secrets of manufacturer safrole

8/11/2019 Secrets Of Manufacturer SAFROLE

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I have distilled bromosafrole lots and lots of times. The problem isthat in theend of the distllation you tend to get a volcano of black ash andsmoke even if

you are careful. I've been wanting to say this for a long while the33% HBr inGAA is the best to use. You can get 90-95% yields in 12-16 hours,and you canjust leave it in the freezer, although an ice chest with lots of iceworks justfine. When you distill it, just be ready to disconnect it and havesomething todump 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 Ialso bought

anhydrous HBr gas in cylinders and would make the solution myself.Both workedgreat, but I dont know how easy it is to aquire some nowadays - Idont have thatproblem. At around 20mmHg the bromosafrole would start distill at175-185!C andcontinue to rise slowly until it reached 212!C, where decompositionoccurred.I generally would stop at 205!C, but sometimes it decomposes evenif you'recareful. I suggest you to be prepared, and check for vaccuum leaksvery

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 youthat a highervacuum will prevent that rapid charcoal-decomposition-volcano fromoccurring.

The decomposition is occuring because the still pot is getting WAYtoo hot.When you only have a few ml's left in the still pot (about 50), coolit downand transfer the remaining liquid to a smaller 100ml flask. Thisshould allowdistillation of the last traces of bromosaf without a problem.

--------------------------------------------------------------------------------

Here is the only bromosafrole (or bromo propenylbenzene) synthesis

you will


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ever need. It proceeds totally anhydrous with pure reagents, andgeneratesno obnoxious fumes to give you away. More than likely, this willspur DEAto 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. draincleaner). Tothis add 30g of NaBr. Stir well and repeatedly. Solution will turnorangeas all the NaBr is turned into Na2SO4. Do not filter, leave crystalsalonein case there is some unreacted NaBr left. If the H2SO4 and DMSO isanhydrous, 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 outcrystals, incase there is unreacted NaBr. In 1 or 2 days solution will proceedas inFester's turning green, then purple, then gradually burgundy.

To understand why this works so well, see Fieser and Fieser"Reagents inOrganic Synthesis" under DMSO monograph.

Note that there are two pathways for HBr to react. Via an ionicmechanism

generates the desirable compound. Via a free-radical route formsterminalbromo compound, which cannot be used (you can try for interestinganalogue,but who cares now that all mind altering chemicals are illegal undertheAnaloges Act, including all those in everyone's brains- imagine,even JesseHelmes committing felony if he has any brain cells left). The crudesassafrass oil contains eugenol, a phenolic compound which inhibitsfreeradical reaction. Thus you will get better product if you don't

purify outsafrole. Also keep reaction mixture away from air and UV light, bothgenerate free radicals.

The final mixture gets 500-1000ml of water added. The crudebromosafrolewhich settles to the bottom is seperated without adding any organicsolvent. If you cool it it gets pretty sticky and syrupy so thewater layercan be just poured off.

Then you add 200ml of ethanol and a 5g tablet of hexamine camping

fuel to


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start the Delepine reaction- you get MDA as the end product. (Well,if youlike MDMA better you can do the tedious methylamin synth in Festersbook orOrg. Synth. Look out for methyl formate which is deadly insidious

poisonlike dimethyl sulfate)

For the Delepine reaction you can use the bomb or reflux overnight,whichdefinitely works. some experimentation is needed here since I stillamunclear as to how much time this takes, or if it really can be runat roomtemp. The reaction with the iodo intermediate can certainly be runat roomtemp, but that requires a conversion to the iodopropenylbenzene comp

withNaI and maybe phase transfer catalysis or insitu with NaI during thebombor reflux.

When the hexamine salt is prepared in solution, then some HCl isadded andagain refluxed overnite. again, possibly this can be run at roomtemp overseveral days- who knows?

Then use typical amine seperation to get the pure product from the

acidicmixture.

Love and trips, Wednesday.

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

Several months ago someone (Pugsley, Wednesday, Uncle Fester orsomeotherAdams family member- my connections indicate they are probably allthe

same) posted a synth for bromosaftrole utilizing the conversion ofNaBr inDMSO with conc H2SO4 and further info for converting the bromocompound toMDA using the Delepine reaction with hexamine (camping fueltablets :) :) !

