Author Topic: Bromosafrole success with PTC - Jon's method does NOT work ! (Read 1667 times)

Dr.Methoxy · « **on:** February 22, 2010, 08:25:33 PM »

Hello.

I posted this method because I've seen a lot of insane things on this board. Jon claims to get super high yield bromosafrole via hydrobromination in AcOH. But his reaction cannot work and does NOT work !!!

1) Jon used 40% HBr. This concentration is not high enough. And I've never seen commercial 40% HBr... 48% ok but not 40 ...
2) He used only 1.9 eq ...
3) His reaction time is only 24h.
4) He doesn't use any PTC but acetic acid.
5) All his reports are brief and not well-explain. The lack of information is very substantial.
6) He often says strange things such as SN2 on bromosafrole works in iPrOH but not in EtOH because this latter blocks the nucleophile. Can anyone explain his theory

Work Up is here :

Quote

3-(2-bromopropyl)benzodioxole :

150 ml of 62% HBr (3 eq. ) and 200 ml of AcOH glacial are mixed in a 500ml RBF. The solution is

cooled with an ice bath and when the reaction has reached 0°C, distilled safrole (108,5g ; 669 mmol)

is gently added with vigorous stirring. The addition of safrole to HBr/AcOH is not really exothermic.

Time * Température [°C] * Color

0 min * 0 * no color

5 min * -1 * NA

10 min * -2 * NA

30 min * -4 * light brown

1h45 * -3 * dirty brown/red

2h30 * -4 * dirty brown/purple

3h * -3 * dirty brown/purple

4h30 * -3 * dirty purple

7h30 * -3 * dirty purple

16h * -1 * dirty purple/red

23h * 2 * dirty purple/pink

35h * 1 * dirty purple/pink

The stirring is stopped and the two phases are let separated, the organic one is at the top. The

mixture is poured on 1l fresh snow and manually stirred with a spatula. The organic phase has fallen

from to top to the bottom because adding water to the heavy aqueous phase has lightened it. After 30

min, the orgnaic layer is separated and the aqueous one is extracted with 2x 50ml CH2Cl2. The

extracts have a weird grey color... They are put again in the separating funnel. While the Na2CO3

solution is being prepared, the DCM solution turned to ... lemon green ! The oraganic phase is

immediatly washed with the carbonate solution and it turned to opaque yellow. The organic phase is

dried over anhydrous MgSO4 and DCM is boiled off. 109,0 g are recovered. TLC shows onyl one product :

safrole.

Dr.Methoxy · « **Reply #1 on:** February 22, 2010, 08:29:45 PM »

The key of success :

1) More eq of HBr are used : 5
2) Concentrated HBr : 62%
3) Using a PTC to carry the ions in the organic phase
4) 5 days of reaction time

--- Hydrobromination ---

150ml of Hydrobromic acid 62% (5 eq) and 12g (29,7 mmol ; 0.08 eq) of aliquat 336

(trioctlylmethylammonium chloride) are added in a four necked double mantel 250ml reactor* fitted

with a thermometer and a mecanic stirrer . The mixture is cooled to 0 celcius. 59.8 g (363 mmol) of

Safrole is added dropwise over 30 min. The reactor is covered with an aluminium foil to protect from

light. The reaction is let at 0 celcius for 5 days under strong stirring. 5 days later the carmine

mixture is made up of two layers. The organic one is at the top. The mixture is poured in a 1000ml

beaker full with crushed ice. The organic phase wich is now at the bottom is separated and weighed

out. 92,3 g were recovered. Yield** = 91% if all the PTC is in the organic phase, if this is not the

case yield will be higher. Aqueous phase is extracted with 2x50 ml DCM. Organic phases are mixed,

then washed with 100ml water, 100ml NaOH 0,01 M and 100ml water again. The orange solution (pH = 7)

is dried over anhydrous MgSO4 for the night.

Notes :

* The reactor was flushed with nitrogen to eliminate oxygen wich can cause radical formation. This

step was important because pure chemical-grade safrole was used and it does not contain any phenol.

Distilled sasafras oil contains phenolic compound wich can block radical reactions.

** This is not a true yield because some unreacted safrole is still in the bromo. Yield must be

calculated from distilled bromosafrole.

All reagent but the PTC have been bought from sigma-aldrich and are 98+ %.

--- Distillation failure ---

The MgSO4 is removed by filtration and washed with a little DCM. The orange solution was poured in a

250ml vacuum distillation system fitted with a vigrous column. The pH was acidic, therefore a drop of

triethylamine was added to treat that. The DCM was boiled off. When the temperature started rising

the bromosafrole polymerised with a strong heat and gas (meanly HBr) evolution. All the product is

lost. Because of tar, must of glassware was thrown away.

--- Things to know ---

1) Bromosafrole is not very stable. It easily decomposes or polymerises. After let it at RT the pH

changed from neutral to acidic. When you wash the organic phase, you should use NaHCO3 or very very

diluted NaOH. Store it in a dark and cold place.

2) Distillation is tricky even with a strong vacuum. You should avoid it. Last time bromosafrole was

distilled a 0.3 mmHg and only 60% was recovered... A lot of tar was produced at the end of the

distillation.

3) It was quite difficult to separate these 2 compound with TLC. Several solvent system has been used

with little success (AcOEt/Hexane, AcOEt/MeOH, ...). MeOH/Acetone 4:1 gives : Rf(bromosafrole) = 0.8

, Rf(safrole) = 0.85. MeOH:Acetone 9:1 will give better separation.

Naf1 · « **Reply #2 on:** February 22, 2010, 10:46:55 PM »

"SN2 on bromosafrole works in iPrOH but not in EtOH because this latter blocks the nucleophile."

I cannot substantiate the claims, but a Sn2 is the attack of an electrophile by the lone pair on a nucleophile. The nucleophile of course being Bromine, so Jon is saying that ethanol blocks the bromine by virtue of it being a better electrophile for the subsequent Sn2 reaction than the more highly substituted isopropanol.

And when steric hindrance around the electrophilic center increases Sn2 is disfavored and E2 becomes predominate.

Also, thank you for this great write-up!

timecube · « **Reply #3 on:** February 22, 2010, 11:50:03 PM »

I haven't tried the reaction myself, but there are previous reports of success using similar methods to the first you described:

http://www.erowid.org/archive/rhodium/chemistry/halosafrole.txt
http://www.erowid.org/archive/rhodium/chemistry/phenyl-2-bromopropane.html

shroomedalice · « **Reply #4 on:** February 23, 2010, 06:33:34 AM »

the way I have been thinking would be the easiest and best route is to put the alkene in acetic acid the gas the
solution with HBr gas. I would think this would be the most successfull.

this way water is not a problem and the whole process should be a lot quickers.

there are quite a few patents dealing with anhydrous HBr in acetic acid and one that deals directly with this idea of gassing the two.

so I think it should work.

I wonder why jons does not work. that does make me wonder to be honest.

still any thing I have found on WD that is a problem to the bee's gets deleted.

I still ask that the post in vacuuos that I asked to be removed be removed and more so now. it would seem
that some people dont get the idea that somethings are not to be talked about.

Vesp · « **Reply #5 on:** February 23, 2010, 06:37:23 AM »

shroomedalice, what are the references that you speak of?

2bfrank · « **Reply #6 on:** February 23, 2010, 08:27:58 AM »

This is all abit confusing. I always assumed that sN2 reactions, work best with a polar aprotic solvent, I think I understand that GAA could be used, but if alcohol is in the mix, this would create a solvent shell, that the bromide anion would have to get clear of, in order to attack the electrophilic Carbon. Be it alcohol or water due to using concentrated HBr, is surely going to reduce the rate to a very long period. Hence the 5 day suggestion. Gassing may have merit, but it would be good to get a ref.

