|
|
| Author |
Message |
nubee
Master Archiver
|
| Joined: 18 Feb 2005 |
| Posts: 215 |
| Location: homeless |
18648.26 Points
|
|
|
Asarone to TMA-2;
Fri Feb 18, 2005 1:04 pm |
 |
|
 :
ive read up on this topic a bit, seen a few different methods;
whats the "best" way atmo...?
preferably from experience,
factors to take into consideration ;
Yield, Reagents, Complexity, |
|
| Back to top |
|
 |
ApprenticeCook
DILLIGAF
|
| Joined: 12 Feb 2005 |
| Posts: 162 |
| Location: Australia |
8486.38 Points
|
|
|
Mon Feb 21, 2005 4:31 am |
|
|
The only method i know of that doesnt require to much in the way of strange reagents would be the one on rhodiums site... check the mirrors we have links to provided by the watcher for details.
calmus oil --> Arasone --> 2,4,5-trimethoxy-benzaldehyde --> 2,4,5-trimethoxy-phenyl-2-nitropropene --> TMA-2
or if you can get nitrites:
arasone --> 2,4,5-Trimethoxyphenyl-2-nitropropene --> 2,4,5-Trimethoxyphenyl-2-propanone --> TMA-2
Both methods are on rhodium mirrors, just try and look this board is not for repeating information that is already readily availible... if you cant do either of these methods you may need to research the reactions of arasone, also another page on rhodium....
-AC |
|
| Back to top |
|
|
nubee
Master Archiver
|
| Joined: 18 Feb 2005 |
| Posts: 215 |
| Location: homeless |
18648.26 Points
|
|
|
Mon Feb 21, 2005 9:37 am |
|
|
ive read the "guide" you refer to with theis statement, but can you clarify what getting the nitrites is about...?
 i was hoping with this thread to get some feedback regarding experience rather than what's allready online and circulated thouroughly, but i also understand that alot of of people may not be into posting much while the forums arent encrypted or secure...[/b] |
|
| Back to top |
|
|
ApprenticeCook
DILLIGAF
|
| Joined: 12 Feb 2005 |
| Posts: 162 |
| Location: Australia |
8486.38 Points
|
|
|
Mon Feb 21, 2005 1:41 pm |
|
|
the documents on rhodium are all tested and the information presented comes from experience, read them....
Get nitrites means if you are able to get nitrite salts... exactly what it says is what it means funnily enough... who would have guessed....
If you read the methods you will see the second i refered you to requires NaNO2 - sodium NITRITE. If you have no access to this chemical then you cant do this method... get it? got it? good.
I have no interest in TMA-2 so i am not going to give you anything apart from the methods on rhodium which do come from experience of the author....
Take it or leave it i dont care...
-AC |
|
| Back to top |
|
|
IndoleAmine
Dreamreader Deluxe
|
| Joined: 09 Feb 2005 |
| Posts: 681 |
| Location: Bahamas |
18717.10 Points
|
|
|
Mon Feb 21, 2005 4:59 pm |
|
|
I'm not sure - but does the pseudonitrosite route work with asarone (re: acid-sensitive)?
I remember that Chromic claimed having had success with a buffered peracetic on asarone (with low yields though), and then there's of course the oxone or the O2 wacker...
(Nef is not recommended here, asarone nitropropene won't survive it I think)
i_a |
|
| Back to top |
|
|
nubee
Master Archiver
|
| Joined: 18 Feb 2005 |
| Posts: 215 |
| Location: homeless |
18648.26 Points
|
|
|
Tue Feb 22, 2005 10:49 am |
|
|
firstly:
| Quote: |
|
I have no interest in TMA-2
|
why?
secondly this is something that kinda set me off;
| Quote: |
Ritter:
Take it from someone who knows: Randolph Carter has been around here since day 1 but it appears his writing skills (when you can actually read what he wrote) are far advanced compared to his proficiency in organic synthesis. There is no way he produced the ultra-high yields of TMA-2 via Leukart reaction as claimed in the writeup at Rh&--8217;s. Phenylacetones simply do not work as well as other ketones with this rxn. If the rxn. is run as Randolph described, you will be lucky to isolate anything greater than a 30% yield of primary amine.
|
so i have been thinking that the
| Quote: |
|
Reduction of TMP2NP using Uruishibara Catalyst
|
might be better than Leukart ... |
|
| Back to top |
|
|
IndoleAmine
Dreamreader Deluxe
|
| Joined: 09 Feb 2005 |
| Posts: 681 |
| Location: Bahamas |
18717.10 Points
|
|
|
alterantives to urushibara
Sun Mar 20, 2005 9:48 pm |
|
|
If you have access to it: use LAH to reduce the nitropropene, gives constantly good yield.
If you don't have LAH lying around  : try Al/Hg either directly on the nitropropene (although I honestly don't know if it will work, maybe ask Tetraedr, he should know) or on the 2,4,6-trimethoxyphenylacetone oxime (works, but not realy good)...
