====================================================================

=========
Chloro/Bromo/Iodosafrole Synthesis Notes
====================================================================
=========
Endo1, September 27, 2002:
I have not seen a bromosafrole post in a while so here is a detailed
write up
of SW's bromination variation. I like this variant because very
little HBr
fumes are produced, not much labour involved and the yields are
nice.
The drawback is it requires tech grade HBr in GAA.
To a small "gem" jar is added a stir bar, 500 ml of FREEZER COLD
technical
grade 33% hydrogen bromide in glacial acetic acid and 325 ml of
sasafrass oil
(unknown safrole %) in that order. The jar is promptly capped
tightly and
shakin until homogenous. The reactants are then placed on a magnetic
stirrer
inside of a deepfreeze and stirred vigorously for 24 hours (take
care that
the stirbar is not stuck to the inside of the lid!). The contents of
the jar
are allowed to defrost just enough to pour if solids have formed and
then
they are poured in to a large sep funnel containing about 300 grams
of crushed
ice. Sep funnel is occassionally agetaded until ice is all melted.
Organics
are extracted with 1250 ml of toluene and the acid water layer is
discarded.
The toluene/bromo mix is then washed with 500ml of water and a
little baking
soda is added if necesary untill a clean seperation of the water and
organics
is observed (carefull of foaming and pressure build up). The water
layer is
drained and discarded. 500 ml of fresh water is added. Baking soda
is added
slowly with swirling and venting and then, eventually, shaking and
venting
bewtween adds of baking soda untill saturation of water is observed
by a
small amount of undissolved solids. water layer is discarded and a
second
"baking soda wash" is performed in exactly the same way as above.
Solvent
is distilled off under aspirator vacuum and recycled (see footnote
1). The
next 2 fractions are distilled off also under aspirator vacuum (see
footnote
2) and then the bromosafrole is distilled under vaacuum pump reduced
atmosphere to give about 350 grams of fairly clear bromosafrole.
footnotes:
1: The toluene may contain some HBr so it is re-used only for the
same purpose.
2: It seems fairly evident that there are two main fractions after
the
toluene and before the bromosafrole comes. A tiny bit of unreacted
safrole at
110 and then something else at about 130-140 under SW's aspirator
vaac, it's
got a red tinge to it and is fuming a little bit of HBr and smells
kind of
sweet/irritating, maybe isosafrole or brominated isosafrole? xxx/HBr
azeotrope?
Whatever it is, SW thinks that this stuff is what turns some peoples
bromosafrole
red and is kind of hard to seperate from bromosafrole. It seems the
only time
SW's bromo has a red color to it is when he collects his bromo too
early.
Other Notes:
- Keep in freezer if a wash/distill cannot be performed immediately.
- Attempts have been made to use homemade HBr in GAA but problems
occurred due
to the high mp (the shit kept freezing up bad!) Although the mp
listed in the
MSDS is +17c (I think.... hmm why is it higher than just strait up
GAA?), for
some reason the technical grade obtained by SW never freezes in
the freezer if
the container is not opened i.e. the factory seal is not broken
(The 500ml
bottles of tech HBr in GAA are obtained from supplier). Also, very
little
freezing occurs during the reaction when tech grade is used for
some reason.
- Sorry, not sure exactly what temps the reaction actually runs at.
Just a
regular old deepfreeze. Maybe about -5c?
- Attempts have been made to use a flat bottom erlenmyer flask to do
the
reaction but the stirbar created too much heat and or the stirrer
transferred
too much heat so the concave bottom of a jar was found to be more
suitable.
--------------------------------------------------------------------
------------
hsark:
I have distilled bromosafrole lots and lots of times. The problem is
that in the
end of the distllation you tend to get a volcano of black ash and
smoke even if
you are careful. I've been wanting to say this for a long while the
33% HBr in
GAA is the best to use. You can get 90-95% yields in 12-16 hours,
and you can
just leave it in the freezer, although an ice chest with lots of ice
works just
fine. When you distill it, just be ready to disconnect it and have
something to
dump it in. And whatever you do save whats in the recieving side.
Mainly i used to buy the 33% HBr in GAA from a chem supplier, but I
also bought
anhydrous HBr gas in cylinders and would make the solution myself.
Both worked
great, but I dont know how easy it is to aquire some nowadays - I
dont have that
problem. At around 20mmHg the bromosafrole would start distill at
175-185!C and
continue to rise slowly until it reached 212!C, where decomposition
occurred.
I generally would stop at 205!C, but sometimes it decomposes even
if you're
careful. I suggest you to be prepared, and check for vaccuum leaks
very
carefully. Bromosafrole is generally a clear, reddish-brown sweet-
smelling oil.
The proportions were 1L 33% HBr in acetic acid to 450ml safrole.
Ritter:
I've distilled quite a bit of bromosafrole myself, and can tell you
that a higher
vacuum will prevent that rapid charcoal-decomposition-volcano from
occurring.
The decomposition is occuring because the still pot is getting WAY
too hot.
When you only have a few ml's left in the still pot (about 50), cool
it down
and transfer the remaining liquid to a smaller 100ml flask. This
should allow
distillation of the last traces of bromosaf without a problem.
--------------------------------------------------------------------
------------
Here is the only bromosafrole (or bromo propenylbenzene) synthesis
you will
ever need. It proceeds totally anhydrous with pure reagents, and
generates
no obnoxious fumes to give you away. More than likely, this will
spur DEA
to add new watched chemicals (like what isn't watched already- air,
water ?)
To 100 ml of chilled DMSO add 7.8ml conc. H2SO4 (i.e. drain
cleaner). To
this add 30g of NaBr. Stir well and repeatedly. Solution will turn
orange
as all the NaBr is turned into Na2SO4. Do not filter, leave crystals
alone
in case there is some unreacted NaBr left. If the H2SO4 and DMSO is
anhydrous, so will the HBr be anhydrous.
Add 5 ml of sassafrass oil. Or scale qty of everything up for more
sassafrass. Let sit at room temp. Don't bother to filter out
crystals, in
case there is unreacted NaBr. In 1 or 2 days solution will proceed
as in
Fester's turning green, then purple, then gradually burgundy.
To understand why this works so well, see Fieser and Fieser
"Reagents in
Organic Synthesis" under DMSO monograph.
Note that there are two pathways for HBr to react. Via an ionic
mechanism
generates the desirable compound. Via a free-radical route forms
terminal
bromo compound, which cannot be used (you can try for interesting
analogue,
but who cares now that all mind altering chemicals are illegal under
the
Analoges Act, including all those in everyone's brains- imagine,
even Jesse
Helmes committing felony if he has any brain cells left). The crude
sassafrass oil contains eugenol, a phenolic compound which inhibits
free
radical reaction. Thus you will get better product if you don't
purify out
safrole. Also keep reaction mixture away from air and UV light, both
generate free radicals.
The final mixture gets 500-1000ml of water added. The crude
bromosafrole
which settles to the bottom is seperated without adding any organic
solvent. If you cool it it gets pretty sticky and syrupy so the
water layer
can be just poured off.
Then you add 200ml of ethanol and a 5g tablet of hexamine camping
fuel to
start the Delepine reaction- you get MDA as the end product. (Well,
if you
like MDMA better you can do the tedious methylamin synth in Festers
book or
Org. Synth. Look out for methyl formate which is deadly insidious
poison
like dimethyl sulfate)
For the Delepine reaction you can use the bomb or reflux overnight,
which
definitely works. some experimentation is needed here since I still
am
unclear as to how much time this takes, or if it really can be run
at room
temp. The reaction with the iodo intermediate can certainly be run
at room
temp, but that requires a conversion to the iodopropenylbenzene comp
with
NaI and maybe phase transfer catalysis or insitu with NaI during the
bomb
or reflux.
When the hexamine salt is prepared in solution, then some HCl is
added and
again refluxed overnite. again, possibly this can be run at room
temp over
several days- who knows?
Then use typical amine seperation to get the pure product from the
acidic
mixture.
Love and trips, Wednesday.
====================================================================
=========
Several months ago someone (Pugsley, Wednesday, Uncle Fester or
someother
Adams family member- my connections indicate they are probably all
the
same) posted a synth for bromosaftrole utilizing the conversion of
NaBr in
DMSO with conc H2SO4 and further info for converting the bromo
compound to
MDA using the Delepine reaction with hexamine (camping fuel
tablets :) :) !
Also, there were some negative comments from some narc (chem
baiting) who
disparaged the small amounts of sassafrass oil that were called for
in the
reaction, implying the process wasn't useful in production qty's,
and
implying the hexamine reaction was some sort of joke. (prob. some
community
college grad in the DEA)
We have done some experimentation with the bromination procedure;
and
although not alot of detailed info was originally given, we feel
that alot
more attention should be given to the potentially revolutionary
procedure.
First, 30g or so of NaBr was to be reacted with the theoretical (for
HBr
product) amount of conc. H2SO4 in 100ml anhydrous DMSO; and then
adding 5ml
of sassafrass oil to the resultant crude mixture of HBr and NaSO4 in
the
resultant DMSO solution. Objection to the procedure was the high
amount of
DMSO that was required in the reaction for the small amount of oil.
Evidently, criticism was of the premature narc oral ejaculate before
you
experiment variety, since we found that only about 5g of NaBr
dissolves in
the DMSO anyway- but that 30g (and much more...) of NaBr reacts
without the
whole mass first dissolving in the DMSO.
Evidently, the higher solubility of NaBr vs. the NaSO4 product
drives the
reaction so that all the NaBr is converted to HBr without the total
amount
being first necessary to dissolve. As the author notes, the first
"Reagents
in Organic Synth" book explains the unusual solubility and
reactivity of
inorganic halides and other compounds in DMSO. The solution does
gradually
turn orange, and magnetic stirring accellerates the process, and
undboubtably converts most of the NaBr into HBr. Since some NaBr
might be
trapped within a shell of NaSO4, some sort of stirring is neccessary
to
break up the undissolved mass.
****We will next try NaI, but wanted to get this out as it may be a
few
weeks until we can safely procure some NaI (thanks alot, cranksters,
for
making anything with -I- suspect, NaI, HI, whatever, ha ha)****
In conclusion, it appears that practically any reasonable conc. of
HBr in
DMSO can be obtained (up until the point of heavy fuming) with the
method.