I haven't been around here myself, but WHERE the fuck is Jon.

shroomedalice · « **Reply #7 on:** February 23, 2010, 11:07:00 AM »

I never said anything about alcohol but belstien does have a ref for acetone.

here is the ref I spoke about

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.

you will also notice that the origonal carter ref does not use aqua HBr it uses 33 HBr in acetic acid.

I have no question as to this working and I am setting up to test this on another allyl benzene
but my question and I dont want it answered is does the ammonia work for the swap with the
bromine or does it not.

the references I have seen say that methylamine work so I feel like it is worth the experement.

I do belive in all honesty that jon did produce what he said the way he did it.

I do notice though his information that he has supplied is very lacking.

but that is the way the game is played no matter what side your on. my self I like to have
my info set in stone so I give my info as a belife or tested data. I dont always test this
my self but I do know people I trust that do these things for me.

if they dont do things the way I belive things should be done I dont ask them again.

Enkidu · « **Reply #8 on:** February 23, 2010, 07:00:56 PM »

Aren't you worried about breaking the methylene bridge?

t8er · « **Reply #9 on:** February 23, 2010, 07:44:36 PM »

got about 1 week n a bit and new glass should be here

been interested as hell to try bromo route, and when i get a chance i will try it also, (still got another rabbit im chasing atm)

I also try'd too follow jon and yes its very cryptic indeed, i beleive jon has got it down, its just a matter finding it out for ourselves with the hints he drops here and there.

i dont think jon would rave about something that doesnt work, and if he doesnt want to give all the details thats cool, but im sure with the hints and bits we do have im sure it will only be a matter of time and a lot more people will be nailing this sucker to wall as well.

hope ya nail it shroom

swim out

patience USE THE FORCE

Dr.Methoxy · « **Reply #10 on:** March 20, 2010, 05:50:32 PM »

Quote from: Naf1 on February 22, 2010, 10:46:55 PM

"SN2 on bromosafrole works in iPrOH but not in EtOH because this latter blocks the nucleophile."

I cannot substantiate the claims, but a Sn2 is the attack of an electrophile by the lone pair on a nucleophile. The nucleophile of course being Bromine, so Jon is saying that ethanol blocks the bromine by virtue of it being a better electrophile for the subsequent Sn2 reaction than the more highly substituted isopropanol.

And when steric hindrance around the electrophilic center increases Sn2 is disfavored and E2 becomes predominate.

Also, thank you for this great write-up!

Bromine is not the nucleophile for this reaction !!! It's the leaving group an the nucleophile is the amine... Alcool solvent must not be used in the first reaction because R-OH groups can attack the nucleophile before the bromide to create Ph-CH2-CH(OEt)-CH3. And the SN2 must be done in non-protic polar solvent such as DMSO, DMF, NMP, HMPTA, ... I don't see the difference between EtOH and iPrOH.

This reaction has previously done in commercial HBr 33% in AcOH with good yield.

Quote

125ml (56.9 g ; 704 mmol ; 2 eq) of 33% HBr in AcOH are added in a 300 ml RBF previously flushed with N2. The flask is cooled with an ice bath to 0 celcius. 56,2 g of pure safrole are added dropwise during 1h. The mixture is let stirred for 36h at 0 celcius. The yellow solution is poured in 300ml ice/water. The bottom orgnic layer is separated out, washed with water,NaHCO3 solution and water again. The light green bromosafrole is weighed out : 77,3 g, 92% .

Naf1 · « **Reply #11 on:** March 21, 2010, 02:41:24 AM »

I was actually referring to the reaction between the alcohol and the hydrogen halide, you are right though I did call bromine the nucleophile (oops long weekend).

-vanadium- · « **Reply #12 on:** April 04, 2010, 10:47:42 AM »

Quote from: Dr.Methoxy on March 20, 2010, 05:50:32 PM

This reaction has previously done in commercial HBr 33% in AcOH with good yield.

Quote

125ml (56.9 g ; 704 mmol ; 2 eq) of 33% HBr in AcOH are added in a 300 ml RBF previously flushed with N2. The flask is cooled with an ice bath to 0 celcius. 56,2 g of pure safrole are added dropwise during 1h. The mixture is let stirred for 36h at 0 celcius. The yellow solution is poured in 300ml ice/water. The bottom orgnic layer is separated out, washed with water,NaHCO3 solution and water again. The light green bromosafrole is weighed out : 77,3 g, 92% .

why did you make it again ? your first synthesis with AcOH/HBr was easy and gave a very good yied, huh ?

jon · « **Reply #13 on:** April 04, 2010, 07:03:03 PM »

okay i'd like to clarify things a bit yes ammoia does work it has to be gasses into ipa and since ipa is'nt a very good solvent for ammonia it works best if the ipa is super cold in a dry ice acetone bath that wy you can achieve supersaturation.
(as high as 30%
i'm not going to engage in penis size contests here that's best done at frat houses and whatnot
btw nice work dr. mothoxy very thorough. yes of course you don't bother to distll alkyl halides with high b.p.'s
does ammonia work i've made it work at lower concetrations like 12% eve3n.
but higher concentrations allow for sn2 to go further to the right and eliminations are minized i still got 50% using 12% concentration. ipa allows for a weak nucleophile such as amonia to reat with bromosafrole, as to the question of blockage or caging of nucleophiles by protic solvents this applies to specific situations the nuclephile is weak and bears an anion then polar aprotic solvents enrgize the reactant by donating charge in this case the nu does not bear an anion and is realtivlely strong.
(j. march adv organinc chemistry aka the chemist's bible)
the key factor is the exclusion of water and it is done like so.
no drying funnel is neede in fact when gassing ipa the drying tube sometimes gets clogged and you get back gassed(not very fun)
so here's the trick supersaturate 1.25-1.5 moles of naoh in water like 80 ml h2o for every 100 grams for ex: allow this to cool
use a pressure equalized drop funnel to drop this onto the nh4cl.
the stochiometry of the nh3 to bromo compound idealy is 20/1 but you can fudge and get away with 15/1
exiting the gas generation vessel consisting of a round bottom a stillhead and a drop funnel atop the still head glass or plastic tubing bunged by a rubber or cork stopper (note methylamine will attack cork) this goes into a suckback trap (very important) and this leads into the chiled solution the end of the tube should have a ceramic gas dispersion attachement or steel wool for improvisers lilke myself.
the naoh is dripped onto the nh4cl at a rate that the ipa absobs it ie. one should'nt be able to smell any nh3 comming from the solution being bubbled into.
once all the naoh is driped onto the nh4cl the drop funnel removed the still head stoppered and the round bottom shaken to mix the contents .
this works well because this is'nt very exothermic so very little h2o is carried over into the alcohol the contents of the suckback trap are poured into the recieving vesel and the whole thing weighed for the amount of nh3 this converted to g/moles and the amount of bromsafrole/iodosafrole to be added hence calculated.

jon · « **Reply #14 on:** April 04, 2010, 07:11:31 PM »

excuse my grammtical errors please, the presure vessel could be some fancy caliometer or a parr apparatus.
in the reall world the cheapest fire extinguisher you can buy at walmart is good for 1-2 uses.
ammonia rxns are best tun at 100C and for 4-5 hours.
it takes longer the standard workup given in the reichpatent is optimal.
a water aspirator is used to remove the nh3 and the alcohol until no more alcohol is noted (use your nose)
acidfy to congo red (ph3) extract wtih ether (more like toulene avoid xylenes (high boiling point)
the aqueous basified to ph 12 and a brown to yellow oil should fall to the bottom also you will note tar this is the e2 by-product that poymerized.
man my fingers are tired i'll get back with you in a sec

mmkkkay
it's pretty self explanatory what to do from this point.

bromination:
my method is pretty simple, glacial acetic acid sodium bromide eqimolar h2so4 allow to react cool add safrole keep 0 C for 24 hours workup as described above the conc of the hbr in the acetic acid is optimally 40% don't worry if you see two phases.
and don't disturb at all or you will entrain some of the product in the salt (nahso4)
simple yet elegant.
personally i don't like the idea of fooling with hbr gas this is a handy alternative.
yes 1.9 mole of hbr to 1 mole alkene gets the job done any questions just ask.
this would be fun to try on myristicn and parsely apiol too

lugh · « **Reply #15 on:** April 04, 2010, 10:51:58 PM »

This old thread says that jon's method does work very well at least for dr strangelove but of course not so well for hellman/hellski/synthetikal:

'Grab your seats' (Safrole + HBr) - the Hive BB
the Hive BB
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'Grab your seats' (Safrole + HBr)

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Author Topic: 'Grab your seats' (Safrole + HBr)
dr.strangelove
Junior Member posted 07-01-99 10:08 AM

This is going to set you all on your ears.
I have seen it, and it is true.

