Isodillapiole Pseudonitrosite and Nitropropeneby Antibody2
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In a 2l erlenmeyer flask, vented out of doors thru hose attatched to side arm, 0.4 moles of iso-dillapiole (mw 228) is dissolved with stirring in 750mls Et2O and chilled to 5C in an ice/salt bath. To this is added 2 moles NaNO2 dissolved in 400mls dH2O, forming a lower layer. Stirring is slowed to lowest setting and 1 mole of H2SO4 dissolved in 400mls ice cold dH20 is added dropwise over 6 hours, and allowed to sit an additional 6 hours with no stirring, ice bath was maintained throughout. After shaking rxn vessel, entire contents is decanted into a 4l beaker containing 2l dH20, after some swirling, the etheral layer with canary yellow precipitate is decanted and gravity filtered, the filtercake washed with a portion of EtOH, vacuum filtered and air dried.
Yield: 85% or 0.34 moles pseudonitrosite derviative of iso-dillapiole (mw 319).
0.34 moles of the above pseudonitrosite was dissolved 600mls EtOH containing 0.85moles of KOH, care being taken that temperature did not rise above 30C. This took several hours, finally forming a turbid reddish brown solution, that was vacuum filtered. The filtrate was stirred in an ice bath while 800mls 2M HCl was added dropwise over 30-45 minutes, followed by an additional 1000mls of ice cold dH20. Stirring was stopped and mixture was vac filtered, yeilding 0.26 moles of bright orange gooey crystals. The crystals were dissolved in the minimum amount of freshly boiled IPA that was required to fully dissolve the crude nitropropene, slowly cooled to RT, placed in the freezer overnight and vac filtered in the morning.
Yield: 73% or 0.24 moles of 2,3-MeO 4,5-MDP2NP (mw 288) as bright yellow/orange crystals, mp 84°C.