Also, there were some negative comments from some narc (chembaiting) whodisparaged the small amounts of sassafrass oil that were called forin thereaction, implying the process wasn't useful in production qty's,

and


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implying the hexamine reaction was some sort of joke. (prob. somecommunitycollege grad in the DEA)

We have done some experimentation with the bromination procedure;

andalthough not alot of detailed info was originally given, we feelthat alotmore attention should be given to the potentially revolutionaryprocedure.

First, 30g or so of NaBr was to be reacted with the theoretical (forHBrproduct) amount of conc. H2SO4 in 100ml anhydrous DMSO; and thenadding 5mlof sassafrass oil to the resultant crude mixture of HBr and NaSO4 inthe

resultant DMSO solution. Objection to the procedure was the highamount ofDMSO that was required in the reaction for the small amount of oil.Evidently, criticism was of the premature narc oral ejaculate beforeyouexperiment variety, since we found that only about 5g of NaBrdissolves inthe DMSO anyway- but that 30g (and much more...) of NaBr reactswithout thewhole mass first dissolving in the DMSO.

Evidently, the higher solubility of NaBr vs. the NaSO4 product

drives thereaction so that all the NaBr is converted to HBr without the totalamountbeing first necessary to dissolve. As the author notes, the first"Reagentsin Organic Synth" book explains the unusual solubility andreactivity ofinorganic halides and other compounds in DMSO. The solution doesgraduallyturn orange, and magnetic stirring accellerates the process, andundboubtably converts most of the NaBr into HBr. Since some NaBrmight be

trapped within a shell of NaSO4, some sort of stirring is neccessarytobreak up the undissolved mass.

****We will next try NaI, but wanted to get this out as it may be afewweeks until we can safely procure some NaI (thanks alot, cranksters,formaking anything with -I- suspect, NaI, HI, whatever, ha ha)****

In conclusion, it appears that practically any reasonable conc. ofHBr in

DMSO can be obtained (up until the point of heavy fuming) with the


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method.Further, the enhanced reactivity of halides in DMSO and theinherentlyanhydrous nature of the procedure and lack of mess and fumes makeit, at

least for the time-being the method of choice for bromination ofsubstituted allyl-benzenes. ................. Postscript: Althoughwe areinterested in MDMA only, the use of the Delepine reaction for makingMDA isa valid method. In fact, the original post is the first time we haveseenthe reaction used in any underground chemistry texts. The narccalled it"cute", but in fact the Delepine reaction has the cleanest andhighestyields out of any reactions for converting an organic halide into a

primaryamine. (assuming that camping fuel tablets contain some small amountofinert binder with a majority of hexamine, there's no reason thattheycouldn't be used for the Delepine reaction)

We would be very interested in hearing from any parties who havedone theexperimentation required for evaluating the conversion ofbromosafrole orother brominated allyl-benzene compounds at *room temperature* as

the postspeculated upon. *Room temp reaction of the bromo compound withhexamine(camping fuel tablets) and further room temp cleavage of thehexamine salt(HCl in alcohol reaction) would make a complete synth that could becarriedout in the complete highly desired "mayonnaise jar" glassware setfor themasses*.

Also, the use of sassafrass oil instead of pure distilled safrole

mightvery well provide higher yields (although not tried here). Its wellknownthat phenolic compounds inhibit the formation of a-bromo sidereactionsthat occur via the free-radical process (March, "Advanced OrganicChem",and many others); and sassafrass oil has plenty of phenolicsincludingeugenol in high conc.

the Professional.


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

Subject: Re: Re: MDA from MDP2PFrom: "guest"

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 methodfor> brominating safrol with 48% HBr actually works. My #1 so farseems to> be starting with MDP-2-Pol and brominating like Fester told us wayback> when chemistry worked differently (apparently). This would seemto> 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. Inthelibrary you will find books that you can read.

When you've discovered how it's done you can post your results toa.d.c forthe rest of us to read. You can connect to www.deganews.com and readold

Eleusis and ZWITTERION posts on this topic. I include a couplebelow.

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 MDMAfromhalo-safrole is shit because the main reaction is the elimination ofHX togive you the alkene (safrole) back again! If I had MDP-2-Pol then Iwouldn't want to brominate it at all. I'd oxidise it to MDP-2-P andreductively aminate the ketone to MDMA.