A friend recently utilized some ancient polish refs that said 48% HBr WILL add to olefins like safrole with NO PTC's and NO other additives.
He used homemade 48% HBr and singledistilled olefin. Stirred for 7 days and achieved over 90% yield. Pulled out the bomb, added 20 g of his bromosaffy and 25 g MeAM.HCl, neutralized the salt w/ NaOH, and cooked it @70 deg. for 16 Hours. Yield over 19 grams.

Most of this stuff is overkill. (underground)
Try this.
dr.strangelove
Junior Member posted 07-01-99 10:34 AM

....and 100% over the counter. ....and requiring minimal chem knowledge.

The amine is present in a nearly 10x molar excess, ensuring high yield. This is one of the most researched reactions in the world. It has been clouded and mystified by the 'Powers that be' but it is real.
Bright Star
Member posted 07-01-99 01:16 PM

Welcome back stranger .... tee-hee ... So what do you attribute the failings of the past? The Time factor? hummmmm .... Heavy stirring? The bromo-addition was done at RT? What made you choose the 48%? All that was availiable? Made your own? What was the concentration of your MeAm? Water solution? Alcohol? What pressure was the bomb? SRV? Droney will ask for a ref .... Well it is a 'standard' reaction and I have wondered why it didn't work
...
I wish I could find out for myself .... I'm on sabatical you see ....*sigh*
ChemHack
Member posted 07-02-99 07:29 PM

The original ref was done at 0C for 12 hours. The abstract is on Rhodium's page.
Questions:
1. What temp did you combine the HBr and Safrole?
2. Safrole is not mincible with aqueous HBr. How fast was this stirring? What was the ratio of acid to safrole?
3. Did the layers become more or less mincible near the end of the rxn.
4. What was the color progression during the hydrobromination?
5. Was the Bromosaf treated with base then distilled as in the ref? If so, what vac/temp did it come over? What color was it?
6. What solvent did you use? The original ref used ethanol, a bomb wouldn't be required for methanol at only 70C. Was methanol used instead?
CHEM GUY
Member posted 07-04-99 03:33 PM

Yes, you are correct! Let me add credablity to your claim sir. I posted this a while back in the Novel Discourse forum. Its title is
"...(MMDA) Derivitives Synthesized from Nutmeg Oil..."
Here it is,...
The full name of this article I am going to paraphrase is "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 saasafrs plant." That same article gives the same reaction method except with safrole with the numbers being... 5 grams of sassafrs oil in 25 mL of HBr (48%). Extracted with two 50mLwashings of ether. The crude bromo-product was 2 grams in 100 mL of methanol containing 40% methylamine (25mL). It was stirred for 4 days, reacted with 50 mL of 10% HCl and washed with two 50 mL of ether. Etc....
NOTE: This reaction can also use ammonia instead.
CHEM GUY
Member
posted 06-24-99 04:06 PM
Does anyone have any info on the bromination with a PTC (Phase trransfer catalyst)? How about with the Wal-Mart water bed conditioner? I have a JOC arctile on this subjuct but not with something as specific as the Wal-Mart stuff. I'd like experimental results please...
jazz9
Member posted 07-04-99 08:50 PM

Could you describe the bomb? e.g. is it a stainless steel pipe? Aren't these sort of methods in the Uncle Fester book SOMM?
jazz9
Member posted 07-04-99 09:00 PM

Isn't that a bit of a wierd omission for the Hive...that good old-fashioned method of doing the amination in a stainless steel, threaded pipe bomb is never discussed.
Yet it must work.
Bright Star
Member posted 07-06-99 10:43 AM

ohhhh .... The Pipe bomb has been discussed thoroughly. Use the search engine. Several have gotten it to work ... Not-me has never tried it ... but you are right ... it must work. I think most bees are impatient ... And that has been their down fall ... But I'd like to hear more of this method ... Dr. Stranglove (or another incarnation ... ) Where are you?
Ranter
Member posted 07-06-99 11:44 AM

Not I (a long time ago) mixed NaBr with a bit of muriatic acid, then mixed it with safrole obtained by extraction with pure grain alcohol from sassafras root bark. Put it in the fridge for a week I think. After a day, the solution turned a particularly beautiful shade of dark red. But it was already red because of the impure oil; still, the color became more beautiful and refractive after a day. Gave up after that because the pipe bomb idea is sketchy at best. Years later ater read that refluxing in ammonia is sufficient, but yields are not great (still, you'll get some MDA). Not me got a tiny bit just by mixing with grocery store ammonia and letting sit, then evaporating on a pyrex dish, a la ketamine. It was very messy.
CHEM GUY
Member posted 07-06-99 11:55 AM

Boy you guy's are impatient! If you just by yourself a magnetic stirrer and wait the required time (~1.5 weeks) you WILL get XTC. The yeilds are a little low (~50%-25%). But when weighted against the cost of making it yourself or buying, god knows what, from Mr Narc, it sounds pretty good. Now there is no 100% yeild method so stopp looking for it. Personally I would rather have lower yeilds than deal with a fucking bomb! Come on people, be safe. I suggest looking up the articles I referenced.
jazz9
Member posted 07-06-99 11:55 PM

The MMDA recipe sounds very tempting. Is there any way to get some figures, that is how much in grams of each reactant? Because what the fuck it wouldn't cost very much money for someone to try this out.
Loki
Member posted 07-07-99 01:45 AM

Would a vibrating mixer work? ( Isaw one on ebay for 10 bucks lol)
------------------
It aint got a thing if it aint got that swing...
Ranter
Member posted 07-07-99 04:08 PM

No, but a vibrating dildo might .
jazz9
Member posted 07-07-99 11:17 PM

RE: the MMDA recipe with Nutmeg oil. I believe nutmeg oil has only 4-6% of myristicin, the precursor oil to MMDA, whereas some other essential oils such as parley seed or dillseed have maybe 10-20% myristicin, which should improve the yield. dr.strangelove
Junior Member posted 07-08-99 12:57 PM

Im pressed for time, (pressed. get it?)(teehee) BUT, ....re; failings of the past; using NH3 instead of MeAM, its just too volatile.temp@ HBr add'n- 25 c. set to 6 on my Thermolyne stirplate. red-burgundy. Finally, the bomb idea is NOT sketcchy.Its EZ as hell. Pressure threads, y'know. And its as close to 100% as you'll ever see. Bright Star- I'll e-mail you soon. ChemHack- You too. Most of you others, too... but I already have the regular guys emails....seiben7
Junior Member posted 07-08-99 01:53 PM

I have done the bromo addition to not-sassy a few times, seems to have worked fine, washed and get final product. I use the NaBr + h2so4 in 100ml freezing dmso, left for 7 days (didn't mean to leave it so long) but have not had a chance to go further, not scared of the bomb, have done similiar reactions. Dr., could you please email me...seiben7@hotmail.com. Haven't tried with nutmeg or others but will attempt soon and report. &
Semtex Enigma
Member posted 07-08-99 04:27 PM