Both are higher yielding than urushibara nickel reduction of the nitropropene.
Or if you like engineering: try reductive amination with ammonia/pressurized hydrogen over raney nickel in MeOH...
Calamus oil (or better distilled asarone) can be converted to 2,4,6-trimethoxyphenylacetone with a PdCl2/O2/benzoquinone wacker oxidation IIRC....
The pseudonitrosite route to nitropropenes looks easy, but involves really toxic intermediates (nitroso compounds) and should be avoided if possible. |
|
| Back to top |
|
|
starl1ght
|
| Joined: 27 Feb 2005 |
| Posts: 9 |
|
0.00 Points
|
|
|
Re: alterantives to urushibara
Mon Mar 21, 2005 11:14 pm |
|
|
| IndoleAmine wrote: |
The pseudonitrosite route to nitropropenes looks easy, but involves really toxic intermediates (nitroso compounds) and should be avoided if possible.
|
The intermediates in the Pseudonitrosite reaction are not N-nitroso compounds which are the very toxic ones.
Do you have any data to indicate the toxicity of the intermediates or is it just a confusion? |
|
| Back to top |
|
|
starl1ght
|
| Joined: 27 Feb 2005 |
| Posts: 9 |
|
0.00 Points
|
|
|
Re: alterantives to urushibara
Mon Mar 21, 2005 11:27 pm |
|
|
| IndoleAmine wrote: |
|
Calamus oil (or better distilled asarone) can be converted to 2,4,6-trimethoxyphenylacetone with a PdCl2/O2/benzoquinone wacker oxidation IIRC....
|
I don't think you do recall correctly. Asarone is a propenyl benzene. Isn't the wacker for allylbenzenes? |
|
| Back to top |
|
|
IndoleAmine
Dreamreader Deluxe
|
| Joined: 09 Feb 2005 |
| Posts: 681 |
| Location: Bahamas |
18717.10 Points
|
|
|
my fault
Tue Mar 22, 2005 6:14 pm |
|
|
No, I have no data about the toxicity of the pseudonitrosites (and am aware that they aren't nitroso compounds), but I thought having read something about toxicity of pseudonitrosites...
(but my memory fools me sometimes; see below)
About Wacker and asarone: yes, you're right - my fault...
The only methods I could think of now are ozone and electrochemical oxidation - the former is well known, the latter described in EP0247526 "Process for preparing 3,4-dimethoxyphenylacetones"..
short excerpt:
Isoeugenol is a propenylbenzene like asarone, and i hope one can replace those crazy electrode materials with something more common - else this is byzantine...
i_a |
|
| Back to top |
|
|
nubee
Master Archiver
|
| Joined: 18 Feb 2005 |
| Posts: 215 |
| Location: homeless |
18648.26 Points
|
|
|
Wed Mar 23, 2005 8:50 am |
|
|
Taken from "(Uncle Fester) Practical LSD manufacture"
"It seems fester has probably never made acid..."
"The first edition contianed 115 pages, of which only about 70 pages actually had anything to do with LSD synthesis, the rest mostly about Fester's pet project: TMA-2 synthesis. "
The section on asarone is of a higher grade/help:
:How good this is SWIM'd like to know ... but it's definately alot less toxic and easier, especially if using the "method two" construction of his electro-cell.
See European Patent 0,247,526 titled "A
Process for 3,4-dimethoxyphenylacetone Preparation." This process
uses a simple electrochemical cell to convert the propenyl-benzene to
the corresponding phenylacetone in very high yield. The procedure
given also works with 2,4,5-trimethoxypropenylbenzene (asarone),
and probably also with iso-safrole. It is my opinion that it will work
with all propenylbenzenes.
There are great advantages to the use of an electrochemical cell in
clandestine synthesis. The solvents and the salts can be reused over
and over again, making for a very low profile. The reagent doing the
transformation is electricity, available at the nearest wall socket. The
transformer, multimeter and alligator-clip wiring can all be obtained at
Radio Shack with zero suspicion attached. This method comes with
my highest recommendation.
To do the reaction, a 1000 ml beaker must be rigged up as shown in
Figures 6 and 7.
A central piece of
stainless steel having a
surface area of about 100 cm2
actually in contact with the
solution is securely clamped
into place down the center of the beaker.
On each side of this stainless steel piece,
securely clamp into place two pieces of
graphite, roughly equal in size, having a
total surface area in contact with the
solution of about 70 cm2. All three of
these electrodes should run
straight down into the flask, and a
constant distance of 1 cm should
separate the surface of
the anodes from the
cathode. This is very
important, as the anodeto-
cathode distance determines the voltage at which this cell runs. It is
also very important that shorts between the anode and cathode be
prevented. The current must flow anode-to-cathode through the
solution, not through a short!