Further, the enhanced reactivity of halides in DMSO and the
inherently
anhydrous nature of the procedure and lack of mess and fumes make
it, at
least for the time-being the method of choice for bromination of
substituted allyl-benzenes. ................. Postscript: Although
we are
interested in MDMA only, the use of the Delepine reaction for making
MDA is
a valid method. In fact, the original post is the first time we have
seen
the reaction used in any underground chemistry texts. The narc
called it
"cute", but in fact the Delepine reaction has the cleanest and
highest
yields out of any reactions for converting an organic halide into a
primary
amine. (assuming that camping fuel tablets contain some small amount
of
inert binder with a majority of hexamine, there's no reason that
they
couldn't be used for the Delepine reaction)
We would be very interested in hearing from any parties who have
done the
experimentation required for evaluating the conversion of
bromosafrole or
other brominated allyl-benzene compounds at *room temperature* as
the post
speculated upon. *Room temp reaction of the bromo compound with
hexamine
(camping fuel tablets) and further room temp cleavage of the
hexamine salt
(HCl in alcohol reaction) would make a complete synth that could be
carried
out in the complete highly desired "mayonnaise jar" glassware set
for the
masses*.
Also, the use of sassafrass oil instead of pure distilled safrole
might
very well provide higher yields (although not tried here). Its well
known
that phenolic compounds inhibit the formation of a-bromo side
reactions
that occur via the free-radical process (March, "Advanced Organic
Chem",
and many others); and sassafrass oil has plenty of phenolics
including
eugenol in high conc.
the Professional.
====================================================================
=========
Subject: Re: Re: MDA from MDP2P
From: "guest" <guest@webshack-cafe.com>
Date: 1997/11/08
> Man, this has to be some of the most confusing research I've done.
> Could someone (Eleusis, maybe....) tell me exactly which method
for
> brominating safrol with 48% HBr actually works. My #1 so far
seems to
> be starting with MDP-2-Pol and brominating like Fester told us way
back
> when chemistry worked differently (apparently). This would seem
to
> drive the reaction towards the bromnation side, due to the
willingness
> of that alcohol to leave in place of Br.
> So c'mon, gimme some insights.
Why don't you try doing a bit a basic research? Visit a library. In
the
library you will find books that you can read.
When you've discovered how it's done you can post your results to
a.d.c for
the rest of us to read. You can connect to www.deganews.com and read
old
Eleusis and ZWITTERION posts on this topic. I include a couple
below.
Otherwise you'll have to contend with me taking the piss out of you.
And when you've made your halo-safrole what next? The yield of MDMA
from
halo-safrole is shit because the main reaction is the elimination of
HX to
give you the alkene (safrole) back again! If I had MDP-2-Pol then I
wouldn't want to brominate it at all. I'd oxidise it to MDP-2-P and
reductively aminate the ketone to MDMA.
If I wanted bromo-safrole I'd make it from safrole using a phase-
transfer
catalyst to allow non-polar safrole to mix with polar aq. 47% HBr.
More
likely, I'd use aq. 37% HCl or, I presume, even aq. 32% HCl would
work to
give chloro-safrole. See: Addition of hydrohalogen acid to alkenes:
Landini & Rolla, JOC 45, 3527, (1980). JOC = Yes, that's Journal of
Organic Chemistry to you. Phase-transfer catalysts can be extracted
from
hair and fabric conditioners. The cationic surfactants mentioned on
the
ingredients of such stuff will easily suffice as phase-transfer
catalysts.
But remember, when you use a surfactant to mix two immiscible phases
you
must stir them at 500 rpm or better, otherwise nothing will happen.
Keep
the temperature on the low side otherwise you'll zap that delicate
methylenedioxy bond. So, why are you phaffing about with 47% HBr
when you
can walk over to the local hardware shop and do something similar
with 32%
HCl?
Eleusis contends that aq. 47% HBr can't be used to make bromo-
safrole under
normal conditions.
This is the original article that sparked it all off, where Carter
describes the addition of HBr to Alkene.
H. E. Carter, Metabolism of Amino Acids, J. Biol. Chem. 108, 1935, p
623.
200 gm. of glacial acetic acid containing 150 gm. of hydrogen
bromide were
placed in a 500 cc. bottle in an ice bath and 100 gm. of allyl
benzene were
added. A rubber stopper was wired in the bottle and it was allowed
to come
to room temperature slowly with occasional shaking. In 10 to 12
hours the
original two layers merged into a clear red solution. After 24 hours
the
contents of the bottle were poured on crushed ice. The crude bromide
was
separated and the water layer extracted with petroleum ether. The
two
fractions were combined, washed with water and sodium carbonate, and
dried
over anhydrous sodium sulfate. The petroleum ether was distilled
through a
20 cm. column and the residue was fractionated. The yield of crude
bromide
(90-95 per cent pure) was 235 gm. (92 per cent of the theoretical
amount).
Eleusis contends that Fester was talking through his arse when he
described
the prep. of bromo-safrole using this method. By implication,
Eleusis
implies that most of the rest of Fester's book is made up.
====================================================================
=========
From: jmt0165@u.cc.utah.edu (Jon Taylor)
Subject: Newest MDMA Synthesis
Date: 18 Apr 1994 17:10:03 -0600
This is an MDMA sysnthesis I OCR's out of my copy of
_Secrets of
Methamphetamine Manufacture_, which will probably end up being the
one
that I put in the next revision of my MDMA FAQ. I thought I'd also
post
it as a separate file as well.
-Jon
CUT HERE
/\/\/\/\/\/\/\/\/\/\/\/\
MDMA Synthesis: Bromosafrole method
Scanned fom _Secrets of Mthamphetamine Maufacture_
A good alternative to the Ritter reaction is a two step
procedure
first reacting safrole with hydrobromic acid to give 3,4-
methylenedi-
oxyphenyl-2-bromopropane, and then taking this material and reacting
it with either ammonia or methylamine to yield MDA or MDMA
respectively. This procedure has the advantages of not being at all
sensitive to batch size, nor is it likely to "run away" and produce
a
tarry mess. It shares with the Ritter reaction the advantage of
using
cheap, simple, and easily available chemicals.
The sole disadvantage of this method is the need to do the
final
reaction with ammonia or methylamine inside a sealed pipe. This is
because the reaction must be done in the temperature range of 120-
140 C, and the only way to reach this temperature is to seal the
reactants up inside of a bomb. This is not particularly dangerous,
and
is quite safe if some simple precautions are taken.
The first stage of the conversion, the reaction with
hydrobromic
acid, is quite simple, and produces almost a 100% yield of the
bromi-
nated product. See the Journal of Biological Chemistry, Volume 108
page 619. The author is H.E. Carter. Also see Chemical Abstracts
1961, column 14350. The following reaction takes place:
[ Structural diagrams deleted]
To do the reaction, 200 ml of glacial acetic acid is poured
into a
champagne bottle nestled in ice. Once the acetic acid has cooled
down, 300 grams (200 ml) of 48% hydrobromic acid is slowly added
with swirling. Once this mixture has cooled down, 100 grarns of
safrole is slowly added with swirling. Once the safrole is added,
the
cheap plastic stopper of the champagne bottle is wired back into
place, and the mixture is slowly allowed to come to room temperature
with occasional shaking. After about 12 hours the original two
layers
will merge into a clear red solution. In 24 hours, the reaction is
done.
The chemist carefully removes the stopper from the bottle, wearing
eye protection. Some acid mist may escape from around the stopper.
The reaction mixture is now poured onto about 500 grams of
crushed ice in a 1000 or 2000 ml beaker. Once the ice has melted,
the
red layer of product is separated, and the water is extracted with
about
l00 ml of petroleum ether or regular ethyl ether. The ether extract
is
added to the product, and the combined product is washed first with
water, and then with a solution of sodium carbonate in water. The
purpose of these washings is to remove HBr from the product. One
can be sure that all the acid is removed from the product when some
fresh carbonate solution does not fizz in contact with the product.
Once all the acid in the product is removed, the ether must be
removed from it. This is important because if the ether were allowed
to remain in it, too much pressure would be generated in the next
stage inside of the bomb. Also, it would interfere with the
formation
of a solution between the product and methylamine or ammonia. It is
not necessary to distill the product because with a yield of over
90%,
the crude product is pure enough to feed into the next stage. To
remove the ether from the product, the crude product is poured into
a
flask, and a vacuum is applied to it. This causes the ether to boil
off.
Some gentle heating with hot water is quite helpful to this process.
The yield of crude product is in the neighborhood of 200 grams.
With the bromo compound in hand, it is time to move onto the
next step which gives MDA or MDMA. See Chemical Abstracts
1961, column 14350. Also see Journal of the American Chemical
Society, Volume 68, page 1805 and Journal of the Chemistry Society,
part 2 1938, page 2005. The bromo compound reacts with ammonia
or methylamine to give MDA or MDMA:
[ Sructural diagram deleted ]
To do the reaction, 50 grams of the bromo compound is poured
into a beaker, and 200 ml of concentrated ammonium hydroxide (28%
NH3) or 40% methylamine is added. Next, isopropyl alcohol is added
with stirring until a nice smooth solution is formed. It is not good
to
add too much alcohol because a more dilute solution reacts slower.
Now the mixture is poured into a pipe "bomb." This pipe should be
made of stainless steel, and have fine threads on both ends.
Stainless
steel is preferred because the HBr given off in the reaction will
rust
regular steel. Both ends of the pipe are securely tightened down.
The
bottom may even be welded into place. Then the pipe is placed into
cooking oil heated to around 130 C. This temperature is maintained
for about 3 hours or so, then it is allowed to cool. Once the pipe
is
merely warm, it is cooled down some more in ice, and the cap
unscrewed.
The reaction mixture is poured into a distilling flask, the
glass-
ware rigged for simple distillation, and the isopropyl alcohol and
excess ammonia or methylamine is distilled off. When this is done,
the residue inside the flask is made acid with hydrochloric acid. If
indicating pH paper is available, a pH of about 3 should be aimed
for.
This converts the MDA to the hydrochloride which is water soluble.