If you get a moment to spare, could you boot that stuff over to me email addy? Thanks good doctor...
Semtex_Enigma@hotmail.com

dither
Member posted 07-08-99 06:26 PM

Was a vacume distilation done to seperate the unreacted saf from the bromo? If so, what temp did they come over at. Peace D
Gadget
Member posted 07-08-99 08:07 PM

I can't be reading this corectly, are we saying that some sassy oil, Hbr, MeAM HCl, NaOH and a pipe "bomb" is all one needs to create X if one is patient??? Ohhh, I got to be reading this incorectly, There has to bee a catch, It could NOT be this easy. I am off to the library to see if it has the referenced material. Any one ever grow their own sassy plants? This sure sounds promising for the backyard type of guy (like me) How did your "friend" manufacture the HBr? This can't bee for real, but it sure looks like it is. This sounds like something I could figure out

seiben7
Junior Member posted 07-08-99 09:03 PM

I did not distill the sass from the bromosass, just dissolved in ether and washed. From what I understand not necessary since the conversion is almost 100%. Gadget, you really don't even need a bomb, just patience, days...room temp or with low heat and stir for days, could work...the second part has not been completed as of yet, I wish to complete process with Nutmeg or other...shall experiement, hopefully will be a good weekend.
equarius
Member posted 07-09-99 02:06 AM

CHEM GUY; searched for your MMDA thread, but couldn't find it. Sounds like its worth discussing again. Hate to break this to you guys but nutmeg oil isn't going to make any MMDA, until after the myristicin is isolated.
CHEM GUY
Member posted 07-09-99 04:36 PM

I hate to break it to you, equarius, but,...That article just use a methanol extract of nutmeg and they got XTC. Granted you need alot of nutmeg to get a good amount of oil but IT CAN BE DONE! The article wouldn't lie. If you don't believe me look the article up. I referenced it towards the top of this post.
Postit
Member posted 07-09-99 10:46 PM

Do you think ammonium acetate can be sunstituted for plain ammonia?
CHEM GUY
Member posted 07-10-99 02:32 PM

That's a good question. I know you can use NH4OH. I will look it up in my references tonight and get back to you. By the way, why do you want to know? How hard would it be to make the NH4O(CO)CH3 into NH3 or NH4OH any way? Why not get the methanol and add that fertilzer crap, NH4SO4, to it. Add NaOH to liberate the NH4OH and the Na2SO4 will precipatate out. NH4SO4 + NaOH + (in alcohol) --> NH4OH + Na2SO4
CHEM GUY
Member posted 07-10-99 02:35 PM

Holy shit I just noticed I got the formula wrong!!!! Fuck me! NH4SO4 should read (NH4)2SO4 the formula shoyld read:
(NH4)2SO4 + 2 NaOH + (in alcohol) --> Na2SO4 + 2 NH4OH Sorry, next time I'll proof read!
jazz9
Member posted 07-10-99 07:24 PM

"The crude bromination product was dissolved in methanol containing methylamine and stirred for several days"
1. How much MeAm.HCl would you need?
2. If you use MeAm.HCl would you also have to add some 25% NaOH? How much?
3. Would 99%IPA work instead of methanol?
CHEM GUY
Member posted 07-10-99 08:15 PM

Later in my posting I quoted this for this method. "The crude bromo-product was 2 grams in 100 mL of methanol containing 40% methylamine (25mL)." This was concerning safrole not nutmeg extract, but I'm sure it will work for nutmeg as well. And yes IsoPropylAlcohol would work just fine, if it dissolves both products. ( the bromo- and NH3 or NH2CH3 or the like) I'm not sure if you can use NH2CH3HCl, but it's easy enough to find out. I know NH4OH works.
Jiggs
Member posted 07-11-99 07:00 PM

In the above recipe it calls for 25 ml of 40% aqueous methylamine in 100 ml of methanol to aminate 2 g of the bromo-product. To substitute methylamine.HCl, would this be correct instead of 25 ml 40% MeAm: 25 g MeAm.HCl in 25 ml dH2O plus 60 ml of 25% NaOH solution. I got these proportions from TS2.
iudexk
Member posted 07-15-99 07:44 AM

Is there a reason why no-one use iodosafrole? I thought the rxn would proceed faster and at room temp. w/it. I am
seiben7
Junior Member posted 07-15-99 01:18 PM

You can use iodo but you have to make the bromo or chloro product first then do the iodo switch, extra step. But, you're right, the reaction will
run faster, higher yields, and at room temp. Never tried it myself. Osmium?
iudexk
Member posted 07-16-99 07:10 AM

Why not just dream of bubbling HI thru safrole or make anhydrous HI in situ w/DMSO and add safrole?
CHEM GUY
Member posted 07-16-99 02:43 PM

NEVER USE IODIDIC ACIDS WITH ETHERS! Iodidic acids split ethers. Thats why nobody uses HI with safrole or the like.
ROR + HI, cold --> ROH + RI

I don't know how it splits asymetrical ethers. If you want to use an iodo- compound definitly substitue the Cl or Br with I in an acetone solution of NaI.
jazz9
Member posted 07-16-99 05:00 PM

I was looking thru Total Synthesis 2 last night and there's a section there about brominating safrole with 48% HBr, but Strike claims it only works with 48% HBr in acetic acid, i.e. 48% aqueous HBr doesn't work.
jazz9
Member posted 07-16-99 05:04 PM

See page 143 of Total Synthesis 2 by Strike.
CHEM GUY
Member posted 07-16-99 05:22 PM

Strike isn't patient. In the artilce I read it stated that it took most of the 7 days of stirring at room tempature to brominate "most" of the safrole. "Most" probably means over 50%. For most people 7 days is to long to wait. But if you are patient 48% HBr will work. I would add an excess amount of HBr. If you really want a higher % HBr just dry it with CaCl2. I don't think CaCl2 reacts with HBr.
ReFlux
Member posted 07-16-99 06:14 PM

Regarding HI - I had read some stuff on Rhodium's site (regarding in-situ prepared HI via NaI & H2SO4 in DMSO) that seems to indicated that HI will iodate safrole. Also I've seen other reports of this. Isn't the presence of H20 neccessary for the ether cleavage via HI? Also, it is possible to iodate alkenes w/ just iodine and Alumina.
-ReFlux
ReFlux
Member posted 07-16-99 06:19 PM

Also, was the addition to HBr done at 25C or -25C ? (Not clear from the post Dr.!) What I'm getting at is that at higher temps the addition of HBr proceeds via free-radical process and not in the desired position. How can you be sure that you did not simply amminate this wrong bromo compound (who's resulting amine is mildly psycho active)?
-ReFlux
CHEM GUY
Member posted 07-17-99 03:52 PM

The bromination isn't always in the proper position, but the majority of it is. When you think about does it really matter that some of your produst isn't as powerful? The cost of this proceedure off sets all minor side product formation. By the way my article says at room temp, (+25 C). Concerning the need for water for the clevage of ethers,... I don't know for sure, but do you think that you're going to be able to remove all the water? Also, since the H2O doesn't appear in the equation it would then be a spectator ion and act as a catalyst. ROR + HI --> RI + ROH

hellman
Member posted 07-17-99 10:03 PM

Well come on then, lets C-sum results, I am 100% sure that if it is as easy you say, they will come,- i mean everybody would drop what they're doing and freaking switch, ^ Sometimes I wonder about accelerants like h2so4 in the reaction, not to much as to produce too much p2pol, Gee Dr strange glove, If you could just lay it on the line.! with write-up, THAT SURE WOULD BE SOMETHING. It would be the ultimate recipe. 6 reasons why you should bromonate safrole,.
1) your safrole can be dirty(Within reason)
2) No isosafrole
3) no Pdcl2 ordering
4) No HgCl2- that sure would be nice
5) no p-benzoquinone-
6) even no Dimethyl formamide( DMF)

