or C(9)], 56.7 [y, C(6,8)], 58.8 [t, C(10-NCH2)], 126.8 [d, C(4')], 128.5 [d, C(2',6',3',5')], 136.2 [s, C(1'))]; 15N NMR (DMSO-d6) ppm 48.25 [N(7)]; 77Se NMR (DMSO-d6) ppm 88.42 [Se(3)]. Analysis calculated for C15H22ClNO4Se: C, 45.64; H, 5.62; N, 3.55; Se, 20.00. Found C, 45.77; H, 5.80; N, 3.48; Se, 1985. ##STR25##

Workup

  1. customThe flask was equipped for simple distillation under a rapid stream of nitrogen
  2. temperatureThe reaction mixture was heated to 140°-145° C.
  3. temperatureHeating
  4. customfor 5 hours
  5. distillationDuring this time, a small amount of water and hydrazine distilled out
  6. additionwas then poured into ice-water (200 mL)
  7. customThe white suspension which formed
  8. extractionwas extracted with ether (5×40 mL)
  9. washThe combined ether extracts were washed with brine (30 mL)
  10. dry with materialdried (K2CO3) overnight
  11. filtrationAfter filtering out the desiccant
  12. temperaturethis ether solution was cooled to 0°-5° C. in an ice bath
  13. filtrationthe resulting orange precipitate was filtered
  14. customrecrystallized (methanol, decolorizing carbon)

Sources & evidence

ORD record
ord-0cc2495728e243f4a46ddc908270b209
Source dataset
uspto-grants-1993_12
Patent number
US05268481

Reaction notes

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