Good strong shaking of the mixture ensures that this conversion is
complete. The first stage of the purification is to recover
unreacted
bromo compound. To do this, 200 to 300 ml of ether is added. After
some shaking, the ether layer is separated. It contains close to 20
grams of bromo compound which may be used again in later batches.
Now the acid solution containing the MDA is made strongly basic
with lye solution. The mixture is shaken for a few minutes to ensure
that the MDA is converted to the free base. Upon sitting for a few
minutes, the MDA floats on top of the water as a dark colored oily
layer. This layer is separated and placed into a distilling flask.
Next,
the water layer is extracted with some toluene to get out the
remaining
MDA free base. The toluene is combined with the free base layer, and
the toluene is distilled off. Then a vacuum is applied, and the
mixture
is fractionally distilled. A good aspirator with cold water will
bring
the MDA off at a temperature of 150 to 160 C. The free base should
be clear to pale yellow, and give a yield of about 20 ml. This free
base
is made into the crystalline hydrochloride by dissolving it in ether
and
bubbling dry HCl gas through it.
====================================================================
=========
Subject: Bromosafrole Prep from Uncle Fester
From: Lasertek <lasertek@dct.com>
Date: 1996/05/17
Members of the alt.drugs.chemistry discussion group:
My many thanks for the opportunity to get on board and engage in a
food fight
with someone named Eluisis. As a token of my appreciation, I'm going
to leave
you with some of my original research on a couple of topics which
may
interest you. I think anyway it's original. If anyone comes up with
references
covering these topics, let me know.
PREPARATION OF BROMOSAFROLE FROM 48% HYDROBROMIC ACID
A greatly improved procedure using 48% HBr to make bromosafrole is
my own
invention, and it is with unbounded pride that I offer this advance
to the
field of MDA manufacture. This procedure is both quicker and much
higher
yielding than the procedure worked out by the jackass who wrote the
article
for the Alabama Academy of Science cited earlier. This so-called
researcher
was hired by the DEA to fool around with 48% HBr to see if it could
be used
to make MDA or MDMA from sassafras oil. They had busted someone
with 48% HBr
and a load of sassafras, and to make their case they needed to show
that it
could be done. The result is a testimonial to the power of money -
for it,
some people will say anything. I just wonder who is rotting away in
a cage
as a result of his inflated claims.
You bought this book for the straight poop, so let your Uncle be
your guide.
To get good yields of bromosafrole from 48% HBr and sassafras oil,
mix one
part sassafras oil with one part glacial acetic acid and two parts
48% HBr
in a suitable-sized flask. Chill this mixture down in ice, then
with strong
magnetic stirring pass a stream of dry HCl gas into the solution for
about
an hour. See Chapter 5 for the dry-HCI gas-generator. How much HCl
to pass
into solution? Well, for a batch using 50 ml of sassafras oil, the
amount of
dry HCl generated by dripping 75 to 100 ml of sulfuric acid onto a
half-full
500 ml flask of salt-hydrochloric-acid paste is about right. A
little bit
more wouldn't hurt. Good ventilation is required!
As the dry HCI passes into the solution, it dehydrates the 48% HBr,
causing
it to react with the safrole. The dehydration and the reaction both
generate
a good deal of heat, so fresh ice will periodically have to be put
into the
bath around the reaction flask. The temperature of the reaction
shouldn't
be allowed to rise above 10-15! C. The reaction mixture first turns
green
then blue, then purple, and finally burgundy. When the bubbling
with dry
HCl is finished, stopper the flask and continue stirring in the cold
for two
days. Sometime around a day into this stirring, no separation of
phases can
be seen when stirring ceases.
The amount of dry HCl produced by dripping sulfuric acid onto salt
will vary
with the exact conditions, so the batch should be checked for
reaction before
quenching it on ice. It doesn't hurt to add too much dry HCl,
within limits,
but too little won't dehydrate the acid sufficiently. To check
this, after
the day of stirring is done, pour some of the reaction mixture into
a beaker,
then from beaker, return it to the reaction vessel. This leaves a
coating of
the reaction mixture on the glass in the beaker. Fill the beaker
with water
to rinse away the fuming acids, empty it, and sniff inside the
beaker for the
aroma of the organics clinging to the glass. If it still smells
like the
candyshop fragrance of sassafras oil, an additional bubbling with
dry HCl is
going to be required, followed by another day of stirring in the
cold. After
the first batch or two, it's easy to gauge how much dry HCl one is
getting.
If the aroma has changed to something more chemical and fruity, yes
just like
phenylacetone, sufficient HCl has been added.
When two days of stirring are completed, the batch is poured onto
crushed ice
as in the other methods. When the ice has melted, a little bit of
toluene is
added (a volume about equal to the amount of sassafras oil used),
and the
water-bromosafrole mixture shaken. Prior to adding toluene, the
bromosafrole
will likely be on the bottom of the container, but adding toluene
and shaking,
it should be floating on top. It's still burgundy-colored.
Separate the
bromosafrole layer with a sep funnel, and then wash it with about 3
volumes
of water. Add bicarb slowly until the fizzing stops. This will
knock out
the carried-over HBr, HCI and acetic acid. Shake some more, then
add a little
more bicarb to make sure all the acid has be neutralized.
Separate the toluene-bromosafrole, and place it in a distilling
flask. Distill
off the toluene at normal pressure, then vacuum-distill the
remaining
bromosafrole. A vacuum that distills safrole at 110!C will distill
bromosafrole at about 140-145! C. Some chlorosafrole distills at
about 125!C.
It can be used as is, or the chlorosafrole can be converted to
iodosafarole
according to the directions found in the "Psychedelic Amphetamine"
chapter in
this book. The yield is about 66-75% conversion to bromosafrole,
with the
remainder being unconverted safrole and chlorosafrole. Bromosafrole
smells
a lot like phenylacetone. It may turn pink on standing, and should
be stored
in a freezer until used.
With this posted, has anyone ever discussed the bad effects that the
zinc
galvanizing on steel pipes has on the next stage of the reaction
with ammonia
or methylamine? White crystals galore! It most be stripped off in
dilute
HCL prior to use.
Along a similar line of thought, has the reaction of safrole with
dry HCl in
toluene been considered? Chlorosafrole has interested me for some
time.
It too smells like phenylacetone. My experiments indicate that HCl
adds
poorly to safrole at slightly elevated temps. About 10% yield in a
three
week reaction time. Higher temps would be needed to bring about
reaction,
but below the about 100C temp where ether cleavage with HCl happens.
Once
one has chlorosafrole, what good is it? It can be converted to
iodosafrole
by refuxing with 2 moles of NaI in acetone, and then filtering out
the NaCl
precipitated, boiling off the acetone under vacuum, and recovering
the
iodosafrole by extraction with toluene. What good is iodosafrole?
Compare
to the 2 halogen propyl benzenes listed in JACS 68, pages
1009-11(1946).
Similar chloro derivatives give small yields, whereas the bromo
derivative
of safrole gives a decent yield of product at lower temp. I see a
trend here.
The iodine is a better leaving group, and should give a superior
yield at
lower reaction temp. Read over all the relevant lit before
proceedings Also
know that a significant amount of mail I've recieved indicates that
the
presence of a significant (that means more than incidental) amount
of water
in the pipe bomb with bromosafrole yields excessive amounts of tar.
Just
adding 40% mehylamine or 28% NH3 to the alcohol is too much water.
This is
fine for making meth or benzedrine by this method, but for MDA some
dehydration is called for.
I hope this contribution to the discussion group causes serious
exchange.
I also hope you've enjoyed meeting my friend down the street
LASERTEK.
He's not a chemist, rather he works metal using a laser. He hasn't
had so
much fun since he discovered your group.
Best, Fester
====================================================================
=========
Ritter
Yup, that's the procedure I've been touting for years now. I don't
know how
many times I have to say that Fester actually did something right
this time!
The only variation I've made on his procedure is to bubble in about
half again
as much HCl(g) as Fester calls for. Other than that the reaction
procedes
EXACTLY the way he quotes it, color changes and all! Just make sure
the ice
bath is kept chock full of ice for the entire duration of the rxn.
====================================================================
=========
From: lamont@hyperreal.com (Lamont Granquist)
Newsgroups: alt.drugs
Subject: Re: Newest MDMA Synthesis
Date: 19 Apr 1994 20:31:00 GMT
Message-ID: <2p1f24$2bd@news.u.washington.edu>
jmt0165@u.cc.utah.edu (Jon Taylor) writes:
> This is an MDMA sysnthesis I OCR's out of my copy of
_Secrets of
>Methamphetamine Manufacture_, which will probably end up being the
one
>that I put in the next revision of my MDMA FAQ. I thought I'd also
post
>it as a separate file as well.
According to J-Forensic-Sci 35(3):675-697 this isn't the best method
of
making methoxylated amphetamine derivatives. The author claims that
yields are low, synthing the intermediate is time consuming
(although
so is synthing MD-P2P), and potentially hazardous -- I don't know
why
its hazardous, but the author references ANALOG 9(3):1-10 which
is an article by Hansson, R.C. entitled "Clandestine Laboratories
Production
of MDMA."
It is suggested that the synths using cyanoborohydride, aluminum
amalgam,
borohydride or Raney Ni catalysis from MD-P2P would be more likely
to be used.
The two former ones are preferred as the borohydride method has a
lower yield
and the catalysis requires the construction or purchase of a
hydrogenation
unit.
====================================================================
=========
Subject: Iodosafrole Secrets: the DMSO Method
Date: 1997/05/08
The iodosafrole method of producing MDMA and MDA is indeed viable;
being one
of those multikilagram processes here in the Netherlands someone was
asking
about.
The key is using the DMSO method of producing anhydrous HI. NaI is
dissolved
in DMSO and then an equimolar amount of H2SO4 is added. Na2SO4
precips out.
The reason the process works is that DMSO has the peculiar property
of
dissolving lots of NaI. (the solubility is much higher for NaI than
for
NaBr, making the HI process much better for large qty- make note of
this you
crank manufacturers) (will phoshorus and iodine be obsoleted?? :)
And DMSO makes such acids particularly active. And HI is not likely
to
cleave ether substituted allyl benzenes like apiole, asarone, and
myristicin.