Seeya Dudes,
Who's gonna be the bromo man?
equarius
Member posted 07-18-99 01:40 AM

heck, now we don't even need sassafras, or even safrole. Just some nutmeg extracted with ethanol. And glassware, we don't need no stinking glassware. Now it's as simple as borrowing a bottle of nutmeg, brominating by stirring with aquaous HBr, then throw it in Mom's pressure cooker for a few days, and presto, instant "XTC". if it's written down then it's gotta be true.
e(gladI'mnottheonlyskeptic)quarius
CHEM GUY
Member posted 07-18-99 11:25 AM

Remember though, the 48% aqueous HBr needs to be in a molar excess. Try about 2-5x molar excess. If you want more sketchy info go to the "seriuos chemistry forum" and go back 100 days. You'll see the thread I speak of. Read it, it has good info about refluxing and some kinks that they have worked out. Later in the week I will post an article concerning PTC's (PhaseTransferCatalysts). It talks about how to speed up the bromination by adding Quarentary Ammoinuim Salts in about a 1-.1 molar amount. In general the article says any Q-A-S that isn't very water soluble will drasticly speed up the process.
Ollie-RSM
Junior Member posted 07-19-99 08:37 AM

I'm pretty new here, so please excuse my ignorance. Several people have been praising this brimination/debromination pathway to ecstacy because it can be used with nutmeg extract as well as safrole. But if myristicin is the precursor in nutmeg, wouldn't the final product have a methoxy group hanging off of it, making it different from MDMA? Is the term "ecstacy" used here to denote MDMA as well as its derivitives?
Thanks
ORSM
hellman
Member posted 07-20-99 12:42 AM

The problem here seems to be how to obtain an accurate 48% Hbr. The DMSO reaction involving bromide's with h2so4 WILL LEAD TO PROBLEMS, I have data that suggests that the Hbr is oxidised again by the h2so4, giving elemental bromine, This though can be rectified by using phosphoric acid instead,.I believe this might be one of the contributing factors that is giving everybody such inconsistant results. HBR- the problem child, How about passing a stream of H2S into some bromine and water, no good I'm sorry, You'd then have to seperate the bromine from the Hbr,.I hear you say. Fuck that,.DR weirdmitts, please respond. Don't just.......

hellman
hellman
Member posted 07-20-99 01:21 AM

chem guy, Strikes post, re: superior Hbr..., gives no success at all, infact it ends worse than it started. Are you comments fueled by optimism, or fact. Just because some girl named pugsley write's some shit, it doesn't make it fact. There is a rollcall over in the methods section on successfull bromination, Nothing complete yet.
Please prove me wrong,.
hellski
equarius
Member posted 07-20-99 01:38 AM

Ollie, you are correct. The association of MMDA with ecstacy is wrong and only made in this one thread. Here ecstacy or X is synonymous with either MDMA or MDA. I encourage you to completely ignore this thread and instead buy Strikes book. Read up on Wacker oxidations and the performic to yield MD-P2P, then read up on al/hg and sodium borohydride reductions to yield final product. They are the well established proven paths, unlike HBr. hellman; I hope you're correct because that could provide a nice pathway for final bromination of, say, DOB or 2-CB. Please add your wisdom to the thread about getting elemental Br from pool NaBr.
Osmium
Member posted 07-20-99 03:00 AM

Elemental bromine:
2NaBr + 2HCl + H2O2 ------> 2NaCl + 2H2O + Br2
Can be used to prepare elemental bromine or iodine in situ. Other oxidisers can be used, too. But H2O2 is the cleanest, reacting quantitatively and producing only water. It was posted innummerable times.
CHEM GUY
Member posted 07-21-99 02:13 PM

Hellman,
I wanted you to read the post because it points out a textbook source and it also tells you some faliures. First off I learned it that thread that refluxing is stupid, it fucks up everything. Next, I learned that a PTC will definitly help out the process. You can even chloronate with a PTC. If you wanted you could chloronate with the PTC and then replace the Cl with I so it would be easier to replace with the amine group. Thirdly, learn from others mistakes. You are right that just because someone writes something down it's so. But academic sources are different. I have academic sources. Sorry to bitch, just because a lot of peoples lab skills SUCK doesn't mean it doesn't work. Hell, if they can't do this route I bet you they can't do any of the other more sensitive routes.
Seedcrystal
Member posted 07-26-99 12:55 AM

This is off topic, but I see alot of talk and descriptions of aminating with bombs, but noone ever mentions seeling the bomb. For gods sake man wrap some teflon tape around those threads.
Nocturnal
Member posted 07-26-99 05:21 AM

ChemGuy, I am very interested in your post about brominating sassy where you say to stir for 7.5 days. Would you be willing to write out the whole procedure with *Details* on how much HBr to use, how much sassy, etc.?
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StAy Up FoReVeR!
nocturnal_raver@hotmail.com
hellman
Member posted 07-26-99 08:29 PM

Sorry guys, move on. It's just not worth it, Believe me, you reasarch it for about 20hrs, then you'll see why.

hellman
CHEM GUY
Member posted 07-29-99 09:07 PM

hellman, I have found no reference that states that the 48% WILL cleave the ether groups. If you have a reference, insight, or experience please write it down rather than speak unfounded wisdom. I try to back up all my claims with references rather than opinoins and when I do state my opinion I make sure that its stated as an opinion rather than fact. I don't mean to sound uppity, but this is an unresolved issue that really needs to be ressolved. I'm going to continue my research into this avenue unless someone can finally put a stop to this madness. (And props to who ever does) Proposed route: 5x molar excess of 48% HBr to safrole-like compound. With and without a PTC. No refluxing, from my research refluxing doesn't work.minimal heating. Another route: 37% HCl with a PTC, no refluxing just added heat. The base catalysized amine displacement of the halogen DEFINITLY works so there is no arguement here, just arguement over the halogen addition. Anyone care to answer?
Nocturnal
Member posted 07-29-99 10:49 PM

This is concerning the first post. Wouldn't one have to use anhydrous 66% HBr to brominate the safrole? Correct me if I'm wrong, but in order to brominate safrole using 48% HBr you wouldn't you have to add acetic acid to the HBr? Also, you say your friend put not-methylamine and the bromo compound into the "bomb". Don't you have to add some kind of alcohol as well?
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StAy Up FoReVeR!
nocturnal_raver@hotmail.com
hellman
Member posted 08-02-99 12:47 AM

ChemGuy,
I'm sorry, I don't know what you are referring too, ether bonds?. Look, here is my 2 cents(Pseudo Fact-lots of facts, lots of opinions) Why are you wasting time with this, nobody can get it to work, as far as I am concerned dr strangegloves doesn't know shit, infact he probably stirs just that,. I thought it was too good to be true when Dr Fuckgloves posted it, Junior member..That alone should of given it away, and now he's gone, funny. let it go,I did, I know it hurts, just let it go. Buy a Pd coin, and a O2 cylinder, these are far more OTC than KBR,HBR. On the other hand if you can come up with a working method, I take my toupe of to ya'. As ol' zwiterion said, Maybee having anhydrous Hbr, under pressure, might in fact work,. It just too messy. Sorry Dude
hellman
CHEM GUY
Member posted 08-08-99 01:41 AM

First 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.I hope this helps,...
Sleeper
Junior Member posted 08-09-99 11:47 AM

One can get bromosafrole in close to 100% yield (with anh.HBr made from 48% aq.acid and phosphorus pentoxide). The amination in a sealed pipe is another story. The yields are low (below 25%), if you can even get it to work. Let the dinosaur rest,there are better ways.