If I wanted bromo-safrole I'd make it from safrole using a phase-transfercatalyst to allow non-polar safrole to mix with polar aq. 47% HBr.Morelikely, I'd use aq. 37% HCl or, I presume, even aq. 32% HCl wouldwork togive chloro-safrole. See: Addition of hydrohalogen acid to alkenes:Landini & Rolla, JOC 45, 3527, (1980). JOC = Yes, that's Journal ofOrganic Chemistry to you. Phase-transfer catalysts can be extractedfromhair and fabric conditioners. The cationic surfactants mentioned on

the


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ingredients of such stuff will easily suffice as phase-transfercatalysts.But remember, when you use a surfactant to mix two immiscible phasesyoumust stir them at 500 rpm or better, otherwise nothing will happen.

Keepthe temperature on the low side otherwise you'll zap that delicatemethylenedioxy bond. So, why are you phaffing about with 47% HBrwhen youcan walk over to the local hardware shop and do something similarwith 32%HCl?

Eleusis contends that aq. 47% HBr can't be used to make bromo-safrole undernormal conditions.

This is the original article that sparked it all off, where Carterdescribes the addition of HBr to Alkene.

H. E. Carter, Metabolism of Amino Acids, J. Biol. Chem. 108, 1935, p623.

200 gm. of glacial acetic acid containing 150 gm. of hydrogenbromide wereplaced in a 500 cc. bottle in an ice bath and 100 gm. of allylbenzene wereadded. A rubber stopper was wired in the bottle and it was allowed

to cometo room temperature slowly with occasional shaking. In 10 to 12hours theoriginal two layers merged into a clear red solution. After 24 hoursthecontents of the bottle were poured on crushed ice. The crude bromidewasseparated and the water layer extracted with petroleum ether. Thetwofractions were combined, washed with water and sodium carbonate, anddriedover anhydrous sodium sulfate. The petroleum ether was distilled

through a20 cm. column and the residue was fractionated. The yield of crudebromide(90-95 per cent pure) was 235 gm. (92 per cent of the theoreticalamount).

Eleusis contends that Fester was talking through his arse when hedescribedthe prep. of bromo-safrole using this method. By implication,Eleusisimplies that most of the rest of Fester's book is made up.


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

From: [email protected] (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 ofMethamphetamine Manufacture_, which will probably end up being theonethat I put in the next revision of my MDMA FAQ. I thought I'd alsopostit as a separate file as well.

-Jon

CUT HERE/\/\/\/\/\/\/\/\/\/\/\/\MDMA Synthesis: Bromosafrole methodScanned fom _Secrets of Mthamphetamine Maufacture_

A good alternative to the Ritter reaction is a two stepprocedurefirst reacting safrole with hydrobromic acid to give 3,4-methylenedi-oxyphenyl-2-bromopropane, and then taking this material and reactingit with either ammonia or methylamine to yield MDA or MDMA

respectively. This procedure has the advantages of not being at allsensitive to batch size, nor is it likely to "run away" and produceatarry mess. It shares with the Ritter reaction the advantage ofusingcheap, simple, and easily available chemicals.

The sole disadvantage of this method is the need to do thefinalreaction with ammonia or methylamine inside a sealed pipe. This isbecause 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,andis quite safe if some simple precautions are taken.

The first stage of the conversion, the reaction withhydrobromicacid, is quite simple, and produces almost a 100% yield of thebromi-nated product. See the Journal of Biological Chemistry, Volume 108page 619. The author is H.E. Carter. Also see Chemical Abstracts1961, column 14350. The following reaction takes place:

[ Structural diagrams deleted]


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To do the reaction, 200 ml of glacial acetic acid is pouredinto achampagne bottle nestled in ice. Once the acetic acid has cooleddown, 300 grams (200 ml) of 48% hydrobromic acid is slowly added

with swirling. Once this mixture has cooled down, 100 grarns ofsafrole is slowly added with swirling. Once the safrole is added,thecheap plastic stopper of the champagne bottle is wired back intoplace, and the mixture is slowly allowed to come to room temperaturewith occasional shaking. After about 12 hours the original twolayerswill merge into a clear red solution. In 24 hours, the reaction isdone.The chemist carefully removes the stopper from the bottle, wearingeye protection. Some acid mist may escape from around the stopper.