(See Feiser and Feiser in Reagents for Organic Synthesis vol. 1 for
details)
Extraction of iodosafrole left to your own imagination. Our trade
secret!!
Finally, amination is done at room temp with methylamine for MDMA or
with
hexamine (via Delepine process) to get MDA or other analog.
Happy trails! Pugsley and Wednesday.
====================================================================
=========
From: nobody@REPLAY.COM (Anonymous)
Subject: Pugsley: on Bromosafrole via DMSO Method/ Various topics,
advice
Date: 1997/08/31
Congratulations to the poster on getting the DMSO method of
bromosafrole
synthesis to work. Its incredibly easy- but too easy for anyone to
believe it
works. Its the amination thats the more difficult part. Be careful
if you
decide to make your own methylamine via the formaldehyde/NH4Cl
method- it
gives off alot of methyl formate at the start, which is really nasty
stuff,
almost as bad as dimethyl sufate. It turns into formic acid in your
lungs.
Big Mr. Yukk sticker on that one. Another chemical given off,
formylal, has
a nice smell and is relatively safe, but masks the danger involved.
I'm still interested in hearing in this NG from anyone doing the
Delepine
reaction with hexamine camping fuel to get MDA. Bromosafrole has
given mixed
results. Iodosafrole works at room temp. I don't see too much
problem with
getting NaI, since it can be diverted from table salt and
photographic
applications. I don't know if CRSB sells it, but they should. (if
they stay
in business) I don't think that meth labs use it, since in aquious
media,
H2SO4 turns it into elemental Iodine plus whatever salt of Na.
DMSO doesn't
suffer from that problem.
I still see a lot of synthesis and talk on methcathinone. Very
little said
about cyclization products, which is one of a couple reasons some
people can't
seem to make it. There were some posts here a while ago referencing
the
specific papers on the subject. I didn't have to time to go to the
library
and dig all that stuff up.
Never keep academic papers or chemistry books of any kind on your
property if
you are making "stuff". Memorize, memorize, memorize. Try to use
anything
but commercial glassware if you can. A suprising amount of
chemistry can be
done with spagetti sauce jars and various types of tubing. Even
holes can be
drilled in spagetti sauce lids and brass pipe fittings soldered, for
various
operations involving gases.
For exampe, I performed the entire asarone and anethole
pseudonitrosite
syntheses for TMA and PMA respectively, using nothing other than
sauce jars
and a large pyrex juice dispensers as containers. One sauce jar has
two
fittings attached to it so that an outlet tube for the N2O3 could be
attached,
plus an inlet for air from a fish tank bubbler. The pyrex juice
dispenser was
used to contain the etherial solution of essential oil.
(By the way, PMA or 4-MA as Schulgin calls it, is quite the roller-
coaster
ride. Except you start out at the top of a gigantic hill, instead
of
gradually making your way to the top. And it hits real suddenly.)
I think a DA would really think twice about going after someone who
had no
paper evidence of drug chemistry efforts, and just a bunch of old
jars lying
around. If you ever read accounts of DEA busts, they always tell
about all
the drug and bomb making Loompanics books they find. If all they
find are
Nancy Drew mystery novels, they'd look pretty silly.
Various people have been asking about where they can buy essential
oils.
There are a number of web site based mail order suppliers. Just
type
"essential oil" into AltaVista. For example 16oz of anise oil
costs $12.
Same price for sassafrass. Calamus oil costs anywhere from $60-200
for 16oz
depending on where you buy it. Make certian to get the Indian oil.
The
others have no asarone in them. Nutmeg and elemi oil are reasonable
also.
Parsley seed oil has gone up to about $100/16oz. If you isomerize
it to
isoapiole, it makes way cool DMMDA.
Well, thats all the comment I can think of for now. I really
haven't been
doing much in quite number of months. I get burnt out on making
drugs and
find new interests. I've never had any desire to make money that
way. After
all, anyone smart enough to make their own druggs can probably make
alot of
money legit. Its always been a curiosity thing. I am eagerly
awaiting
Fester's "Advanced Meth Chemistry Book". That should be interesting.
Wednesday sends her good wishes.
Best Regards,
Pugsley
====================================================================
=========
From: jrhardin@mail1.sas.upenn.edu (Josh R Hardin)
Subject: Pugsley & Wednesday Please Read
Date: 1997/09/07
First, let me thank you for the excellent information about the
DMSO-Bromosafrole method. For those of you unfamiliar with it, I
strongly suggest searching dejanews. Basically, it uses DMSO, NaBr
(from
darkroom supply houses), and H2SO4 (drain cleaner) to synthesize
anhydrous HBr which converts Sassafras oil to Bromosafrole. This
method
is better than using commercially available HBr.
The authors suggest that after obtaining Bromosafrole, a 5g tablet
of
Hexamine camping fuel can be added to start the Delepine reaction to
convert it to MDA. Does anyone have any references for the Delepine
reaction? Is the mixture refluxed, cooked in a pipe bomb, or
allowed to
sit for a period of time? Does anyone have any numbers? The other
method of converting bromosafrole to MDA via ammonia and isopropyl
alcohol or ammonia hydroxide gives poor yields (20%) and doesn't
smell
too good to the neighbors.
In another post, Pugsley discusses iodosafrole. This method uses
DMSO,
NaI, and H2SO4 to yield anhydrous HI. NaI is easily diverted from
salt
licks. I believe that the recipe is 100ml chilled DMSO + 7.8ml
H2SO4 +
43g NaI. Although this can be used for making speed without having
to
purchase red phos or iodine, can it be used for MDA? If one were to
use
the HI to convert sassafras oil to Iodosafrole, could it be
converted to
MDA via the Delepine reaction? How? Let's use the example of 5ml
Sassafras oil + 100ml DMSO + 7.8ml H2SO4 + 43g NaI. After it has
reacted
for a day or so, there should be iodosafrole - right? Now, would
adding
a 5g Hexamine camping fuel tablet start the delepine reaction? What
are
the times and methods - reflux, bomb, let sit? How do the yields
compare
to the bromosafrole methods?
Finally, in their amazing post about pseudonitrosites, the authors
state
that the method can be used on various propenyl benzenes. This
would
allow isosafrole to be easily converted to MDA. Howver, in Fester's
Practical LSD Manufacture, he states that it will work on all
propenyl
benzenes EXCEPT isosafrole. Howver, the two procedures are
different.
Will it work? What is DMMDA like?
Thanks for the help.
BTW, please do not respond to this e-mail account. It is not mine.
I
can be reached at:
iodosafrole@hotmail.com
Thanks,
HI Guy
====================================================================
=========
From: Secret Squirrel
Subject: COME MOCK MY DMSO FAILURE
Date: 1997/06/03
Let me first apologize for the outburst. After investing so much
time
and energy into the project, to have it fail miserably at the end
was
frustrating, to say the least. I greatly appreciate Pugsley's and
Wednesday's contributions to poor chem trench grunts everywhere.
That said, prepare the mudslings for my crappy technique.
Keep in mind none of this actually happened and the entire post
is pure fiction :).
The DMSO was purchased anhydrous at the local homeopathy shack (it
even says "for use as solvent only" *grin*). It would freeze solid
when put in the fridge (a good sign). Kodak anh. KBr (from darkroom
supply) was used in place of NaBr, molar scaled up of course.
Sassafrass oil was used straight to take advantage of eugenol, etc.
I was unable to locate ocotea cymbarum locally. The relative
quality
of the essential oil I have no idea nor reference for, all that can
be
said is that it was expensive.
175ml DMSO was chilled(frozen) in an acetone-rinsed 500ml round-
bottom
and the flask placed in an ice-water bath. There was then added
30.6g
H2S04 drain cleaner with some evolution of heat. The drain cleaner
was
slightly discolored brown even though it came from a sealed
container
(although the container is probably a year old). Looking at the
container
now, the acid is dark brown-red with chunks, disgusting; evidently I
had
drawn off the undisturbed clearer top part when doing this, but
still
undoubtedly introduced impurities. I hadn't realized it at the
time, or
even much later.
69.3g KBr was then added. The initial granules falling into the
flask
produced a fine mist, much like ammonium chloride forming above a
bottle
of muriatic and a bottle of ammonia placed next to each other,
which
shot up a bit and gave me a bit of a gag. Perhaps the addition
order
should be reversed. The soln turned orange, and began to stink.
The
stench is a lot like garlic, and exactly like the smell of the
sweaty
guy who had the locker next to mine in high-school gym class (ugh).
A lot of KBr remained undissolved despite repeated stirring with a
glass
rod, as expected.
10ml sassafras oil was pipetted in. The stink changed from garlic/
sweat
to garlic/sweat/bandaids. The soln turned brownish-red with a sort
of
mobile greenish band on top. The flask was tightly stoppered, then
entirely enclosed in a ziplock bag, which still didn't keep in all
the smell, and left on a dark shelf at room temp for 2 days with
occasional swishing and/or stirring. It turned entirely brownish-
red.
The solids remained on the bottom throughout, being broken up upon
stirring.
My notes are missing for the next part, but around 600 ml of
distilled
water was added in two portions, the entire thing getting dumped
into a
liquor bottle. A dark red, clear oil settled to the bottom; the
aqeuous
layer turned cloudy tan as the solids dissolved into it. The aq
layer
was poured off, and the oil washed with a bit more H2O. Yield of
oil was
(guessing) maybe 7 or 8 ml.
To the oil was added 400ml denatured alcohol and 10.2g crushed
camping
fuel, which was used straight but was nice and white crystalline. A
few small pieces of fuel didn't dissolve right away, but had after
the soln sat one day. The soln was left alone until the 3rd day,
when
heating was attempted, but aborted due to pesky interlopers. The
4th
day the soln was finally refluxed on steam bath for about 6 hrs. It
sat one more day (good undisturbed lab space is hard to come by).
The soln remained a reddish tea color.
50ml muriatic driveway cleaner (31.45% HCl) was then added in
increments.
The first 20ml produced loads of fine white needle crystals, filling
the
500ml flask halfway and nearly giving me a heart attack for the few
seconds
until my brain realized there were just too many and they were
probably
ammonium chloride and unreacted hexamine. As the rest of the HCl
was added,
the crystals all dissolved, but then gradually a white ppt formed,
snowy and
unlike the needles. The flask was refluxed on steam bath about 4
hrs and
then sat for a day. The ppt did not dissolve with heat.
