
DISCLAIMER: THE FOLLOWING INFORMATION IS FOR INFORMATIONAL PURPOSES OR
ACADEMIC STUDY ONLY. CHECK YOUR LOCAL, STATE AND FEDERAL LAWS, AND PROCURE
THE NECESSARY PERMITS BEFORE UNDERTAKING ANY OF THE REACTIONS DESCRIBED
BELOW. NEITHER BOZAKIUM  NOR UNCLE FESTER SHALL BE HELD LIABLE FOR USE,
MISUSE, INJURY, DEATH, IMPRISIONMENT OR FELLATION DUE TO THE APPLICATION OF
THIS INFORMATION. 

                        "Festerlytic Hydrogenation"

Preface:
         As those of you who have been following the chem scene this year
know, the new book from Uncle Fester has been promised and promised by
Loompanics since March or so of this year, with the release date continually
being pushed back, despite the word that it was "at the printer's" in June.
I have been privy to the manuscript of a very,dare I say, revoloutionary
chapter of this book since much earlier this year, and out of respect for
the author's need to make a living, not divulged any "trade secrets" though
I have told of said formula's most vital element, and teased of the
simplicity this new Fester Method. 
        Now several months later, and nearly a year since the book was
written it is still not available and we are now told by 'Panics to expect
it in September sometime. Yeah, right (sarcasm here folks). Anyway, while
discussing this with Fester, I mentioned how I had teased the swarm with
hints of the new method , but hadn't divulged any "trade secrets". The
embittered Fester, pissed at the gravelly hand-job Loompanics has been
giving him(allegedly due to management changes or something) defiantly
trumpeted "Divulge Trade Secrets!" I nearly busted at nut with both
excitement and relief that I could now share this breakthrough with you,
the scientific world. My shit-eating grin still aglow, Uncle excitedly gave
me two new references which promise to significantly shorten reaction time.
It is now my great honor to share this knowlege in the interest of the
furtherment of science. Enjoy.
                                --- Bozakium 1998


                          THE 1998 FESTER FORMULA:

Electrocatalytic Hydrogenation of Ephedrine,
                                       Pseudoephedrine
                                             And
                                                Phenylpropanolamine
                                  
Abstract:

        Reduction of the hydroxyl group of various 1-phenyl-2-aminopropanols
and their substituted amino variants are easily and efficiently carried out
by electrocatalytic hydrogenation of their respective acetic esters at a
palladium or palladium-plated electrode in a divided electrolytic cell. Use
of a lamb's skin prophylactic as an inexpensive yet effective cell divider
is also demonstrated in this experiment.
 
Materials:

One (1) gram of purified ephedrine, pseudoephedrine or phenylpropanolamine.
One troy ounce ingot of palladium
Glacial acetic acid
Concentrated sulfuric acid
Sodium hydroxide
Anhydrous HCl gas source
pH-indicating paper
Toluene
Kling-Tite Naturalamb brand condoms
Lead or graphite electrode 1/2-inch wide by five inches long
Six one-inch alligator clips
Several feet of 16 to 20 gauge insulated copper wire
Variable DC power supply
Ammeter capable of measuring up to 3 amps, with resoloution to 1/10 of an amp
Voltmeter (optional)

Procedure:

        One gram of ephedrine, pseudoephedrine or PPA hydrochloride is
placed in a large test-tube along with 5-7 mL of glacial acetic acid. The
test tube is heated in a water bath until all the ephedrine(in this case)
hydrochloride is dissolved. A few drops of concentrated sulfuric acid are
added. Mix it all together and LOOSELY stopper the end of the test tube to
prevent steam from entering. Heat the water bath to just about boiling, and
use it to heat the test tube and its contents for a few hours. This forms
the acetic ester of the  ephedrine, pseudoephedrine or PPA used in the
reaction.
        The solution should appear clear and water-like, completely
homogenous. After heating, the reaction mixture can be kept stoppered as is
for a few days, but it's best to use it immediately after it's cooked.
        Next, mix up a solution of 5 mL of concentrated sulfuric acid in
100 mL of water. Take a 250 mL beaker, and place it on a magnetic stirrer.
Clip a well-scrubbed Kling-Tite Naturalamb condom in one side of the
beaker, and place a piece of lead 1/2 inch in diameter and a few iches long
inside the condom. On the other side of the beaker, stand up a one-ounce
ingot of palladium. Using alligator clips, make contact with the ingot, and
wth the piece of lead. They are your two electrodes. Next, pour most of the
dilute sulfuric acid solution into the beaker. Save enough that some can be
poured into the condom so that the solution levels are about equal inside
the condom and the beaker. The ingot of palladium should be almost
completely immersed. The alligator clip should be up out of the solution,
and there should be enough space left to add the ester reaction mixture
from the test tube to te beaker without causing the solution level to reach
the alligator clip.
        The surface of the palladium ingot should be lightly sanded prior
to use. This increases its surface area a little and exposes fresh, clean
metal. The piece of lead should be scrubbed free of grease and dirt. The
wire lead to the palladium ingot can be clipped to the side of the beaker
with a clothes pin or paper clip to prevent the ingot from falling over
during the course of the reaction. A DC current meter (ammeter) should be
put in series with the wiring. A good one can be had at Radio Shack for
under $50.00.
        The wires are first hooked up so that the palladium ingot is
connected to the positive pole of the DC power supply, and the piece of
lead to the negative. The typical one- ounce ingot will have a face with an
area of about six square centimeters immersed in the solution and one
square centimeter  up out of the solutuion. Only count the area on the side
facing the lead piece. The back side doesn't count because significant
current doesn't reach it. With this typical ingot apply about two amps for
30 seconds to one minute. Oxygen will bubble freely from the ingot, and
hydrogen from the piece of lead. Blackening will be noted on the edges of
the ingot, where the current is most intense, and a lighter discoloration
on the flat face of the ingot. This pre-treatment is called anodizing. It
has been found that anodizing increases the ability of the palladium ingot
to adsorb hydrogen when the wiring is turned around, and the ingot is made
the cathode.
        Next, redo the wiring so that the palladium ingot is attached to
the negative pole of the DC power supply, and the piece of lead to the
positive. Turn the juice back on and run between one and two amps of
current for about 20 minutes. At first, the amount of hydrogen generated at
the palladium ingot will appear small. This is because the Pd adsorbs
hydrogen so well. After about five minutes of current passage, the whole
surface of the ingot will freely bubble off hydrogen. 
        After the 20 minute charging with hydrogen, begin magnetic stirring
of the solution, and pour in about half of the ester reaction mixture from
the large test tube. Adjust the current flow from the variable power supply
so that a current of about 50 milliamps per square centimeter of palladium
surface flows. If one has about six square centimeters of the ingot facing
the piece of lead immersed in the solution, a current of about 300
milliamps is called for. This will result in some gassing off of hydrogen
from the edges of the ingot, but over the rest of its surface the hydrogen
will react before it bubbles off. The lead anode will form a brown layer of
lead oxide, and will not dissolve at all in the sulfuric acid solution.
Some surface particles will be kicked off the lead when it's first
charging, but they don't make it through the condom. The lead anode can be
replace with a piece of platinum if desired, but lead is a lot cheaper.
Graphite is amother possibilty.
        Keep an eye on the  current meter, as the current flow can change
as the reaction progresses. Keep the current flow around 300 mA (0.3 amp)
for the size ingot given in this example. When 1000 coulombs ( a coulomb is
a unit of charge equalling one amp-second) have passed into the solution,
add the other half of the ester reaction mixture from the test-tube., and
continue at 300 milliamps until 3000 coulombs have passed through the
solution.  Let us use the 300 mA current to show an example of these
calculations: At 300 milliamps, 1000 coulombs pass in 1000 / 0.3 Amps =
3333 seconds, or a little under one hour. 3000 coulombs pass in 10,000
seconds, or two hours, 45 minutes.
        3000 coulombs per gram of feed material has been found to give good
yields of a fine product, but by no means consider this number to be
optimal. It may well be that a greater yield would be obtained by passing
more current. It may also be that pseudoephedrine and PPA differ from
ephedrine in their ease of electrocatalytid hydrogenation. I don't think
that any harm can come from passing more current, within reasonable limits,
so by all means experiment with the amount of current passed.
        During the course of thi reduction, the color slowly changes from
its initially clear color to slightly tinted with yellow. It's not known
whether this color change is due to some of the condom soaking out, or if
it's a byproduct of the reaction. In any case, it's a remarkably clean
reaction. 
        When the desired amount of current has passed, the work-up and
isolation of the product is very simple. The Kling-Tite condom is removed
from the beaker. after pulling out (no pun intended) the lead electrode,
the jimmy hat is, as is custom in some parts, flushed down the toilet. The
anode can be used over and over. The palladium cathode is then rmoved and
rinsed off. It too can be reused an INNUMERABLE (Bozakium's  emphasis)
number of times. The process of  anodizing the palladium will have to be
repeated prior to each run. Some fresh metal may have to be exposed on
occasion by light sanding of the metal surface. An ingot of palladium
should last for a lifetime.
        The reaction mixture should be poured into a sep funnel, and a 20 %
NaOH solution should be added with shaking until the solution is strongly
(13 + pH) alkaline to pH paper.
        Extract with two 50 to 100 mL portions of toluene. This should be
plenty for one-gram  of product. THe toluene extracts are then bubbled with
dry HCl to get the crystalline hydrochloride product. After  rinsing them
off with some fresh toluene, they are spread out to dry.
        The most pleasantly surprising finding is that crank produced by
this method doesn't give one the body and soul-wrenching hangovers so
typical of the product made by the iodine-red phosphorous method.. This is
a highly desirable way to keep one's own party rocking and rolling.
        If one should wish to produce more than a gram or so at a time, a
larger palladium cathode should be used. Linking together more ingots of
palladium would get pretty expensive, so a more economical alternative will
be detailed. That alternative is electroplating some copper or brass screen
with a thick coating of palladium.
        The simplest way to get this section of screen electroplated with
palladium is to go to the yellow pages, look under electroplaters and find
one who plates palladium. Ask for a plate build-up of several thousandths
of an inch, so that enough Pd is deposited to last a while..
        The Pd plated screen would then be used exactly like the ingot.
First it must be anodized, then charged up with hydrogen in exactly the
same way. The sole difference is that the greater surface area of the
screen facing the condom-encased anode requires a correspondingly greater
amount of current to be passed. Then, during the course of the reduction,
again 50 milliamps per square centimeter of surface area facing the anode
is used. The total of 3000 or so coulombs per gram of feed material doesn't
change by increasing the size of the electrode.
        An alternative to this is plating the screen yourself, anodically
dissolving a portion of the ingot to form a PdCl2 solution then..... sorry
folks, this all of the manuscript I have, but I'm sure palladium plating is
no national secret (yet).
        There is a company that sells an electroplating kit consisitin of a
power supply, metal solution and a 'pen' electrode. As soon as I find their
paperwork among my rubble I  will post it. 
        The lastest word from Fester is a couple of references from Indian
journals on electroplating graphite electrodes with palladium, essentially
giving a Pd black on C catalyst in the cell! 