The reaction mixture is now poured onto about 500 grams ofcrushed ice in a 1000 or 2000 ml beaker. Once the ice has melted,thered layer of product is separated, and the water is extracted withaboutl00 ml of petroleum ether or regular ethyl ether. The ether extractisadded to the product, and the combined product is washed first withwater, and then with a solution of sodium carbonate in water. Thepurpose of these washings is to remove HBr from the product. Onecan be sure that all the acid is removed from the product when somefresh carbonate solution does not fizz in contact with the product.

Once all the acid in the product is removed, the ether must beremoved from it. This is important because if the ether were allowedto remain in it, too much pressure would be generated in the nextstage inside of the bomb. Also, it would interfere with theformationof a solution between the product and methylamine or ammonia. It isnot necessary to distill the product because with a yield of over90%,the crude product is pure enough to feed into the next stage. Toremove the ether from the product, the crude product is poured intoa

flask, and a vacuum is applied to it. This causes the ether to boiloff.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 thenext step which gives MDA or MDMA. See Chemical Abstracts1961, column 14350. Also see Journal of the American ChemicalSociety, Volume 68, page 1805 and Journal of the Chemistry Society,part 2 1938, page 2005. The bromo compound reacts with ammoniaor methylamine to give MDA or MDMA:

[ Sructural diagram deleted ]


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To do the reaction, 50 grams of the bromo compound is pouredinto a beaker, and 200 ml of concentrated ammonium hydroxide (28%NH3) or 40% methylamine is added. Next, isopropyl alcohol is addedwith stirring until a nice smooth solution is formed. It is not good

toadd too much alcohol because a more dilute solution reacts slower.Now the mixture is poured into a pipe "bomb." This pipe should bemade of stainless steel, and have fine threads on both ends.Stainlesssteel is preferred because the HBr given off in the reaction willrustregular steel. Both ends of the pipe are securely tightened down.Thebottom may even be welded into place. Then the pipe is placed intocooking oil heated to around 130 C. This temperature is maintainedfor about 3 hours or so, then it is allowed to cool. Once the pipe

ismerely warm, it is cooled down some more in ice, and the capunscrewed.

The reaction mixture is poured into a distilling flask, theglass-ware rigged for simple distillation, and the isopropyl alcohol andexcess ammonia or methylamine is distilled off. When this is done,the residue inside the flask is made acid with hydrochloric acid. Ifindicating pH paper is available, a pH of about 3 should be aimedfor.This converts the MDA to the hydrochloride which is water soluble.

Good strong shaking of the mixture ensures that this conversion iscomplete. The first stage of the purification is to recoverunreactedbromo compound. To do this, 200 to 300 ml of ether is added. Aftersome shaking, the ether layer is separated. It contains close to 20grams of bromo compound which may be used again in later batches.

Now the acid solution containing the MDA is made strongly basicwith lye solution. The mixture is shaken for a few minutes to ensurethat the MDA is converted to the free base. Upon sitting for a fewminutes, the MDA floats on top of the water as a dark colored oilylayer. This layer is separated and placed into a distilling flask.

Next,the water layer is extracted with some toluene to get out theremainingMDA free base. The toluene is combined with the free base layer, andthe toluene is distilled off. Then a vacuum is applied, and themixtureis fractionally distilled. A good aspirator with cold water willbringthe MDA off at a temperature of 150 to 160 C. The free base shouldbe clear to pale yellow, and give a yield of about 20 ml. This freebaseis made into the crystalline hydrochloride by dissolving it in ether

and


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bubbling dry HCl gas through it.

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

Subject: Bromosafrole Prep from Uncle FesterFrom: Lasertek 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 afood fightwith someone named Eluisis. As a token of my appreciation, I'm goingto leaveyou with some of my original research on a couple of topics which

mayinterest you. I think anyway it's original. If anyone comes up withreferencescovering these topics, let me know.