125ml H2O was added, which dissolved the ppt and turned the soln
opaque
tan. A dark clear red oil settled out (I assumed it to be unreacted
bromosaf).
The pH at this point was less than 3, determined by indicator paper.
The
oil was seperated and the aq soln extracted with 3x20ml 1,1,1-TCE.
The TCE
extracts were combined w/ the oil and set aside.
80ml 25% NaOH (lye) in water was added to make the aq soln strongly
basic.
After shaking, a (small amount of) red-brown oil settles to the
bottom.
The oil was sep'd and the aq layer extracted with 3x20ml 1,1,1-TCE.
The
TCE extracts were orange-ish. The remaining aq soln looks like iced
tea.
Post-mortem dissection of my notes reveals the combined TCE extracts
and
oil did not get an additional water wash. The TCE was distilled off
in a
flask I finally remembered to tare beforehand, leaving 7.4g of a
dark
black-red oily goo, which was dissolved in 12.5ml anh. isopropanol
and
treated with a couple ml of HCl, then evaporated on steam (ala
ZWITTERION,
remember him?) to give a disgusting orange tar (which had to be
scraped off
with acetone), a few grains of probably NaCl, and a whole lotta
stink.
I would guess the stink was from methylamine HCl (from unreacted
hexamine
hydrolyzed during the second part of the Delepine) subliming with
the heat;
it smelled kind of like burning plastic.
A cold beer was then searched for, to no avail, at which point a
mentally and physically exhausted fetal position was assumed, with
soft
crying.
For my next attempt, I'm considering (among other things) doing the
first part of the Delepine in TCE instead of alcohol, which would
allow
me to see the progress of the rxn, harvesting the pptd hexamine
salt
and returning the rest to the heat. The salt could then be
hydrolyzed
in a separate reaction. I'm also considering use of the bomb.
====================================================================
=========
Date: Fri, 19 Sep 1997 17:37:07 -0600
From: iodosafrole@hotmail.com
Subject: The Real Info - Please Read
HI can be made by reacting phosphoric acid (it can be purchased at
HOME
DEPOT in the bldg supply section) and NaI or KI. NaI can be found
at salt
licks. HI can also be made by reacting dilute sulfuric (it's not
spelled
with a ph bookworm) with NaI or KI. Now this produces HI gas. So,
using a
variation of Tom Kasper's push pull bullshit, in jug have 5L of
phosphoric
acid connected by neoprene automotive feul tubing to a champagne
bottle
containing NaI, Ephedrine or pseudoephedrine, and H2O. Supposedly HI
gas
bubbled through a solution of 1 part ephedrine to 2 or 3 parts water
under
25 psi will make meth without the need for red phos.
The best quench for the Birch is ammonium chloride. Bubble some of
the gas
through some HCl.
There was a post by bookworm in which he said that there was a
"recipe"
that used 75:15:10 ratio in which 75g of NaI or KI:15g
TripleSuperPhophate
(might be tri-sodium phosphate):10g Al. If it works, which I doubt,
the
10g of Al should be AlCl because it is hygroscopic. This is all in
one
jug which is connected to another jug containing phophoric acid. He
claims
that the temp should be under 80C - bullshit - and should take 2-4
days -
bullshit. Follow the 3 hour push/pull by that anon guy in Santa
Barbara.
====================================================================
=========
Subject: Re: HBr + Safrole = ??????
From: eleusis@netcom.com (Eleusis)
Date: 1995/10/15
In article <45nth1$ack@newsbf02.news.aol.com>, truublonde@aol.com
wrote:
> So Fester is a Puss Face? Is the HBr route to MDA a total waist of
time?
> The reaction appears feasable on paper. Does it work at all? Or
are the
> yeilds just pathetic? What modifications would one need to make to
this
> reaction in order to successfully synth. MDA? Any good HBr synth
> directions??? Any good alternatives? And
Reload old articles, starting about 2 months ago. This has been
thoroughly
hashed over. In fact, I just posted a synopsis answer to this
question
about a week ago. Surely that article is still on most servers.
Anyway, if I *were* to do it, I would consult the original H.E.
Carter
article, where I would find the following corrections to Fester's
questionable chemistry deviations:
1) Anhydrous HBr gas is dissolved in glacial acetic acid, not
Hydrobromic
Acid, and definitely not the azeotropic acid.
2) 100g of allylbenzene was used in Carter's, 100g of safrole is
specified
by Fester, but allylbenzene has a mol. weight of 118, while
safrole is
162. That means that Carter was brominating .85 moles, while
Fester is
attempting to brominate 0.62. Fester didn't even bother
converting molar
quantities!
Etc... Otherwise, the process seems facile.
====================================================================
=========
Subject: Re: MDA from MDP2P
From: eleusis@netcom.com (Eleusis)
Date: 1995/11/01
Bromination of Safrole at the secondary carbon of the double bond
proceeds
at less than 5% yield if 48% HBr is substituted for 66% under
pressure, at
which point yields are closer to 85% (J.Bio.Sci. v108).
This is a "minor detail" that changes yield by 80 percentage points.
====================================================================
=========
Posted by ChemHack on the Hive
Chemical Abstracts 1961, column 14350, paragraph e (S.Biniecki &
E.Krajewski) - Safrole + 70% HBr at 0C for 12hours produced 97%
yield of
bromosafrole.
Same source paragraph f - 4.7g bromosafrole + MeNH2 in alcohol
heated 3
hours at 130C, clean-up and treatment with HCl yields 1.4g MDMA and
1.9g
unchanged bromosafrole recovered.
Journal of the Chemistry Society, part 2 1938, page 2008, 4th
complete
paragraph titled Addition of Hydrogen Bromide to Safrole (K.H.Lin &
R.Robinson) - Safrole in solution of perbenzoic acid in benzene was
saturated with hydrogen bromide. On each of next 7 days 1ml of
perbenzoic
acid solution added. [CH: to keep it in solution?] The mixture
shaken and
kept for 17 days. Water washed, treated with sodium carbonate,
washed
again, dried, and distilled giving unspecified yield of colourless
mobile
liquid identified as safrole hydrobromide.
Journal of the American Chemical Society, Vol 68, page 1806, Sept.
1946,
3rd complete paragraph (B.Riegel & H.Wittcoff) - Hydrogen Bromide
gas
bubbled into solution of glacial acetic acid and allylbenzene led to
formation of 2 layers which were dispelled by adding more acid. Rxn
kept
cold overnight, poured into icewater yielding heavy bromide taken up
in
EtOH, aqueous layer extracted and extracts pooled. Washed with
dilute
bicarb then with water then dried over sodium sulfate then distilled
to
yield 71% colorless B-Bromopropylbenzene.
Journal of Biological Chemistry, Vol 108, page 623, 1934/5?, first
complete
paragraph (H.E.Carter) - 200g glacial acetic acid containing 150g
hydrogen
bromide in bottle in ice bath. 100g allylbenzene added, stoppered,
and
allowed to come to room temp slowly with occasional shaking. Two
layers
merged into clear red solution after 10 to 12 hours. After 24hours
contents
poured onto crushed ice, bromide separated, water extracted with pet
ether.
Extracts pooled, washed with water and sodium carbonate, dried over
sodium
sulfate. Distilled bromide was 90-95% pure and total yield was 92%
of
theoretical.
====================================================================
=========
From: The Journal of the Chemistry Society, part 2 1938 page 2005.
379. Experiments on the Synthesis of Substances related to the
Sterols.
Part XXV. by K. H. Lin and Robert Robinson.
This article refers to the bromosafrole as Beta-Bromodihydrosafrole.
[discussion of related compounds deleted]
Addition of Hydrogen Bromide to Safrole.--Only one of the many
experiments
made is here described. A mixture of freshly distilled safrole (8.1
g.), a
solution of perbenzoic acid in benzene (2 cc of 0.3N), and benzene
(100 cc)
was saturated with hydrogen bromide (2 hours). On each of the next
7 days
perbenzoic acid solution (1 cc) was added, and the mixture shaken
and kept
for 17 days. The mixture was then washed with water, dilute aqueous
sodium
carbonate, and again water and the benzene layer was separated,
dried, and
distilled. The fraction (6.5 g), b.p. 145.5-153C at 9.5mm, was a
colourless,
mobile liquid and was identified as the known safrole hydrobromide;
Robinson
and Zaki (J., 1927, 2489) give b.p. 160C at 16mm.
The addition of hydrogen bromide to safrole was also carried out (a)
in the
presence of alpha-heptenylheptaldehyde, and (B) in the presence of
anhydrous ferric cloride. The same beta-bromdihydrosafrole was
obtained in
both cases.
====================================================================
=========
This procedure calls for reactions under high pressure, this is
potentially
very dangerous. See ANALOG, Vol 9, No. 3, Nov 1987, pp. 1-10, by
R.C.
Hansson for additional dangers. Do not try this at home.
From: Chemical Abstracts 1961, column 14350.
Preparation of DL-1-(3,4-methylenedioxyphenyl)-2-
(methylamino)propane and
DL-1-(3,4-dimethoxyphenyl)-2-(methylamino)propane. Stanislaw
Biniecki and
Edmund Krajewski.
Safrole (5.3 g.) added dropwise at 0C to 21 g. 70% HBr, the mixt.
left
14hrs. at 0C, poured on ice, extd. with Et20, and the ext. distd. in
vacuo
yielded 97% 3,4-CH202C6H3CH2CHBrMe (I), n D-24 1.5634.
[Analogously, 5.73g. 4-allylveratrole with 18.6 g. 70% HBr gave 81%
3,4-
(MeO)2C6H3CH2CHBrMe (II), n D-18 1.5605.]
(I) (4.7 g.) with 26 g. 18.2% alc. MeNH2 heated 3 hrs. at 130C, the
solvent
and excess amine distd., the residue acidified with HCl to Congo
red, extd.
with 30 ml. Et2O to remove unchanged (I), the aq. layer treated with
10 g. K2CO3, extd. with Et20, and the exts. distd. gave 1.4 g.
3,4-CH202C6H3CH2CHMeNHMe, n D-19 1.5311, after 1.9g. (I) was
recovered;
hydrochloride m. 148-149C.