Bright Star
Member posted 08-09-99 03:32 PM

If you people knew who Dr. Strangelove really was ... you wouldn't be saying: 'dr strangegloves doesn't know shit,infact he probably stirs just that.'Hellman, you have been around here for a while and if I remember your introduction, you first registered as 'Elusis'. Now, that wasn't very cool. I'm not telling you to believe everything you read either ... but there are alot of 'old-guard' around here with different names ... and I would be careful what you say about them. I do not know why Dr. Strangelove is gone ... but if he still has any spice ... he'll be back. I know this one people, and if he says it works ... it does. PS- the secret to not getting busted is to NEVER SELL THE SHIT. brightstar@hushmail.com

hellman
Member posted 08-09-99 10:41 PM

BrightStar,
It was just a natural logical conclusion for me to pseudo abuse this dr Weirdmits, I know that I had a kinda weird start to the hive, you see my motivation was to enigmatically encourage successfull posts.(fullstop)as well as find out in fact if zwit was really locked up, I thought for some time, strikey was Zwitt, and if you remember my last post as zwitt, strikey boy finally said"no, you are not zwitt, because I speak to him from time to time, enough of this though, So and in my own way I tried to get this dr weirdmits to contribute by decrediting his performance as to spark some kind of response., It did't work, or did it? So you know him huh?
LETS JUST HOPE HE COMES BACK,
P.S I agree with you about not selling, also I believe the only other way of getting caught is through purchasing chemicals.
hellman
dr.strangelove
Junior Member posted 08-10-99 10:35 AM

Wow. I sure stirred the poop, eh? Well, I will address the commentary of one 'hellman' first, where he says it aint worth the time, and to just move on. Who are you, DUDE? (Drone 342 knows now!) Its worth it. My opinion on why the 48% HBr wont cleave the ether group is a simple one. There is a more REACTIVE site for the HBr to work on, ie; the double bond. Markovnikov will tell ya why. The fact that there is 52% water there may help also. Sunlight posted a while back on his observations that 37% HCl wont cleave an ether group while using it to crystallize. My concentration of HBr to alkene was about 1.5:1. Another reason. You would have to have a hell of a high concentration of hBr to cleave an aryl ether linkage. The real trick to brominating safrole this way is with hard stirring. and patience. The bps of safrole and the bromo add'n product are waaayyyyy apart. you'll have no problem distinguishing the two. Reflux- +25c.was the temp.Psychoactivity and a broken molar are the 'proof' I have of activity. HBr addition is intentionally shot down by agent provacateurs to make our efforts less fruit-bearing. OR The fucking cops know it works but disinformation is the real stock-in-trtade of the mind police. Pick the one you like best. equarius-I am the pagan. (not the walrus ) This is the OLDEST method there is. The German and polish chemists that worked this out needed a simple viable method that would work in 1919 or whatever antiquated date they came up w/ this. I find it amusing and paradoxical that the strongest (theory-wise) reaction is the most mystified. As to PTC's well, forget em. I think the addition can be speeded up w/ GAA, but even that isnt needed. Osmium, if you are there, can you lend credence to what Im saying? Fredrich Nietsche would be thankful. I will return soon.
LaBTop
Member posted 08-10-99 12:17 PM

Dear Doctor, this method is ANTIQUE:
In front of me now:
Kaiserliches Patentamt.
PATENTSCHRIFT
Nr 274350
KLASSE 12q. GRUPPE 32.
Ausgegeben den 16.Mai 1914.(!!!!!!!)
(Quote):
Es wurde nunmehr die unerwartete Beobachtung gemacht,dass Halogenwasserstoffsäuren unter geeigneten Bedingungen sich an die erwähnten ungesättigten Verbindungen unter Bildung der bisher unbekannten Alkyloxy-,Dialkyloxy- oder Alkylendioxyarylhalogenpropane anlagern, ohne dass die von vornherein zu befürchtende Aufspaltung der Alkyloxygruppe (n) erfolgt. Die Anlagerung von Halogenwasserstoff erfolgt dabei so, dass das Halogen an das dem Benzolkern näher stehende Kohlenstoffatom tritt. Die Derivate des Allylbenzols, z.B. Methyleugenol, Safrol, Apiol, liefern dabei also in Beta-Stellung substituierte (arylierte) Isopropylhalogenide: etc,etc. Further on I have also in front of me following Polish Reference: Stanislaw Biniecki, Edmund Krajewski 4.III.1960 Acta Poloniae Pharmaceutica
D,L-N-Methylo-beta-(3,4-Metylenodwuoksyfenylo)-Izopropyloaminy I etc.
It descripes :
safrole --HBr--> n-Beta-bromopropane --CH3NH2-->
D,L-n-Methyl-Beta-(3,4-Methylenedioxyphenyl)-isopropylamine .
Btw: The old German scientists from E.Merck in Darmstadt did it a bit faster then you, only a few HOURS.
Btw2: This whole procedure is extensively discussed here before if you would take the time to SEARCH, and the only interesting conclusion from that discussion was: In spite of the messy procedure, you can re use the unreacted bromo intermediate product into the next batch, so in the end, with multiple batches, you can arrive at a nice 75 to 85 % overall yield. SO WHY ALL THIS FUZZ? ITS THE OLDEST METHOD ON EARTH, and not at all hided away !
And Hellman, stop this semi-scientific behaviour, based on too less experience, it makes you the clown of the Hive, better study some more, BUT, I still like you! I do'nt think your an agent provocateur, such a one should have a good chemistry background...... (You were wrong again, time to chance tactics and techniques!) LT/
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EMOTIONSwill always beFREE!
LaBTop
Member posted 08-10-99 12:36 PM

Forgot to mention: Just cook at 120 C the Bromoproduct (Monobromdihydrosafrole) with 4-5 times its volume strong Ammonia in water for a few hours and you have the base.(fluid) But that you do'nt want, so:50 gram of MonoBromedihydroSafrole are just boiled (refluxed) 2 hours at 130 C with 250 gram of MeOH/MeNH2(as strong as possible you can make:MeNH2 gas! in cold MeOH), to get the base which boiles at 20 mm Hg at 155 C., and after that you make either the sulfate or chloride ENDPRODUCT. Can it be easier? So why the mess with a BOMB

? LT/
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EMOTIONSwill always beFREE!
CHEM GUY
Member posted 08-10-99 02:14 PM

I like the response people,... The substutition of the halogen by the amine is old hat for sure. If you can't get that to work, good luck. Now, I glad that someone finally told their HBr molar ratio, but I am surprise at the number (1.5:1). I thought for sure it would be at least 2 to 1. The stirring is a definite for this method, otherwise you get nothing. Personally I would like to have a HCl method, without using it as a gas. The HCl - PTC method looks real good, but the ether cleavage makes me
wary. I think a lot of problems with this method have been wrong ratios and wrong temps. The lower temps seem the way to avoid ether cleavage.
Osmium
Member posted 08-10-99 02:23 PM

Dr. strangelove , tell Nietsche I can't help him much with this, at least right now. Will try to have a look in the next few days. LäBTöp: How do you want to boil MeOH/MeNH2 WITHOUT a bomb at 130°C??? And let's not bee too optimistic with yields. 75-85 definitely is too optimistic.
Osmium
Member posted 08-10-99 02:30 PM

Dr Strangelove, you claimed those high yields! Oh shit, are you sure about it? No wishful thinking? This sounds good, and if you insist on these yields, I will believe you.
LaBTop
Member posted 08-10-99 04:39 PM