PREPARATION OF BROMOSAFROLE FROM 48% HYDROBROMIC ACID

A greatly improved procedure using 48% HBr to make bromosafrole ismy owninvention, and it is with unbounded pride that I offer this advanceto thefield of MDA manufacture. This procedure is both quicker and much

higheryielding than the procedure worked out by the jackass who wrote thearticlefor the Alabama Academy of Science cited earlier. This so-calledresearcherwas hired by the DEA to fool around with 48% HBr to see if it couldbe usedto make MDA or MDMA from sassafras oil. They had busted someonewith 48% HBrand a load of sassafras, and to make their case they needed to showthat itcould 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 ina cageas a result of his inflated claims.

You bought this book for the straight poop, so let your Uncle beyour guide.To get good yields of bromosafrole from 48% HBr and sassafras oil,mix onepart sassafras oil with one part glacial acetic acid and two parts48% HBrin a suitable-sized flask. Chill this mixture down in ice, then

with strong


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magnetic stirring pass a stream of dry HCl gas into the solution foraboutan hour. See Chapter 5 for the dry-HCI gas-generator. How much HClto passinto solution? Well, for a batch using 50 ml of sassafras oil, the

amount ofdry HCl generated by dripping 75 to 100 ml of sulfuric acid onto ahalf-full500 ml flask of salt-hydrochloric-acid paste is about right. Alittle bitmore wouldn't hurt. Good ventilation is required!

As the dry HCI passes into the solution, it dehydrates the 48% HBr,causingit to react with the safrole. The dehydration and the reaction bothgeneratea good deal of heat, so fresh ice will periodically have to be put

into thebath around the reaction flask. The temperature of the reactionshouldn'tbe allowed to rise above 10-15!C. The reaction mixture first turnsgreenthen blue, then purple, and finally burgundy. When the bubblingwith dryHCl is finished, stopper the flask and continue stirring in the coldfor twodays. Sometime around a day into this stirring, no separation ofphases canbe seen when stirring ceases.

The amount of dry HCl produced by dripping sulfuric acid onto saltwill varywith the exact conditions, so the batch should be checked forreaction beforequenching 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 checkthis, afterthe day of stirring is done, pour some of the reaction mixture intoa beaker,then from beaker, return it to the reaction vessel. This leaves a

coating ofthe reaction mixture on the glass in the beaker. Fill the beakerwith waterto rinse away the fuming acids, empty it, and sniff inside thebeaker for thearoma of the organics clinging to the glass. If it still smellslike thecandyshop fragrance of sassafras oil, an additional bubbling withdry HCl isgoing to be required, followed by another day of stirring in thecold. Afterthe first batch or two, it's easy to gauge how much dry HCl one is

getting.


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If the aroma has changed to something more chemical and fruity, yesjust likephenylacetone, sufficient HCl has been added.

When two days of stirring are completed, the batch is poured onto

crushed iceas in the other methods. When the ice has melted, a little bit oftoluene isadded (a volume about equal to the amount of sassafras oil used),and thewater-bromosafrole mixture shaken. Prior to adding toluene, thebromosafrolewill likely be on the bottom of the container, but adding tolueneand shaking,it should be floating on top. It's still burgundy-colored.Separate thebromosafrole layer with a sep funnel, and then wash it with about 3

volumesof water. Add bicarb slowly until the fizzing stops. This willknock outthe carried-over HBr, HCI and acetic acid. Shake some more, thenadd a littlemore bicarb to make sure all the acid has be neutralized.

Separate the toluene-bromosafrole, and place it in a distillingflask. Distilloff the toluene at normal pressure, then vacuum-distill theremainingbromosafrole. A vacuum that distills safrole at 110!C will distill

bromosafrole at about 140-145!C. Some chlorosafrole distills atabout 125!C.It can be used as is, or the chlorosafrole can be converted toiodosafaroleaccording to the directions found in the "Psychedelic Amphetamine"chapter inthis book. The yield is about 66-75% conversion to bromosafrole,with theremainder being unconverted safrole and chlorosafrole. Bromosafrolesmellsa lot like phenylacetone. It may turn pink on standing, and shouldbe stored

in a freezer until used.

With this posted, has anyone ever discussed the bad effects that thezincgalvanizing on steel pipes has on the next stage of the reactionwith ammoniaor methylamine? White crystals galore! It most be stripped off indiluteHCL prior to use.