[Similarly, 7.2g. (II) and 22.5 g. MeNH2 after 10 hrs. at 140C and
similar
working up (NaOH used instead of K2CO3 and CHCl3 substitued for
Et2O in
the last extn.) gave 2.35 g. 3,4-(MeO)2C6H3CH2CHMeNHMe, n D-22
1.5265;
prepn. of the hydrocloride, m. 114-119C, was not successful unless
the
base was purified via the perchlorate, m. 180-181C.]
====================================================================
=========
From: The Journal of the American Chemical Society, volume 68, page
1805
PYRIDINIUM ANALOGS OF THE PRESSOR AMINES. I. THE BENZENE SERIES
by Byron Riegel and Harold Wittcoff
[discussion of other compounds deleted]
Beta-Bromopropylbenzene.--Although this compound had been prepared
previously by Carter by the addition of aqueous hydrobromic acid to
allylbenzene, it was decided to employ an alternative procedure.
The
induction of a rapid stream of hydrogen bromide into a solution of
10g.
of allylbenzene in 25 ml. of glacial acetic acid over a period of
two
hours led to the formation of two layers which were subsequently
dispelled by the addition of 20 ml. more of solvent. The reaction
mixture, having been subjected to low temperatures overnight, was
poured
into ice water to yield a heavy bromide which was taken up in ether
and
combined with the solution which resulted from the ether and benzene
extraction of the aqueous layer. The solution, having been washed
with
dilute bicarbonate and with water, was dried over sodium sulfate.
Thereupon, the solvent was evaporated to obtain a reddish oil which
on
fractionation yielded 12g.(71%) of a colorless liquid which
distilled at
77-80C at 1mm.
====================================================================
=========
Chlorosafrole
JOC 45, 3527-3529 (1980)
16.2 grams (0.1 mole) of safrole was added to a mixture of 50 ml 37%
HCl
(0.5 mole) and 4.0 grams (0.01 mole) of trioctylmethylammonium
chloride
(Aliquat 336), and the two-phase mixture was heated at 115!C (bath
temp)
with magnetic stirring for two hours. The solution was extracted
with
1x20ml and 2x10ml CH2Cl2, and the pooled extracts was freed from
solvent
by evaporation. The dark residue was distilled under aspirator
vacuum
which gave two fractions:
113-135!C - 10.1 grams - Clear, safrole + chlorosafrole
135-165!C - 4.8 grams - Cloudy, chlorosafrole + something.
Chlorosafrole II
16.2 grams (0.1 mole) of safrole was added to a mixture of 150 ml
37% HCl
(1.5 mole) and 4.0 grams (0.01 mole) of trioctylmethylammonium
chloride
(Aliquat 336), and the two-phase mixture was refluxed slowly for 5
hours.
The solution was left to cool, and it was extracted with 3x15 ml
DCM. The
pooled organic extracts was washed with a little dilute Na2CO3,
dried over
MgSO4, and the solvent removed by evaporation. The black residue was
vacuum distilled at 3 mmHg to yield 10.2 grams of clear 2-
chlorosafrole
at 130-150!C. There was also quite a lot of deep red residue in the
distillation flask, probably consisting of the PTC and various
polymerization products.
Using the first procedure, but with 0.5 moles 48% HBr only produced
tar.
====================================================================
=========
US Pat 3,864,115
Preparation of Bromosafrole
65 grams of safrole was dissolved in 100 ml of glacial acetic acid.
At 20!C,
there was added, with stirring, a solution of 100g HBr in glacial
acetic
acid. Stirring was continued for a further 12 hours at room
temperature and
the acetic acid was distilled off under vacuum. The residue was
taken up in
200 ml of benzene and washing was effected several times with, in
each case
100 ml of water. The benzene solution was dried over sodium sulfate.
When
fractionation was effected, 43 grams of bromosafrole of the bp 90!C
at
0.05 mmHg was obtained.
This is the corresponding U.S. patent of the original German patent.
====================================================================
=========
Psychokitty:
JOC 1980, 45, pp3529-3531
"Addition of Hydrohalogenic Acids to Alkenes in Aqueous-Organic,
Two-Phase
Systems in the Presence of Catalytic Amounts of Onium Salts."
The PTC used in this reaction can be replaced with
tetraoctylammonium bromide or
the much cheaper are more easily obtained trioctylmethylammonium
chloride
(Aliquat 336). Other PTCs such as tetrabutylammonium bromide and
triethylbenzyl-
ammonium chloride serve as very poor PTC catalysts due to their
appreciable
solubility in water.
Also, any hydrohalogenic acid solution (HCl, HBr, HI) can be used.
Don't know
about HF though. A mixture of 16.8g of 1-dodecene (0.1 mol) (Note
1), 55.5mL
of 48% hydrobromic acid (0.5 mol), and 5.1g of
hexadecyltributylphosphonium
bromide (0.01) is heated at 115degC (bath temperature) with magnetic
stirring
for 2hr (Note 2). The organic layer is separated (Note 3), the
aqueous phase
was extracted with dichloromethane (Note 4), and the solvent is
evaporated.
The resulting oil is distilled to give 21.4 of pure 2-bromododecane
(Note 5).
By treatment of the distillation residue with petroleum ether 4.8g
(94.0%) of
phosphonium bromide is recovered, which can be reused without
further
purification (Note 6).
Note 1: Don't be silly. Of course I didn't use 1-dodecene.
Note 2: An attempt was made to carry out the reaction in a sealed
round-bottomed
flask surrounded by an oil bath with the temperature monitored by a
thermometor
immersed in the two-phase mixture held in place by a stopper. After
about thirty
minutes, pressure within the vessel increased and the stopper was
blown off the
top of the flask. Thermometor was recovered unbroken. The set-up was
quickly
modified through the addition of a reflux condensor with the
thermometer
relocated to the oil bath to monitor reaction temperature. No
problems were
experienced again and the process continued smoothly. The reaction
mixture was
then stirred for 4 hrs at the required temperature. Although there
had been some
gas evolution before, no reflux of the standard kind was observed.
The 4 hour
reaction was unintended (I lost track of the time). As the reaction
progressed,
the substrate darkened in color and became considerably more
voluminous. A quick
sniff from the top of the reflux condensor indicated a very
significant change
in odor. Smell was consistent with other published reports. At the
completion of
the reaction, the stirring was stopped, and the flask was removed to
cool down.
Note 3: Separation was not too difficult.
Note 4: Solvent was added (toluene) as was dH2O and the phases
separated
cleanly. The solvent layer was then washed with saturated solution
of sodium
carbonate. The evolved carbon dioxide made separation somewhat
difficult making
basification with NaOH probably more desirable. Approximately one
hour was
needed for the separation of phases. The solvent layer was bluish-
black. The
water layer was slightly cloudy. Separation of the organic layer was
commenced
followed by two dH2O washes. Solvent was evaporated to yield a
markedly viscous
black oil that seemed to have a tarry appearance. Smell was pleasant
and NOTHING
like the starting alkene. Assumed the reaction to be successful as
there was a
quantitative change with no apparant cleavage of the ether ring. Had
there been
any ring cleavage, the sodium catecholate would have formed during
the basic
washes and been carried away in the subsequent water washes. But
then again,
sodium carbonate and bicarbonate solutions when mixed with phenol
inhibite the
formation of sodium phenolate. This suggests that the sodium
catecholate
formation may have been retarded due to the sodium carbonate in
solution. In any
case, however, the presence of such a large amount of end-product
substantiantes
the assumption that the reaction did indeed effect some kind of
change in the
1-alkene structure.
Note 5: Distillation was attemted but due to an undetected leak in
the vacuum
system, the process ended in failure. Heat was applied in ever-
increasing
amounts with the assumption that the 2-bromoalkane must necessarily
have a very
high bp. When the attempt was finally abandoned, it was too late.
There was
nothing left in the distilling flask except carbonized material and
tar. Only
DCM was able to remove it after letting it soak for a day. About 1/4
ml of oil
distilled over into the receiving flask. It was deep red, and had a
pleasant
smell to it and was assumed to be the 2-bromoalkane. Being useless
in such an
amount, it was discarded.
Note 6: Since all the product carbonized, this step was omitted.
Another attemt was made. Conditions were identical except the
reaction time was
30 min. This modification was made due to the information found in
the article
regarding the more facile and quick brominations of styrenes when
compared to
typical aliphatic alkenes. End product was less viscous and not as
dark. Not as
voluminous either. Significant odor of starting alkene was detected.
Made the
assumption that in order to be successful, reaction time must be in
the order of
two to four hours.
An attempt at substitution of the bromide atom for that of an azide
was made.
Two phase aqueous azide solution and 2-bromoalkene were reacted
together in a
manner identical to that of a published proceedure (I'll get the
article for you
guys soon). Even when using a very powerful stirrer, mixing of the
two phases
was virtually impossible due to the viscosity of the unpurified
undistilled
2-bromoalkane.
At the end of the reaction, an attempt was made to try reducing the
azide
product (it was assumed that there probably was no 2-azidoalkane
formed due to
the crappy lab technique applied to the previous step, but oh, well,
what the
hell.) Proper proportions of the suspected 2-azidoalkane MeOH and Ca
metal were
reacted the manner detailed in TSI and II. There was the fear that
the PTC
(hexadecyltributylphosphonium bromide) still dissolved in the
suspected
2-azidoalkane would somehow undesirably react with the Ca metal,
thus redarding
the scheme of the reaction. Fears were abated as just a little
bubbling
occurred. In fact, practically nothing happened. The reaction was
assumed to be
a failure. Money was scarce, as was the need to have a working
method. The
1-alkene to 2-bromoalkane to 2-azidoalkane to the final 2-amine
route was
abandoned as there was no detailed established proceedure to follow
printed
anywhere in the literature. The process was immediately substituted
with the
1-alkene to 2-ketone to 2-amine strategy. Have had no regrets
whatsoever.
An attemt was once made to synthesize the 2-amine via the 2-
bromoalkane a long
time ago using the proceedure published in Journal of
Chromatographic Science
Vol. 29, April 1991 pp.168-173 and Vol. 29, June 1991, pp.267-271.