Then into the beaker place a magnetic stirring bar, 25 grams of
NaBr dissolved in 100 ml of water, 500 ml of acetonitrile, and 20
grams of asarone. Note now the depth of the solution in the flask, and
> Stainless steel cathode
Graphite anodes (2)
Figure 6
Electrochemical cell used to convert a
propenylbenzene to the corresponding phenylacetone.
be sure that the required amount of electrode surfaces are in the
solution. I depicted graphite sheet anodes, in Figures 6 and 7, but the
more commonly available graphite rods will work as well.
Now, using alligator-clip wiring, attach one clip to the central
stainless steel cathode, and run it to your DC transformer where it is
connected to the black or negative pole. Another approximately onefoot
long section of alligator-clip wiring is
attached to each of the
graphite anodes; i.e. the
alligator-clip on one end
gets attached to graphite
anode A, while the
alligator-clip on the
opposite end of the wire
gets attached to graphite
anode B. Then remove
some insulation in the
center of the wire, and
make an electric
connection to the
positive and red pole on
the DC transformer.
Next, begin vigorous
magnetic stirring of the solution,
turn on the transformer, and adjust the output of the transformer so
that it is pushing a constant current of about 3.4 amps. All three
of the electrodes should be fizzing away at this point. If one appears
dead, dig the alligator-clip into it to make better contact. Continue
passing electricity until 24,000 coulombs have been passed
through the solution. A coulomb is defined as 1 amp-second, so this
takes about 2 hours at 3.4 amps. The patent states that the temperature
must be kept in the range of 10-306 C, so watch to make sure that
the current
Stainless steel cathode
Graphite anode j - Graphite anode
Figure?
Side view of electrochemical cell.
doesn't heat up the solution too much. Surround the beaker with ice if
this occurs.
The electrochemical cell makes the following compound, an
epoxide:
When the required amount of current has been passed, turn off the
juice and the stirring, and pour the contents of the beaker into a sep
funnel. Allow it to stand for about Vi hour for the phases to fully
separate. An aqueous phase settles out at the bottom of the sep funnel, in
spite of the fact that water and acetronitrile are miscible. This water
phase contains the NaBr. It should be separated off and saved for reuse.
The acetonitrile phase contains the product. It should be poured
into a distilling flask, and the solvent removed under a vacuum. By
packing the receiving flask in dry ice during this process, the
acetonitrile can be recovered for reuse.
The residue of epoxide product left in the flask should be diluted
with 150 ml of ethyl acetate, and poured into a 500 ml flask. Flush the
flask with nitrogen, then add 1.5 grams lithium iodide, and reflux for 5
hours. The lithium iodide catalytically transforms the epoxide to the
phenylacetone.
After the 5 hours of reflux are over, allow the mixture to cool,
then pour it into a sep funnel. Wash the ethyl acetate solution with 50
ml of water to recover the lithium iodide into the water solution.
Separate off the water layer, and evaporate the water to recover the
lithium iodide for reuse. The ethyl acetate solution should be dried
over some anhydrous sodium sulfate, then the ethyl acetate evaporated
off to give about 20 grams of 2,4,5-trimethoxyphenlyacetone. This
light-sensitive substance should be stored in the freezer.
Method Two
Acetonitrile is a quite poisonous solvent, dangerous both in
inhalation from the fizzing electrochemical cell and by absorption
through the skin. It has been my experience that just spilling a little bit of
it on your skin is enough to give you head rushes and make you feel
uncomfortable. The use of acetonitrile can be avoided without loss of
yield by using the alternative procedure in Example 6 in the patent.
The electrochemical cell is constructed in exactly the same way as in
the first method. Then into the electrochemical cell put 400 ml of
dimethylformamide, 200 ml of water containing 27 grams NaBr, and 20
grams asarone. Check the level of the solution, and make sure that the
amount of electrode surfaces are the same as in the first method. Then
begin stirring, and pass the current through the solution exactly as in the
first method.
When the 24,000 coulombs have been passed, pour the contents of
the beaker into a sep funnel, dilute with 1000 ml of a 20% solution of
salt in water, and extract four times with 200 ml portions of ethyl
acetate. The combined extracts, amounting to 800 ml, should be
washed twice with 200 ml portions of a 20% solution of salt in water.
The ethyl acetate solution contains the product epoxide. It should be
evaporated under a vacuum to a volume of about 200 ml, then reacted
with lithium iodide just as in the first method to yield about 20 grams of
2,4,5-trimethoxyphenylacetone.
Recycling of solvents is possible with this method too. Ethyl
acetate can be recovered during the vacuum evaporation by use of a
dry-ice trap. The dimethyl-formamide can be recovered by vacuum
distillation.
Fester then goes on to detail 3 different methods for further conversions...of which i feel the second would be easiest 
Download Festers...
---------------- |
|
| Back to top |
|
|
|
|
|
Powered by phpBB 2.0.11 © 2001, 2002 phpBB Group
Igloo Theme Version 1.0 :: Created By: Andrew Charron
|
Forums
Rhodium
The Hive
Shop
Profile
Log in
Register
Log in to check your private messages
731