which size fits snuggly on its top.
5. One aluminum tube that is the exact diameter size as the polyethylene tubing.
Found at the hardware ste but don’t know what they are used f. They are
sometimes made of brass.
6. One bottle of sulfuric acid drain cleaner.
7. One bottle of concentrated hardware ste muriatic acid 32%?
Assembling the HCl generat is easy.
1. Use the aluminum tubing to burrow two holes to the top of the table-leg
stopper. Use a twisting motion while appling pressure f about a minute
eventually the tube will pop through.
2. Place the table-top stopper over the top of the beer bottle. It’ll fit snugly.
3. Insert the polyethylene tubing into the middle-most hole push through
until the tubing hits the bottom of the beer bottle. with scisss a knife
cut off the polyethylene tubing about two inches from the top of the beer
bottle.
4. Take the entire table-top stopper inserted with the polyethylene tubing off
of the beer bottle. Pour into the beer bottle a volume of sulfuric acid about
an inch high off of the bottom of the beer bottle.
5. Replace the table-top stopper/polyethylene tubing on top of the beer bottle.
Insert the remaining tubing into the last hole of the stopper until about
two inches into the bottle. Cut tubing down to desired length.
6. Pour about twenty milliliters of concentrated HCl into a cup. Extract into
baby syringe until syringe is full 15 mL. NO, the HCl will dissolve
any part of the syringe in any way.
NEITHER THE HCl N THE SULFURIC ACID wILL REACT wITH ANY PIECE OF HARDwARE USED
IN THIS SYSTEM. THIS SET-UP HAS BEEN TESTED MANY TIMES wITH SUCCESS.
7. Insert the syringe into the middle tubing the one that extends to the bottom
of the beer bottle. End should be submerged in Sulfuric acid. If insertion
is difficult, use a knife to scrape the inside of the tubing to allow the
syringe to fit me easily.
8. Securing the set-up with a clamp of some st attached to a st is optional
but desirable.
9. Have hy on the side a container full of water.
The use of this set-up to gas ones solvent/amine is just as easy.
1. with right h, hold the tubing that will expel gas lower into the
solvent/amine solution.
2. with left h slowly start to inject the HCl solution in the syringe into
the sulfuric acid. Once it hits the acid, there will be alot of fizzing
foaming IMMEDIATELY HCl gas will be pumped into the solvent/amine solution.
Foaming is sometimes a problem as it starts to reach the top of the beer
bottle. Simple wait a while let it settle then continue. Sometimes
certain brs of drain opener can cause excessive foaming. If this occurs,
switch brs.
3. One syringe is usually enough f an amount of about 30-40 g of product, but
if me is needed after all the HCl has been injected, slowly SLOwLY remove
the syringe from the tubing, first be letting a crack of air into the system.
BEwARE that this is suddenly going to bring a min rush of HCl from the gassing
tube so make sure that it is submerged when doing this step. To continue, refill
the syringe proceed as described above.
4. Once the gassing is complete, leave the syringe ATTACHED to the injection
tube submerge the gassing tube in the container full of water If the
syringe is attached to the injecting tube, the following sequence will
occur. weigh down the gassing tube somehow as it must remain submerged.
In a few minutes about five the sulfuric acid will cool a bit causing a
sucking-back of the water into the beer-bottle. This will happen very suddenly
very fast, but to wry as the water will only go in as far as the top
of the beer bottle. This is actually an advantage as in this way one is able
to dilute the remaining HCl gas the remaining sulfuric acid. Of course the
bottle will get hot but if left aside f a few minutes it will eventually
cool making opening the container dispensing with the acid solution an easy
task. If the bottle is opened f whatever reason without the above acid
dilution step, HCl gas will be everywhere.
Hope this method will prove useful to you my fellow bees, it sure has been f me!
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
wISDOMwillwIN
Re: DETAILED METHODS for NON-CHEMISTS
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
Methyl_Man (Hive Researcher) 06-05-00 10:40 :
METHYL_MAN’s WRITEUPS of MeOH BENZO WACKER and MeNO2-Al-Hg.
Consult these threads to avoid unnecessairy questions :
http://rhodium.lycaeum.org/clandestine/gonzo/index.html
/perl/showflat.pl?Cat=&Board=methods&Number=13991&page=
&view=&sb=&vc=1″ target=_newhttp://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=13991&page=
&view=&sb=&vc=1 and
/perl/showflat.pl?Cat=&Board=methods&Number=15667&page=
0&view=collapsed&sb=5″ target=_newhttp://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=15667&page=
0&view=collapsed&sb=5 and
/perl/showflat.pl?Cat=&Board=methods&Number=31473&page=
0&view=collapsed&sb=5″ target=_newhttp://hive.lycaeum.org/wwwthreads/perl/showflat.pl?Cat=&Board=methods&Number=31473&page=
0&view=collapsed&sb=5
—————————————————————————————————
Here they are, with minor changes from older versions for greater accuracy.