Although the
2-bromoalkane seemed to be (just seemed to be, mind you) produced in
about 50%
yield, the amine did not form. The process was deemed to suck big-
time, and of
course, was abandoned.
Here are some promising references describing newer and better ways
to
effect 2-bromoalkane formation from 1-alkenes using hydrohalogens
themselves or in their place, hydrohalogen precursors, reacted over
silica
or alumina. Here are the references:
JACS 1990, 112, pp.7434-7436; ibid. 1993, 115, pp.3071-3079
JOC 1988, 53, pp.4477-4482.
====================================================================
=========
Equarius:
1) Aq. 48% HBr:
340g of H2SO4 (drain cleaner est.93%) are added to 1483g of 35% aq.
NaBr solution
(spa shock or something). The solution is distilled at atmospheric.
~425mls cums
(all) over at 104:124 and is discarded. Then ~600mls of 48%HBr comes
over as the
125:128.5 fraction.
2) HBr in GAA:
440g of 48%Hbr is placed in a flask and setup for gassing. Over (not
in) the end
of the gas bubbling tube is placed a single section of glass wool
(nod to
Piglet) which is held in place by tethlon tape. Add a pile of NaCl
just so in
peaks on the surface. H2SO4 is slowly dripped in over many hours and
the gaseous
HBr channeled into 253g of slightly chilled GAA. The solution is a
nice orange
color. Then GAA is weighed again and %age calculated. 28% (w/w) in
this case.
3) BromoSafrole:
352g of 28%GAA is placed in a quart jar sitting in a cold water
bath. 91g of
Safrole (single distilled) are added in 4 portions over ~1 hour.
Note: recycled
Safrole from wacker / halogenation are not appropriate as isoS will
not convert.
Jar covered and stirred for 2d 19h (way overkill). Color progression
is dark
orange to green to deep bright red. The solution is dumped into
~450g of crushed
dIce/dH2O in a sep funnel. Heavy BromoS goes to bottom and is
seperated. The
remainder is extracted with 86mls of pet ether and added to the
BromoS. The
solution should (but wasn't) be washed with a couple portions of
dilute NaBiCarb
solution and best sit overnight with the BiCarb where substantle
crap goes into
the BiCarb water (thank gyro). The pet ether is distilled off. The
remainder is
distilled under vac (~~~28", big 3.9amp fridge pump). 11g of
(iso)Safrole are
collected from the 130:177 fraction. 64g of BromoSafrole are
collected from the
tight 178:181 fraction. Safrole normally comes over at ~140 with
same pump.
Suddenly black polymerized crap comes shooting through the condenser
plugging up
the entire apparatus which is exactly why crude solution must be
washed with
NaBiCarb.
====================================================================
=========
Chem Guy:
From "Analysis of 1-(3-methoxy-4,5-methylenedioxyphenyl)-2-
propanamine (MMDA) Derivatives
Synthesized from Nutmeg Oil and 3-methoxy-4,5-
Methylenedioxybenzaldhyde"
It is in
The Journal of Chromatgraphic Science, Vol. 34, Januuary 1996.
The Nutmeg oil is a methanol extract.
(Quotation)
"BROMINATION REACTIONS
A suspension of nutmeg oil in 48% HBr was stirred vigorously at room
tempature for 7 days. The reaction was then quenched with the
addition
of crushed ice and extracted with ether. The ether extracts were
combined, washed with water, and evaporated to dryness under reduced
presure , and the resultant product oil was analyzed directly by GC-
MS.
AMINATION REACTIONS
The crude bromination product was disolved in methanol containing
methylamine and stirred for several days. The reaction mixture was
evaporated to dryness, and the resultant oil was disolved in 10%
HCl.
The aqueous acid solution was washed with ether and then made basic
(pH 12) by the addition of NaOH pellets. The aqueous base solution
was
extracted with ether, then the combined ether extracts were
evaporated
to dryness under reduced pressure. The resulting oil was analyzed
directly. "
In another arctile concerning this same topic except the oil was
safrole. (Journal of Chromatographic Science, Vol. 29, april 1991,
page
169) It says
"... analysis showed the bromination occured slowly and required
approximately 7 days to consume most of the Safrole.... The results
of
the present study clearly shows that MDMA and related designer drugs
analogues of MDA can be prepared by amine displacement of
bromosafrole
obtained via bromination of the organic steam distillate of the
roots
of the sassafrs plant."
That same article gives the same reaction method:
"Bromination Reactions. Samples of sassafras oil or alkenes (5.0 g
of
safrole, isosafrole, eugenol, isoeugenol, etc.) in 48% HBr (25 mL)
were
stirred at room tempature for 7 days. The reactions were then
quenched
with the addition of crushed ice (25 mL) and extracted with ether
(2 x 50 mL). The ether extracts were evaporated to dryness under
reduced pressure and the resultant product oils analyzed directly.
Amination Reactions. The crude bromination products (2.0 g) were
dissolved in methanol (100 mL) containing 40% aqueous methylamine
(20 mL) and stirred at room tempature for 4 days. The reaction
mixture was evaporated to dryness and the resultant oil dissolved
in 10% HCl (50 mL). The aqueous acidic solution was waqshed with
ether (2 x 50 mL) and then made basic (pH 12) by the addition of
NaOH
pellets. The aqueous base solution was extracted with ether
(2 x 50 mL) and the comgined ether extracts evaporated to dryness
under
reduced pressure. The resultant oil was analyzed directly."
NOTE: This reaction can also use ammonia instead.
=================================
I found two references to benzyl ether groups in my texts. The both
say the benzyl ethers are "split by strong hydrohalogenic acids",
AKA,
--> HX, where X is I, Br, or Cl. But it doesn't say how easily, and
one refernece says "... especially HI" (as we already knew) and it
shows the equation:
"ArOR + HI, concentrated, heat --> ArOH + RI"
Now my question is, how concentrated do HBr and HCl have to be and
how
much heat is required for this? It seems that room tempature may not
be a lower limit for this method but a upper limit of tempature.
Maybe if you did this at 0C for longer than 7 days you wouldn't have
all this trouble?
Next,...
Found this in Journal of Organic Chemistry, 1980, Vol 45, 3527-3530.
"Addition of hydrohalogenic acids to alkenes in aqueuos-Organic, two
phase systems in the presence of catalyitic amounts of onium salts
In previous works we reported that lipophillic quarternary ammonium
and phosphonium salts show a high catalyitic activity in reactions
promoted by hydrohalogenic acids in aqueuos-Organic two phase
systems
such as the conversion of alcohols to the corresponding halides and
the cleavage of ethers. Recently quartenary ammonium salts were
shown
to extract hydrohalogenic acids from their aqueuos solutions into
low
polarity organic solvents."
The article goes on to state the effecivness of the PTC's for this.
But
it also states that this can cleave ether groups as well. The
reference given to this is "Synthesis, 1978, page 771". I haven't
had
time to look this up but I'm sure it will clear some shit up.
================================
From Synthesis, 1978, page 771,...
Cleavage of dialkyl and aryl alkyl ethers with hydrobromic acid in
the
presence of Phase]Transfer catalysts
"Standard methods to hydrolyse ethers require particularly drastic
conditions, e.g. the use of concentrated hydroiodic acid, or a large
excess of concentrated hydrobromic acid in acetic acid or acetic
anhydride at reflux or of pryridine hydrochloride at 200-220 C."
"Reactions were carried out by heating at 115 C under vigorous
stirring
a hetrogenous mixture of substrate (1 mol), 47% HBr (5-10 mol) and
hexadecyltributylphosphonium bromide (.1 mol)"
"Indeed in phase-transfer conditions even aqueous HCl quantitatively
converts alcohols into the corresponding chlorides."
"Attempts to use concentrated HCl or HCl and NaBr failed [to cleave
the ethers]"
The basic reaction:
ArOR + HBr --> ArOH + RBr
I hope this sheds some more light onto this subject.
1) NO HEAT!
2)Cold is good
3)PTC's work if use properly.
4)PTC and HCL don't have the problems that HBr does.
================================
FROM "The Journal of Chromatograpghy science, Vol 29, 1991, page
267-271
"Thus the conjugated bond in isosafrole does not add HBr under the
same
conditions as safrole. Therefore, any isosafrole generated in via
HBr
elimination would not under go readdition and should accumulate in
the reaction mixture."
The conditions were:
Bromination with 48% HBr (aqueuos). Stirred for 7 days @ room
tempature. Quanities- 5 grams safrole, 25 mL 48% HBr.
Quenched with 25 mL crushed ice and extracted with ether.
Analysis at this points showed one major product.
Amination was with 2 grams of the crude bromination product
dissolved
in methanol containing 40% aqueuos methylamine, 20 mL. It was
stirred
at room tempature for 4 days.
For the amination the crude bromo compound was dissolved in 100 mL
of
methanol and 20 mL of aqueous methylamine.
"In summary, these experimants show that HBr treatment of the
various
substitued allylbenzenes found in sassafras oil yeild predomintly
the
2-bromopropane intermedites. Methylamine displacement reactions with
these bromo intermedites yeilds the N-methyl-1-aryl-2-propaneamines
as
the major components."
--------------------------------------------------------------------
-----------
Drone 342:
An idea of mine:
To 235 ml of 10% methylamine in MeNH2 is added 0.89 g
benzyltriethylammonium
chloride and 18.6 g of crushed NaOH. The mixture is stirred
magnetically at rt
for 1 h. 24.5 g bromosafrole is added, and is allowed to react
overnight at room
temperature with stirring. The next day, the solution is check ed
via TLC to
determine completion of the reaction. Once completion is determined,
the
inorganic material is filtered out, and the solution is washed with
H2O. The
solution is dried over MgSO4, and stripped in vacuo. The final
product is
subsequently distilled in vacuo.
--------------------------------------------------------------------
------------
Rev drone:
Alledgedly, chlorosafrole is readily prepard via safrole, HCl, and a
PTC.
This is good, if it is the case. Does anybody have notes on this?
Chlorosafrole isn't as reactive as its heavier analogs bromo- and
iodosafrole.
However, I want to share with you all the magic of yet another
phase-transfer
catalylzed reaction: a variation of the Finkelstein reaction.
