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SYNTHESIS OF MDP2P FR OM 1,3-BENZODIOXOLE

FR IEDEL-CR AFTS ALKYLATION W ITH 2-NITR OPR OPENE
W RITTEN

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SCOOBY DOO

HTM L by Rhodium

To a 3-necked 500 ml flask under a nitrogen atmosphere was added 300 mL of dry DCM, 0.1 mole of 2Nitropropene (8.7g) and 0.5 moles of 1,3-Benzodioxole (61 g). The flask was then secured within a dewar flask
sitting on top of a magnetic stirplate. Dry ice was added to the dewar flask which was filled with acetone until a
temperature of approx -78C was acquired. Once the internal flask temperature of -70C was reached, 0.1
mole (19 g) of TiCl4 was dripped slowly into the stirred solution. The temp started to rise so the addition was
controlled to keep the internal flask temp around -60C to -70C. The flask was then stirred for 30 mins at 70C, by which time the precipitate which formed from the addition had dissipated. The dewar flask was
removed and the stirring solution was allowed to warm up to room temperature, during which time the black
solution will change viscosity and colour.
To hydrolyze the formed nitro-titanium complex, 100 mls of water was added to the solution which was then
refluxed for 2 hours. During the reflux a brown gas (probably NO 2) is evolved. The flask was cooled and vacuum
filtered (cleans it up a lot) the water layer seperated and discarded. The organic layer was then washed with
3x200 mL of 10% NaOH and 1x200 mL of a brine solution. It was then dried with magnesium sulfate, the DCM

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evaporated and resulting orange-yellow oil vacuum distilled. The 1,3-Benzodioxole came over at 40-45C at 10
mbar then a yellow-green fluorescent oil (MDP2P) began distilling at 135C at 3 mbar.
8 grams of MDP2P was collected,
corresponding to 45% yield from 2Nitropropene or 23.5% from 1,3Benzodioxole
(calculated
on
the
amount
of 1,3-Benzodioxole not
recovered during workup).
Reference: Tetrahedron Letters, Vol 29, No 24, pp. 2977-2978 (1988)

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