It still looks to me as re-inventing the wheel... But it's a relatively easy and simple route. Chem Guy: For you, and others interested, the interesting part of the original text(translated by me in english) from the Merck patent: 150 gram Safrole(cold!) are added slowly and under ice cooling to a 500 ccm concentrated HBr solution in water (concentrated at a temp. of zero degrees F. !!!), and several(no numbers!) hours shuttled at the same temperature. The reaction product is dissolved by adding Chloroform, this solution repeatably shuttled with a dilute Soda solution and water and dried with CaCl2. After evaporation of the Chloroform under reduced pressure(vacuum) the MonoBromdihydrosafrole together with a bit Safrole is left over.That reactionproduct is heated for several(no numbers) hours with a 4 to 5 times bigger quantity of strong Ammonia in water solution(no numbers) at 120 degrees Fahrht. and the base which is formed collected in the wellknown way (german:bekannte Weise). The compound is a colourless fluid, which boils at 153 Fahrht. under 19 mm Hg . It builds a good and easy to crystallize acidic Sulfate. The HCl salt builds white needles from F 183 to 185. SHIT!!! Chem Guy,Osmium. now I suddenly realise that those Kaiserlichen scientists in 1914 worked with degrees Fahrenheit !!!!!!! So all temp. in my former posts above must be readed as degrees FAHRENHEIT Damned, this could have caused so many failures in the past. Every modern chemist who reads this patent assumes the degrees to be in Celsius!!!!!This little "F" is the only time in the whole patent they gave the temp. scale, the rest gives only degrees!!!!! If you think and use Celsius degrees, your way too high!!!!!!! EUREKA.....And Ossie, they do not mention a bomb, plain boiling at 130 degrees FAHRENHEIT. Cooling was probably by CO2 dry-ice/acetone packed around the reflux column, or any other deep cooling method which they assumed their duplicating collegues would understand, which is at the Hive not so obvious. So Chem Guy, now we found all those wrong temps, you were right in your suspicion! Ossie, the Polish guy's claimed 63 % for a one time batch, but 73,2 % for repeated batches!!!!! LT/ PS: and I still do'nt know what's so new about this, please enlight me!

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EMOTIONSwill always beFREE!
LaBTop
Member posted 08-10-99 05:52 PM

Who's the one who allways remembers you that when safrole is banned from the earth, you allways still have Eugenol? Here's from the 1914 patent this: The beta-3,4-dimethoxyphenylisopropylamine which is produced in the same way as Example 3 (see: 150 gram Safrole(cold) etc. above) from Methyleugenol is a colourless oil at boiling point 141 to 142 Fahrht. at 5,5 mm Hg. The HCl salt melts at 150 to 151 F. Only difference: they restructured the raw Brome-body with alcoholical Ammoniak, not water/Ammoniak.Now this product is a benzene ring, with 2 O.CH3 groups at the 3,4 position, and our beloved aminated tail.(CH2.CH(NH2).CH3) Who's gonna connect those 2 O.CH3 groups to a Methylenedioxy group?Without damaging the precious "tail"? Another one: 50 gram IsoSafrole(cold!) are added slowly and under ice cooling to a 100 ccm concentrated HBr solution in ClacialAcidicAcid(GAA) (concentrated at a temp. of zero degrees F. !!!), and several(no numbers! 2??) hours shuttled at the same temperature.The reaction product is dissolved by adding Chloroform, this solution repeatably shuttled with a dilute Soda solution and water and dried with CaCl2. After evaporation of the Chloroform under reduced pressure(vacuum) the MonoBromedihydroisosafrole together with a bit IsoSafrole is left over.( I should seperate the leftover iso to use in the next batch, if I were you...use your brain and the method to indicate ketones...filter those crystals off) That reactionproduct is heated for 2 hours with a 4 to 5 times bigger quantity of concentrated alcoholical Ammoniak solution(no numbers) at 100 degrees Fahrht. The Ammoniak and alcohol are vacuumed off and from the leftover is the base liberated by flooding with NaOH or KOH solution. ( = and the base which is formed collected in the wellknown way (german:bekannte Weise). The base is a colourless fluid, which boils at 141 Fahrht. under 12 mm Hg It builds a good and easy to crystallize HCl salt, which melts at 200 to 201 Fahrht. The base is alpha-3,4-Methylenedioxyphenyl-n-propylamine, we know that as MDMA. A benzene ring, at the 3,4 position a O.CH2.O group and the tail is CH.(NH2).CH2.CH3 : Woooow, EXTASY. LT/
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EMOTIONSwill always beFREE!
LaBTop
Member posted 08-10-99 06:13 PM

OOOps, a typo, one M too much, they made MDA, the classic EXTASY ! LT/ Can you imagine them old prehistoric chemists, with no internet to communicate, and a few telephones, and then those crippled write ups, no numbers for time, they all did it by rule of thumb! Must have cost years for others to duplicate that sort of patents. They probably visited each other by horseback! FUCKIN-GERMAN-COWBOY-CHEMISTS !
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EMOTIONSwill always beFREE!
Acme
Member posted 08-10-99 06:22 PM

Labtop,
If I may be so bold, and please not to offend yall by any means, strictly in the interest of science, is it possible you mean MDA instead arises from this procedure possibly?? Also, if the tail is CH.(NH2).CH2.CH3 what the fuck is it again?? Please not to take this wrong, just curious is all, so dont revoke my priveledge to communicate with ya.

Acme
Member posted 08-10-99 06:24 PM

Please disregard the previous post as yall posted the correction as I was
replying.
CHEM GUY
Member posted 08-10-99 06:56 PM

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 aqueos HCl quanittatively 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.
hellman
Member posted 08-11-99 10:41 PM

Yee hee,
I'm gonna cum in my pants, you came back Dr Strangegloves,.It's really true, this is going to make
soooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo many bees happy,. Thankyou, oh thankyou,
Everyone that I have given the shits to except Labtop, I deeply say"hey,hey,hey...what a freakin day"
Dr Strangegloves.
So using 48% HBR,(the rest water?) 1.5 moles of HBR to 1 mole of safrole 25C heat-constant hard stirring for seven days COOL! Please tell us all how you made your HBR, please O' mighty one. Chemguy-I hope your smile on your face is just like mine, sorry for the antics, but in a bizaare way they paid off. Labtop-Since you continue to have this non vaginal fascination with attempting to flame me, I am afraid......Don't bore me, by trying to assinate my chemistry, the people know the truth.. here's some things I've done.
1) HgI2 synth-works
2) CuCl2 synth-works
3) NaI synth-works
4) Benzowacker without benzo
5) Metylamine from glycine-works
6) NaIaddition to ketone-theoretical So all you have is this crappy Borohydride, which is not OTC-(Useless for small time bees) Please don't tell me my chemistry is crap, You won't fool the children of the hive, sonny. They just want results, not a bitch fest. I'm beginning NOT to love you.
hellman
Sorry everybody, this is the last bullshit post I'll post for a while anyway.

Semtex Enigma
Member posted 08-11-99 10:46 PM

Sorry hellman, could you point me in the direction of the Benzo wacker w/o benzo??? Thanks...
ReFlux
Member posted 08-11-99 11:43 PM

Hellman-What's the NaI synth that you worked out? Is is a synth to make NaI or is it some form of creating anhydrous HI using NaI? Just curious!
-ReFlux
hellski
Junior Member posted 08-13-99 06:11 PM

I told you that I've done it and it works 100%. I've done more shit than most bees.
Modesty
Member posted 08-15-99 12:59 AM

Please tell me that this is as good as it looks... Hey LabTop, you wrote:"In spite of the messy procedure, you can re use the unreacted bromo intermediate product into the next batch, so in the end, with multiple batches, you can arrive at a nice 75 to 85 % overall yield." My questions:
1. How is the unreacted bromo intermediate separated? In the final acid/base extraction?
2. What is the yield from a standard run, disregarding possible reuse?
hellman
Member posted 08-16-99 02:57 AM