Along a similar line of thought, has the reaction of safrole withdry HCl in

toluene been considered? Chlorosafrole has interested me for some


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time.It too smells like phenylacetone. My experiments indicate that HCladdspoorly to safrole at slightly elevated temps. About 10% yield in athree

week reaction time. Higher temps would be needed to bring aboutreaction,but below the about 100C temp where ether cleavage with HCl happens.Onceone has chlorosafrole, what good is it? It can be converted toiodosafroleby refuxing with 2 moles of NaI in acetone, and then filtering outthe NaClprecipitated, boiling off the acetone under vacuum, and recoveringtheiodosafrole by extraction with toluene. What good is iodosafrole?Compare

to the 2 halogen propyl benzenes listed in JACS 68, pages1009-11(1946).

Similar chloro derivatives give small yields, whereas the bromoderivativeof safrole gives a decent yield of product at lower temp. I see atrend here.The iodine is a better leaving group, and should give a superioryield atlower reaction temp. Read over all the relevant lit beforeproceedings Alsoknow that a significant amount of mail I've recieved indicates that

thepresence of a significant (that means more than incidental) amountof waterin the pipe bomb with bromosafrole yields excessive amounts of tar.Justadding 40% mehylamine or 28% NH3 to the alcohol is too much water.This isfine for making meth or benzedrine by this method, but for MDA somedehydration is called for.

I hope this contribution to the discussion group causes seriousexchange.

I also hope you've enjoyed meeting my friend down the streetLASERTEK.He's not a chemist, rather he works metal using a laser. He hasn'thad somuch fun since he discovered your group.

Best, Fester

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

Ritter


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Yup, that's the procedure I've been touting for years now. I don'tknow howmany times I have to say that Fester actually did something rightthis time!

The only variation I've made on his procedure is to bubble in abouthalf againas much HCl(g) as Fester calls for. Other than that the reactionprocedesEXACTLY the way he quotes it, color changes and all! Just make surethe icebath is kept chock full of ice for the entire duration of the rxn.

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

From: [email protected] (Lamont Granquist)

Newsgroups: alt.drugsSubject: Re: Newest MDMA SynthesisDate: 19 Apr 1994 20:31:00 GMTMessage-ID:

[email protected] (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 theone>that I put in the next revision of my MDMA FAQ. I thought I'd alsopost

>it as a separate file as well.

According to J-Forensic-Sci 35(3):675-697 this isn't the best methodofmaking methoxylated amphetamine derivatives. The author claims thatyields are low, synthing the intermediate is time consuming(althoughso is synthing MD-P2P), and potentially hazardous -- I don't knowwhyits hazardous, but the author references ANALOG 9(3):1-10 whichis an article by Hansson, R.C. entitled "Clandestine LaboratoriesProduction

of MDMA."

It is suggested that the synths using cyanoborohydride, aluminumamalgam,borohydride or Raney Ni catalysis from MD-P2P would be more likelyto be used.The two former ones are preferred as the borohydride method has alower yieldand the catalysis requires the construction or purchase of ahydrogenationunit.

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


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=========

Subject: Iodosafrole Secrets: the DMSO Method Date: 1997/05/08

The iodosafrole method of producing MDMA and MDA is indeed viable;being oneof those multikilagram processes here in the Netherlands someone wasaskingabout.

The key is using the DMSO method of producing anhydrous HI. NaI isdissolvedin DMSO and then an equimolar amount of H2SO4 is added. Na2SO4precips out.The reason the process works is that DMSO has the peculiar propertyof

dissolving lots of NaI. (the solubility is much higher for NaI thanforNaBr, making the HI process much better for large qty- make note ofthis youcrank manufacturers) (will phoshorus and iodine be obsoleted?? :)

And DMSO makes such acids particularly active. And HI is not likelytocleave ether substituted allyl benzenes like apiole, asarone, andmyristicin.(See Feiser and Feiser in Reagents for Organic Synthesis vol. 1 fordetails)

Extraction of iodosafrole left to your own imagination. Our tradesecret!!

Finally, amination is done at room temp with methylamine for MDMA orwithhexamine (via Delepine process) to get MDA or other analog.

Happy trails! Pugsley and Wednesday.