1) Krishnan, Electrochemica Acta, Vol 21, Pg 449-450 (1976) 

On the Electrochemical Reduction of  Benzyl Cyanide to Phenethylamine with 
a Pd/C Electrode  (note: The title may not be exact due to the illegibility 
of my chickenscratch transcription of my conversation with UF.)

2) Krishnan, Journal of Applied Chemistry, Vol 5, Pg 125-128 (1975)

The greater activity of Pd on C (over straight Pd) results in a shorter
reaction time.

If anyone manages to find these references, please post them at the hive.
I'd also be happy to answer anyone'e electrical questions, as long as you
are not doing anything illegal of course. Enjoy.

     						--- Bozakium

- - - - - -

Rhodium,I think you need to change something on the fester formula on your 
site.The problem is the ester it says add half of it then wait 45 min or 
so then add the other half.Witch is wrong because a gram needs 3000 coulombs 
to be passed.If you add the ester in two parts it will leave half of the 
product unreacted.Why because the second half will not have the right amount 
of time to be hydrogenated.Witch will give a mix of meth and starting feed.
The ester should be added all at one time and ran until 3000 coulombs has 
passed.But on the other hand some people think why not just run longer to 
let the second half have the right amount of time to react.Wrong why because 
the first half of the ester will more and likely be changed back to the 
starting feed. Just trying to help other where others have failed. 

Readyeddie