Success ,
Dr Strangegloves, I followed your post with great interest, and skip Labtop ravel of course, and it works,. Although i only got 14.32 g of final salt., Which went down quite well,. Fuck you labtop, you fraud, and a huuuuge guilt complex,. Bees.....This is the bomb. It's a shame this method doesn't use sodium borohydride, cause it would be right up labtop's alley, LAbtop- what are your friends gonna say when they find out you took credit for their idea,. Chew on that one baby, By your profile your an adolescant, respect starving college fag. Yes labtop, those big spiels of text just show us all here that either you have no friends(plent of time on your hands) or you crave respect more than anybody I've seen. Forget what happened when you were young, with mummy and daddy breakin up, no one cares I can say this because...... Bees,. This method will be the King of all methods.
hellman

hellman
Member posted 08-16-99 03:11 AM

P.S all bees,
I used one an ol small fire extinguiser, packed with broken borosilicate glass(To reduce inside volume). I thought, well, it's pressure rated so it should be safe. I used a barbecue burner, which was hooked up to an outdoor gas lpg cylinder, and got the flow just right to give me a contstant 70C. Every hour or so I poured HOt water into the pot which contained the fire extinguiser, to keep the optimum level/temp accurate. My methylamine came from the everyman pool shock, and sassafras came from glebe NSW Australia, water white no distillation required, just a 28% gaa wash and a few 5% Naoh washes. I just doesn't get any sweeter. Labtop- stop reading my posts, HA HA!
hellman
P.s. Almost forgot,.
I used commercial 48% HBr, i know, but I just had to know where the problems came from,. Ohh and let stirr for 7 days at 20-25C. I also had to resort to simple distillation at normal atmospheric conditions, don't worry it was just a borosiicate blown bulb, 5 cm column, with a nice bit of glass tubing connected by heat fusion, and walah!. Bye, bye
seiben7
Junior Member posted 08-16-99 02:13 PM

Hellman...
You are the man. I will be following this work closely and so far everything looks great. No more flames just friends... Say it.
&
Penis Seinfeld
Member posted 08-16-99 06:45 PM

This seems real fishy to me. Dr. Strangelove replied to hellman on the 10th. Hellman replied to his reply on the 11th, expressing his excitment about the Doc's return. Now, Hellman says that he let it stir for 7 days. Maybe another day to get the amine and work up and all that good stuff. He posted that on the 16th. You do the math kiddies. Doesn't matter anyhow, cause I have a hunch that this works . And I wouldn't want hellman to accuse me of undercutting him, as he has already done. Ohhhhh gyroooooogearrrrrrrrlooseeeee, whereeeeeee areeeeeeee youuuuuu It's coming.......
PS
hellman
Member posted 08-16-99 11:38 PM

Sorry, P.S. I did actually begin this operation just after Bright stars reply, I was in command of this 48% stuff, and brightstar's response gave me the little oomph i needed, also I did stir only 6 days and let settle 3 hours into the seventh day, work up took under 2 hours after the bomb, Here in Australia it is the 17th/8/99. I hope this helps,. Your making me feel like Labtop, I don't care though. It really works, and it really is easy, my job here at the hive is done,. We now have OTC mdma. goodbye for the last time all. hellman Also, i end posts quite often with helski, but never do i post with it as my name.
Nocturnal
Member posted 08-18-99 04:37 AM

Fellow bees, the following text is how I plan to start dreaming about making honey. I take no credit for this at all, it is just a bunch of imformation gathered from this thread and all over the internet. If any of you can work out any bugs, or find anything wrong with this info, please correct it.
Overview:
* (Precursor) Sassafras Oil -> Safrole
* (Precursor) Ammonia + Formaldehyde -> Methylamine.HCl
* (Synthesis) Bromomination of Safrole
* (Synthesis) Amination of Bromosafrole
Materials:
* Hot Plate/Stirrer
* Sassafras Oil
* (48%) Hydrobromic Acid (HBr)
* (28%) Ammonia
* (37%) Formaldehyde Solution
* Water
* Large Pot
* Frying Pan
* NaOH
* Glacial Acetic Acid
* Ethanol
* HCl
Step 1: Sassafras Oil -> Safrole
Wash the sassafras oil with an equal ammount of glacial acetic acid. Then, wash the oil with water. Last, wash with ethanol.
Step 2: Ammonia + Formaldehyde -> Methylamine.HCl
Pour 125ml (28%) ammonia into a beaker. SLOWLY add 245ml (37%) formaldehyde solution while stirring. Stir for 16 hours. Pour solution into the frying pan. Fill the large pot half way with water. Set the large pot on the hot plate and place the frying pan on top of the pot. Boil for an about an hour, or til all the water has evaporated. Stir occasionaly. Dump the remaining material into a beaker filled with 200ml (31%) HCl while stirring. Dump the solution into the same fryng pan and bring to a boil for 5 hours. Set aside to let cool.
Step 3: Bromination of Safrole
Pour the *required ammount* of HBr into a beaker. Set it on the hot plate and heat to 25C. Slowly add the safrole while stirring. Continue this stirring for seven days.
*Ratio for HBr to safrole is 1.5:1 moles
Step 4: Amination of Bromosafrole
Combine 20g bromosafrole and 25g methylamine.HCl in a pipe bomb. Neutralize the solution with NaOH. Cook at 70C for 16 hours.
------------------
StAy Up FoReVeR!
nocturnal_raver@hotmail.com
placebo
Junior Member posted 08-18-99 05:07 AM

Sounds too damn easy don't it! can anyone verify this? Is it really this easy? Also what would SWIM do if they had access to Hbr gas how would this proposed synth change? Any comments appreciated!

------------------
Remember it's all in your mind!
Bromine
Member posted 08-18-99 08:41 AM

Sorry for the threadspace used: but the implication in many parts of this thread is that no pipe bomb is needed. Why waste the extra effort, nocturnal?

Semtex Enigma
Member post

jon · « **Reply #16 on:** April 04, 2010, 11:18:01 PM »

really what is is is'nt who's right and who's wrong.
sometimes people will attempt a synthesis once or twice and fail then throw thier hands up and say "well it does'nt work"
but especially with patents there's usuallly one or two parameters that are off adn what it takes is diligence adn persistence to find out which parameters are wrong and adjust them properly to optimize the synthesis or even get it to work

micro · « **Reply #17 on:** April 05, 2010, 04:14:31 PM »

Btw, would it be possible to directly gas the safrole/allylbenze with gaseus HBr, instead of using 62% aqueus HBr or the 40% HBr in glacial acdtic acid?

shroomedalice · « **Reply #18 on:** April 06, 2010, 05:19:20 AM »

yes I agree with this idea jon its best that the operator has an understanding before realy using a synthesis.

Still I belive there will be a day that we can publish like the rest of the world with out being persicuted.

2bfrank · « **Reply #19 on:** April 07, 2010, 01:13:50 PM »

Yes good read, I also want to apologize to the aurthor and other participants, as my earlier confused comments were based on me responding to one post and not actualy reading what this thread was about. Reading this, being about reacting an alkene with HBr, and then an Sn2 reaction between NH3 and the bromosafrole. I earlier wrote that the neuclophile was Bromine, and waffled on some non inteligent waffle. Doesnt show much respect to the aurthors, hence apologies.

Author Topic: Bromosafrole success with PTC - Jon's method does NOT work ! (Read 1667 times)

Dr.Methoxy

Bromosafrole success with PTC - Jon's method does NOT work !

Dr.Methoxy

Re: Bromosafrole success with PTC - Jon's method does NOT work !

Naf1

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timecube

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shroomedalice

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Vesp

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2bfrank

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shroomedalice

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Enkidu

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t8er

Re: Bromosafrole success with PTC - Jon's method does NOT work !

Dr.Methoxy

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Naf1

Re: Bromosafrole success with PTC - Jon's method does NOT work !

-vanadium-

Re: Bromosafrole success with PTC - Jon's method does NOT work !

jon

Re: Bromosafrole success with PTC - Jon's method does NOT work !

jon

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lugh

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jon

Re: Bromosafrole success with PTC - Jon's method does NOT work !

micro

Re: Bromosafrole success with PTC - Jon's method does NOT work !

shroomedalice

Re: Bromosafrole success with PTC - Jon's method does NOT work !

2bfrank

Re: Bromosafrole success with PTC - Jon's method does NOT work !