Yes, a little quaternary ammonium salt, a dash of CaBr2 (I've heard
rumors NaBr
works too), and a person can readily convert alkyl chlorides to
bromides without
breaking a sweat.
Synthesis 34, (1984)
J. Chem. Soc. Chem. Comm. 1250 (1986)
Isr. J. Chem. 26, (1985) 243
For those who prefer iodides:
US Pat. 3992432 (1976)
CA 72, 115271 (1970)
J. Chem. Soc. Chem. Comm. 879 (1974)
Synth. Comm. 16, (1986) 1029
--------------------------------------------------------------------
------------
J. Am. Chem. Soc., 1993, 115, 3071. "Surface-mediated reactions 3 -
Hydrohalogenation of alkenes". The article uses HCl in CH2Cl2 with
silica or
Al2O3 as the catalyst. The yields are excellent from what I
remember, and react
time quick. It seemed to me that
the addition of water really fucked things up though.
--------------------------------------------------------------------
------------
Osmium/Gnasher:
Attempts to induce direct cyclisation of 2-hydroxy- or 6-hydroxy-
safrole by
Adams method did not succeed due to the facile fission of the
methylenedioxy
group under HBr-AcOH treatment. However, the methylenedioxy group
was stable up
to 2hr in the presence of dry HBr in non-polar solvents such as
CHCl3.
Reaction of o-allylphenols with dry HBr a solution of the
appropriate o-allyl-
phenol (1mmol) in dry CHCl3 (15ml) at 0c was saturated with HBr.
After keeping
for 2hr, the reaction mixture was poured into ice water (50ml), the
CHCl3 layer
washed with water until neutral, dried (Na2SO4) and evaporated to
furnish the
corresponding o-(2'-bromopropyl)phenol in >95% yield as a dark brown
liquid.
The treatment of dillapiole with dry HBr gave a mixture of (I) and
2-bromodill-
apiole in CHCl3, it exclusively led to 2-bromodillapiole in DMF
medium.
When 2-hydroxy- and 6-hydroxy-safrole where treated in with dry HBr
in CHCl3,
the bromopropyl derivative was the main product (over 95%).
Experimental:
2-Bromodillapiole
Dillapiole (11.1g, 0.05 mol) in dry DMF (100 ml) was saturated with
dry HBr at
0!C. After keeping for 2hr, it was poured into ice-cold water
(300ml), extracted
with CHCl3, the organic layer washed with H2O until neutral, dried
over anhydrous
Na2SO4 and evaporated to furnish 2-Bromodillapiole (14.9g).
Ref: Indian J. Chem. Sect. B, Vol 25, 1150-54 (1986)
--------------------------------------------------------------------
------------
Ritter:
There really is no point to fussing around w/ nasty HBr(g) solutions
in DMF,
AcOH, DMSO, etc to make bromosafrole.
This procedure works perfectly for smaller quantities of the 2-
brompropane.
The thermal decomposition isn't much fun to deal with in quantities
greater
than 50g.
Synthesis of 1-(3,4 methylenedioxyphenyl)-1,2-dibromopropane
18ml 48%HBr(aq), 10ml dH2O and Isosafrol(4.2g, .0258mol)is dissolved
in 10ml
ethyl ether with vigorous mag stirring. Rxn is chilled to -10'C
(salt/ice bath).
N-bromosuccinimide (4.6g, .0258mol) is slowly added portionwise over
10min and
stirring is continued an additional 5min. Stirring is stopped and
phases are
separated. Aqueous layer is re-extracted w/ 10ml additional ether.
Organic
phases are combined, washed with 10ml 10% sodium bicarbonate then
10ml saturated
NaCl soln and finally evaporated to yield 8g of title product as a
thick
greenish oil(90-96% yield). Product does not yield a solid crystal
with any
known crystallization solvent and also decomposes upon heating/
distillation
therefor is best characterized as the monobromocompound.
2-Bromosafrole
The above produced dibromo compound is carefully thermally
decomposed in a
standard vacuum distillation rig using an oil bath. Since copious
quantities
of HBr are produced as decomposition product it only make sense to
use a water
aspirator as vacuum source. When pot contents reach approximately
100!C
dehalogenation takes place and 2-bromosafrole starts to distil over.
Depending
on vacuum, rxn. may start at lower temp. Do not allow pot contents
to excede
130!C or glassware will rapidly fill with charcoal from uncontrolled
decomposition! Yield of water white 2-bromosafrole was found to be
in the 80-90% range.
Another thing, I'm not much of a Uncle Fester fan however I must
give him credit
for his bromosafrole rxn which uses HCl to dehydrate 48% HBr. It
really does
work exactly as he describes it! Yields are high with very little
unreacted
safrole to separate from product and it can be scaled to any size
imaginable.
--------------------------------------------------------------------
------------
Easy Bromosafrole Synthesis by Berserker
This is a revolutionary new method to halogenate ketenes with
Markinokov selectivity,
by reacting them with a phosphorus trihalogenide in the presence of
silicon dioxide
catalyst. To make others, just substitute safrole with 10 mols of
another alkene.
A suspension is made by stirring 5g of SiO2 (silicon dioxide) into a
solution of
10 mol safrole in 25ml dichloromethane. To this, add a solution of 4
mol PBr3
(phosphorus tribromide) in 10ml DCM over the space of 10 minutes at
room temperature.
The solution is then stirred for around 30 minutes. The SiO2 (still
in suspension)
is filtered out and then washed with 15ml DCM. The combined liquid
is washed with
a 10% sodium bicarbonate solution, until no more gas is liberated,
then twice with
brine, and the organic extract is dried with sodium sulfate. The
solvent is then
allowed to evaporate, giving pure bromosafrole.
Yields vary from between 50% to 100%.
The SiO2 is 70-250 mesh powder, or can be prepared by grinding glass
into a fine
powder, and washing it with acid. Both silicon dioxide and
phosphorus tribromide
are unsuspicious chemicals, and can be ordered with ease from well-
stocked chemical
suppliers.
Source: Journal of the Brazilian Chemical Society, Vol. 12, No. 5
(2001)
--------------------------------------------------------------------
------------
Addition of Hydrogen Bromide to Safrole
JCS 2008 (1938)
A mixture of freshly distilled safrole (8.1g), a solution of
perbenzoic acid in
benzene (2cc of 0.3N), and benzene (100ml) was saturated with
hydrogen bromide
(2 hours). On each of the next 7 days perbenzoic acid solution (1ml)
was added,
and the mixture shaken and kept for 17 days. The mixture was then
washed with water,
dilute aqueous sodium carbonate, and again water and the benzene
layer was separated,
dried, and distilled. The fraction (6.5g, bp 145.5-153!C/9.5mmHg)
was a colourless,
mobile liquid and was identified as the known safrole hydrobromide;
Robinson and
Zaki (J, 1937, 2489) give bp 160!C/16mmHg.
The same beta-bromodihydrosafrole was obtained in both cases. The
product was
identical with the hydrobromide made under ordinary conditions and
it did not react
with potassium phthalimide, which is an indication of sec-bromide
structure.
--------------------------------------------------------------------
------------
1-(3,5-dimethoxy-4-hydroxyphenyl)-2-bromopropane
a mixture of 4-allyl-2,6-dimethoxyphenol (2.5g, 13mmol), HBr (40%,
in
glacial acetic acid, 15 ml) was shaken and placed in a darkroom for
a
week. Then the bulk of the acetic acid was removed under reduced
pressure
and the remaining acetic acid was removed by co-distillation with
ethanol.
The residue was cooled in a ice-bath and slowly mixed with anhydrous
K2CO3
(1-2g), and the resultant mixture was purified by column
chromatography to obtain
1-(3,5-Dimethoxy-4-hydroxyphenyl)-2-bromopropane as a colourless oil
(3g, 84%)
Reference: J Chem Research (s) 1999 (2): 158-159
--------------------------------------------------------------------
------------
Derivatives of amphetamine. E. Muszynski (Akad. Med.. Warsaw).
CA 58:3334 (1963); Acta Polon. Pharm. 18, 471-8 (1961) (in Polish).
Safrole (10 g.) and 0.1 g. HgCl2 in 5 vols. AcOH was satd. with HBr.
left 2 days
at 0!, neutralized with NaHCO3, extd. with Et2O, and distd. to give
73.3%
1-(3,4-methylenedioxyphenyl)-2-bromopropane (I), b15 162-5!. nD16
1.5628.
Methyleugenol (II) brominated analogously gave 36.5%
1-(3,4-dimethoxyphenyl)-2-bromopropane (III), b10 171-2! nD18
1.5614.
I (7.3 g.), 36 g. 10% alc. NH3, and 0.8 g. Cu2O heated 7 hrs. at
160!, alkalised to pH 9
with 40% NaOH. extd. with Et2O, and the ext. treated with 1:1 H2SO4-
EtOH gave 1 g.
1-(3,4-methylenedioxyphenyl)-2-aminopropane sulfate, and 4.2 g.
unchanged I.
II (2.9 g.) added at 0! to 9.3 g. 70% HBr, the mixt. left 12 hrs. at
0!, hydrolyzed, extd.
with Et2O, and the ext. distd. yielded 80.9% III. III (10 g.)
treated similarly with NH3
gave 3.4 g. 1-(3,4-dimethoxyphenyl)-2-aminopropane sulfate and
recovered 4.9 g. III.
Acetyleugenol (63.6 g.) in 80 ml. AcOH oxidized 5 hrs. with 256 g.
KMnO4, the MnO2
filtered off, the filtrate concd. to 800 ml., treated with 40 g.
KOH, refluxed 90 min.,
acidified with 50% H2SO4 to Congo red, evapd. to dryness, and the
residue extd. with
Et2O yielded 41.5 g. homovanillic acid (IV), m. 142!. IV (33.5 g.),
21.8 g. KOH, 25 ml.
EtOH, and 55.3 g. MeI refluxed 1 hr., treated with 11 g. KOH,
refluxed 1 hr., cooled,
filtered, acidified with HCl, and extd. with Et2O gave 33.9 g.
homoveratric acid (V),
m. 97!. V (20 g.) in 13 ml. AcOH passed at 430-50! through ThO2 on
pumice yielded
30.8% 3,4-dimethoxyphenylacetone.
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