=================================================================================
Methyl Man’s MeOH version of the benzoquinone wacker
Materials:
400mL MeOH (methanol)
50mL distilled H2O
150g p-Benzoquinone
2g palladium (II) chloride (PdCl2)
178g safrole
DCM (methylene chloride; dichloromethane)
NaCl (non-iodized table salt)
Sodium bicarbonate (baking soda)
5% NaOH
HCl (hydrochloric acid, from muriatic acid)
Magnesium sulfate drying agent (epsom salts baked in 400?XF oven for 2 hours)
Method:
1. In a 2L flask fitted with a reflux condenser and addition funnel place 400ml MeOH, 50ml dH2O,
150g p-Benzoquinone and 2g PdCl2 and leave to stir for a minimum of 60 minutes. Note that a recent
improvement has been discussed which involves stirring the PdCl2 in the solvent (MeOH in this case) for
several hours before adding the water and benzoquinone. It is likely that this does enhance yields a bit by
ensuring maximum efficiency of the PdCl2??s catalytic action. Either way will work well, however. If you let
the PdCl2 stir alone for a while, when you then add the water and benzoquinone, let them stir for an hour as
well before beginning the next step so as to ensure complete dissolution of the benzoquinone.
2. Place 178g safrole mixed with a bit of MeOH in an addition funnel.
3. Add safrole dropwise from the addition funnel over 60 minutes or more. However, when the addition is
about 80% finished, apply low heat just sufficient to start a mild reflux (cold water through the condenser).
4. After the safrole addition is complete, leave mixture stirring and refluxing for 8 hours. (If you must stop at
this point and resume another day, be sure to put the mixture in the freezer, sealed well. The raw ketone
decomposes unless stored at freezer temperatures.)
5. Filter out the solids present in the mixture, which are hydroquinone (the degradation product of the
benzoquinone) and PdCl2. This can be done by vacuum filtration or by simple gravity filtration with coffee
filters. Many prefer gravity filtration with this synthesis because the solids produced in this reaction are very
fine and are problematic to filter with vacuum. Don??t try to recycle the PdCl2, as it is too difficult to
separate from the hydroquinone to be worthwhile.
6. Flood mixture with 1.7L 3N (~10%) HCl. (Here’s the quick math: add 500mL of 31% HCl [muriatic acid] to
1150mL H2O to get 1.65L ~10% HCl?Xclose enough for this purpose.)
7. Extract flooded mixture with 3 portions of DCM (1 x 500mL, 1 x 250mL, 1 x 100mL) in a large separatory
funnel. The desired raw product, MDP-2-P (??ketone??), migrates into the DCM as an oil. Separate the
DCM/ketone layers and combine them.
(Note: when you first hit it with the DCM you will probably observe a bit of scum which will float on top of
the water layer, which will work its way down during these three extractions to appear as a blob of spongy
semi-solid interface. It??s actually very mobile and easy to work around; simply avoid allowing it into your
DCM separations. The same thing will happen in your washes in steps 10, 11 and 12 below, but by then you
will be quite the pro at working with it.)
8. Extract water layer with a final small amount of DCM.
9. Add this final small DCM extraction to the combined oil/DCM solution from step 8.
10. Wash the ketone/DCM solution with saturated sodium bicarbonate in water twice (500mL each wash).
11. Wash the ketone/DCM solution with saturated NaCl 3 times (400-500mL each wash).
(Note: as you do these bicarb and salt water washes, you should be seeing the ketone/DCM solution getting
progressively more greenish colored; this is visible in the film of solution that runs down the inner surface of
the sep funnel).
12. Wash the ketone/DCM solution 3 times with 500mL 5% NaOH (500mL each wash). If you did step 5, you
will have a very easy separation.
(Note: you should also see a very noticeable color change upon doing the first of these three washes wherein
the ketone/DCM layer becomes a strange, thick reddish-brown, almost orange color. This happens as the
NaOH pulls the majority of the solvated hydroquinone into its layer, cleaning the ketone. The NaOH layer in
the first wash will be very dark brown, almost black in fact. The next two will be a far lighter, watery, orangy
color.)
13. Dry the ketone/DCM solution with ~50g magnesium sulfate.
14. Distill off the DCM using mild heat on a water bath and ice-cold water through the condenser. This will
take several hours.
15. Add 50mL of high-oleic safflower oil (no additives!!) to the ketone oil as a buffer to prevent the ketone
from scorching in the distilling flask.
16. Vacuum distill the ketone/buffer oil mixture. This also will take a few hours, but not as long as distilling
the DCM off did.
17. At 100 to 140?XC (wherever your particular vacuum dictates), a minor amount of safrole might come over.
If your safrole-to-ketone conversion was good, there should only be a very small amount. If it is only a few
drops to a milliliter or two, you can leave it in, and not change/clean receiving flasks. If you are a stickler for
purity, discard it. It will not harm anything later if you leave it in. But if it??s more than a couple of milliliters,
get rid of it.
