spanner
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Piperic acid to piperanol
Hi therte guys, had a dream the other night where someone got up to the piperic acid stage but was having heaps of trouble oxcidising the pieric acid
into piperanol , he tried the potasium permanganate in water with the piperic acid suspended in water but with no luck, Is there anyone out there who
has successfully oxcidise piperic acid to get piperanol via any other method such as copper sulfate or via any other method you help would be much
appreciated and in return will post a simple method of processing bulk peper and solvents in an area no larger than a bathtub
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ctrlphreak
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I'm now really interested in knowing how you overcame the nitroethane problem inherent in this. Because I know that a reason this reaction has been
not experiemnted in a lot of ways is because of the need for NitroEthane.
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spanner
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My friend has aquired it through a friend who works for a major oil company plus it can be readly made i have included a nitroethane RXN for you
Nitroethane below
Nitroethane forms a colorless to oily liquid with a pleasant odor. It has a melting point of –50 Celsius, and a boiling point of 115 Celsius.
Nitroethane is only very slightly soluble in water, but miscible in alcohol, and ether. It is also soluble in chloroform. Nitroethane forms explosive
salts when treated with strong bases. It can be made by reacting ethyl bromide with sodium nitrite.
Method 1: Preparation of nitroethane
Materials:
1. 45 milliliters (1.5 fluid oz.) of ice water 7. 30 grams (1 oz.) of sodium nitrite
2. 75 milliliters (4 fluid oz.) of 98% sulfuric acid 8. 27 grams (0.95 oz.) of ethyl bromide
3. 75 milliliters (4 fluid oz.) of 95% ethyl alcohol 9. 1250 milliliters (42.2 fluid oz.) of ice water
4. 60 grams (2.1 oz.) of potassium bromide or 52 grams (1.8 oz.) of sodium bromide 10. Five 90-milliter portions (five 3 fluid oz. portions) of
diethyl ether
5. 10 grams (0.35 oz.) of anhydrous calcium chloride 11. Three 75-milliliter portions (three 2.5 fluid oz. portions) of ice cold water
6. 500 milliliters (16.9 fluid oz.) of dimethylformamide (DMF) 12. 15 grams (0.52 oz.) of anhydrous magnesium sulfate
Summary: Nitroethane is readily prepared by condensing ethyl bromide with sodium nitrite. The ethyl bromide can be made on site by the interaction of
ethyl alcohol with potassium or sodium bromide in the presence of concentrated sulfuric acid. The ethyl bromide once prepared, can be purified by
distillation. Once the reaction between the ethyl bromide and sodium nitrite is complete, the reaction mixture is extracted with ether, the ether
removed, and the resulting remaining nitroethane then distilled to recover the purified product.
Hazards: Wear gloves when handling concentrated sulfuric acid, and use caution. Ethyl alcohol, dimethylformamide, and ether are highly flammable.
Ether can form explosive mixtures with sir, so use caution and extinguish all sources of ignition.
Procedure:
Step 1: Preparation of ethyl bromide
Into a standard flask (see illustration below), equipped with motorized stirrer or other stirring means, addition funnel, and thermometer, place 45
milliliters (1.5 fluid oz.) of ice water. Thereafter, slowly and carefully add in 75 milliliters (4 fluid oz.) of 98% sulfuric acid. Then place this
acid mixture into an ice bath, and chill to about 0 Celsius. Afterwards, place 75 milliliters (4 fluid oz.) of
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95% ethyl alcohol into the addition funnel, and then slowly add this ethyl alcohol, drop-wise, to the acid mixture. During the addition of the
alcohol, stir the acid mixture and maintain its temperature around 0 Celsius at all times. After adding in the ethyl alcohol, slowly add in, 60 grams
(2.1 oz.) of potassium bromide or 52 grams (1.8 oz.) of sodium bromide, in small portions at a time, over a period sufficient to keep the reaction
mixture at 0 Celsius. After the addition of the bromide salt, continue to stir the entire reaction mixture for about 30 minutes, and thereafter, pour
this entire reaction mixture into a distillation apparatus, and distill-off the ethyl bromide at 38 Celsius. When no more ethyl bromide passes over or
is collected, stop the distillation process, and then recover the ethyl bromide from the receiver flask. Then add to this collected ethyl bromide, 10
grams (0.35 oz.) of anhydrous calcium chloride, and then stir the entire mixture for about 10 minutes—thereafter, filter-off the calcium chloride.
Finally, re-distil this ethyl bromide using a fractional distillation apparatus at 38 Celsius. After the distillation process, collect the ethyl
bromide and store it in an amber glass bottle in a refrigerator until use.
Figure 049. Advanced apparatus for the preparation of ethyl bromide.
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Figure 050. Standard distillation apparatus for the recovery of ethyl bromide.
Step 2: Preparation of nitroethane
Into a standard flask, equipped with motorized stirrer or other stirring means, place 500 milliliters (16.9 fluid oz.) of dimethylformamide (DMF),
followed by 30 grams (1 oz.) of sodium nitrite. Thereafter, stir this entire mixture to form a uniform mix, and then place this mixture into a
cold-water bath. Afterwards, carefully and gradually add in, 27 grams (0.95 oz.) of ethyl bromide (prepared in step 1), over a period sufficient to
keep the reaction mixtures temperature below 25 Celsius at all times. During the addition, rapidly stir the reaction mixture and maintain its
temperature below 25 Celsius. After the addition of the ethyl bromide, continue to rapidly stir the reaction mixture for about 6 hours at a
temperature below 30 Celsius. After 6 hours, pour the entire reaction mixture into a suitable sized beaker, and then add in 1250 milliliters (42.2
fluid oz.) of ice water. Thereafter, extract this aqueous mixture with five 90-milliter portions (five 3 fluid oz. portions) of diethyl ether, and
after the extraction process, combine all ether portions, if not already done so, and then wash this combined ether portion with three 75-milliliter
portions (three 2.5 fluid oz. portions) of ice cold water. Note: after each extraction and washing portion, the ether will be the upper layer each
time. After the washing portions, dry the collected washed ether portion by adding to it, 15 grams (0.52 oz.) of anhydrous magnesium sulfate, and then
stir the entire mixture for about 10 minutes—thereafter, filter-off the magnesium sulfate. Now, place this dried filtered ether mixture into a
distillation apparatus, and distill-off the ether at 40 Celsius. When no more ether passes over or is collected, stop the distillation process, and
then recover the left over remaining residue (after it has cooled). Finally, place this left over recovered residue into a distillation apparatus, and
distill over the nitroethane at 115 Celsius. When no more nitroethane passes over or is collected, stop the distillation process, and recover the
nitroethane (after it has cooled). Then place this nitroethane into an amber glass bottle and store it in a cool dry place until use.
this synth was taken from the Kings chemistry survival guide first edition
[Edited on 10-7-2006 by spanner]
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spanner
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Come on guys someone help my friend out here this process is a good way, why has nobody gone down this path, the nitro is not that hard to source or
make and the way things are going its getting harder and harder to acquire safrole so an otc method such as pepper should be investigated for the
future
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solo
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Mood: ....getting old and drowning in a sea of knowledge
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Reference Information
(Piperic Acid)
(Piperonol)
source for physical data,
http://chem2.sis.nlm.nih.gov/chemidplus/chemidlite.jsp
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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