18. At anywhere from 25 to 40?XC above the temperature your safrole usually comes over with the same
vacuum, the ketone should begin coming over. You should get about 100 to 120g ketone. The color of the
ketone coming over will likely be a pale, fluorescent-looking greenish yellow. In fact it looks not unlike
anti-freeze?Xa similar ??neon green.?? You can stop distilling when the rate of ketone coming over has slowed
to an agonizing one drop per 90 seconds or so. At this point there is so little left that it is probably not worth
your time to wait for a drop per 1.5 minutes (it??s not worth mine anyway).
19. Immediately store your precious fluid in the freezer in an airtight sealed flask or bottle. Happy cooking!
———————————————————————————————————
The MeNO2-Al-Hg reductive amination according to Methyl Man
Since the appearance of Ritter’s writeup of this method in Total Synthesis II, much discussion has taken place
about it but, it has sometimes seemed, little has been clarified. This is due in large measure to the sensitivity
of this reaction to even the most minor changes in its many variables. With this writeup, I hope to provide a
clearer view of the method and to allow others to benefit from the hard-won experience of someone (not me)
whom we’ll call Mr. A. Ritter’s original writeup, while inspiring, lacked details about the many nuances that,
once understood, allow the amateur chemist to really understand this reaction’s dynamics. Thus I have tried
with this writeup to help the neophyte who has only physical observations and scant written material to guide
him (although I suspect and hope that it may even help a few more seasoned cooks as well).
The first thing I’d like you to look at is the array of interrelating variables in this reaction that make it so
delicate. They are as follows:
1) the thickness/type of the aluminum
2) the consistency (i.e. flat, ground, etc.)
3) the amount of HgCl2 used in relation to the amount of aluminum
4) the addition rate of the MeNO2/MDP-2-P
5) the size of the reaction vessel in relation to the scale of the reaction
6) the ability to effectively stir the reaction
7) the coldness of the water through the reflux condenser (yes, even that!)
The above factors are sort of submitted in an order of importance (#1 being most important), but in reality
they are all inextricably related. I observed firsthand the trials and tribulations of Mr. A as he struggled to
match up the correct combination of ratios and conditions that would allow a smooth, consistent reaction
and predictable results every time. Finally, after lots of frustration, confusion, losses, and—in the end—a
revelation, the perfect set of elements was hit upon and recorded.
The scale Mr. A chooses to perform this reaction on is half-scale to the scale in the Ritter writeup, which was
55g aluminum and 50g MDP-2-P. Therefore this writeup will illustrate the reaction on a scale of 27.5g aluminum
and 25g MDP-2-P. The subject found for his own personal reasons that this smaller scale was much easier to
manage (not the least of which is that even with a huge 4-liter separatory funnel, at this smaller scale it gets
pretty filled up!). There’s no doubt that the original larger scale can be successfully applied, although it would r
require adjustments in the glassware capacity, stirring method, and probably other elements.
MATERIALS and APPARATUS:
– 27.5g Reynolds Wrap Heavy Duty aluminum foil
– 25g MDP-2-P
– 20 mL MeNO2 of 99+% purity
–750 mL MeOH + 50 mL more for addition funnel + additional small amounts that will be needed later to thin
the mixture
–400mg HgCl2
– 2-liter 2-neck flat bottom flask
– reflux condenser (400mm preferable)
–250mL or 500mL addition or separatory funnel
– cooling setup (bucket, water pump, tubing, 1 large bag ice)
METHOD:
1. Weigh 27.5g of Reynolds Wrap Heavy Duty aluminum foil (NOTE: it HAS to be Reynolds and it MUST be the
heavy duty stuff) and then tear it by hand or cut it with scissors into small rectangles approximately 1″ by
.75″. Settle down with this task with a good CD or TV show because it is tedious and may take about
1.5 to 2 hours.
2. With a coffee grinder, “grind” these pieces of foil for durations of about 10 seconds. Fill the coffee grinder
only loosely (about two thirds full—don’t stuff it! That will adversely change the consistency of the
ground foil). It will probably take about 4 to 5 “loads” in your grinder to do the whole amount of foil,
depending on the size of your grinder. (In actuality, the foil does not get “ground,” but rather, each
individual piece just gets compacted and compressed. If it is compressed too heavily, the inner surfaces
of the foil nuggets may be rendered inaccessible to the Hg/MeOH solution, changing the timing of the
amalgamation and maybe even causing an incomplete or failed reaction.) When properly done, the foil
should be in gnarled little nuggets about the size of long-grain rice grains and should look really tight and
small. The smaller, the better for good stirring.
3. Place a 3″ stirbar in your 2L flat bottom flask and onto your stirplate. Add the foil nuggets to the flask and
then proceed to set up your glass, support and clamps so that the reflux condenser and addition/sep
funnel are securely affixed and your flask is well-centered on the stirplate (this will be critical when you
begin to attempt stirring!). Also, prepare your cooling, i.e. attach the inflow and outflow tubes to the reflux
condenser.
4. Carefully add the 400mg HgCl2 to 750mL MeOH to a tightly sealable bottle and shake to dissolve all HgCl2.