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

=========

From: [email protected] (Anonymous)Subject: Pugsley: on Bromosafrole via DMSO Method/ Various topics,adviceDate: 1997/08/31

Congratulations to the poster on getting the DMSO method ofbromosafrolesynthesis to work. Its incredibly easy- but too easy for anyone tobelieve it

works. Its the amination thats the more difficult part. Be careful


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if youdecide to make your own methylamine via the formaldehyde/NH4Clmethod- itgives off alot of methyl formate at the start, which is really nastystuff,

almost as bad as dimethyl sufate. It turns into formic acid in yourlungs.Big Mr. Yukk sticker on that one. Another chemical given off,formylal, hasa nice smell and is relatively safe, but masks the danger involved.

I'm still interested in hearing in this NG from anyone doing theDelepinereaction with hexamine camping fuel to get MDA. Bromosafrole hasgiven mixedresults. Iodosafrole works at room temp. I don't see too muchproblem with

getting NaI, since it can be diverted from table salt andphotographicapplications. I don't know if CRSB sells it, but they should. (ifthey stayin business) I don't think that meth labs use it, since in aquiousmedia,H2SO4 turns it into elemental Iodine plus whatever salt of Na.DMSO doesn'tsuffer from that problem.

I still see a lot of synthesis and talk on methcathinone. Verylittle said

about cyclization products, which is one of a couple reasons somepeople can'tseem to make it. There were some posts here a while ago referencingthespecific papers on the subject. I didn't have to time to go to thelibraryand dig all that stuff up.

Never keep academic papers or chemistry books of any kind on yourproperty ifyou are making "stuff". Memorize, memorize, memorize. Try to useanything

but commercial glassware if you can. A suprising amount ofchemistry can bedone with spagetti sauce jars and various types of tubing. Evenholes can bedrilled in spagetti sauce lids and brass pipe fittings soldered, forvariousoperations involving gases.

For exampe, I performed the entire asarone and anetholepseudonitrositesyntheses for TMA and PMA respectively, using nothing other thansauce jars

and a large pyrex juice dispensers as containers. One sauce jar has


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twofittings attached to it so that an outlet tube for the N2O3 could beattached,plus an inlet for air from a fish tank bubbler. The pyrex juicedispenser 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-coasterride. Except you start out at the top of a gigantic hill, insteadofgradually making your way to the top. And it hits real suddenly.)

I think a DA would really think twice about going after someone whohad nopaper evidence of drug chemistry efforts, and just a bunch of oldjars lying

around. If you ever read accounts of DEA busts, they always tellabout allthe drug and bomb making Loompanics books they find. If all theyfind areNancy Drew mystery novels, they'd look pretty silly.

Various people have been asking about where they can buy essentialoils.There are a number of web site based mail order suppliers. Justtype"essential oil" into AltaVista. For example 16oz of anise oilcosts $12.

Same price for sassafrass. Calamus oil costs anywhere from $60-200for 16ozdepending on where you buy it. Make certian to get the Indian oil.Theothers have no asarone in them. Nutmeg and elemi oil are reasonablealso.Parsley seed oil has gone up to about $100/16oz. If you isomerizeit toisoapiole, it makes way cool DMMDA.

Well, thats all the comment I can think of for now. I reallyhaven't been

doing much in quite number of months. I get burnt out on makingdrugs andfind new interests. I've never had any desire to make money thatway. Afterall, anyone smart enough to make their own druggs can probably makealot ofmoney legit. Its always been a curiosity thing. I am eagerlyawaitingFester's "Advanced Meth Chemistry Book". That should be interesting.Wednesday sends her good wishes.

Best Regards,


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Pugsley

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

From: [email protected] (Josh R Hardin)Subject: Pugsley & Wednesday Please ReadDate: 1997/09/07

First, let me thank you for the excellent information about theDMSO-Bromosafrole method. For those of you unfamiliar with it, Istrongly suggest searching dejanews. Basically, it uses DMSO, NaBr(fromdarkroom supply houses), and H2SO4 (drain cleaner) to synthesizeanhydrous HBr which converts Sassafras oil to Bromosafrole. This

methodis better than using commercially available HBr.

The authors suggest that after obtaining Bromosafrole, a 5g tabletofHexamine camping fuel can be added to start the Delepine reaction toconvert it to MDA. Does anyone have any references for the Delepinereaction? Is the mixture refluxed, cooked in a pipe bomb, orallowed tosit for a period of time? Does anyone have any numbers? The othermethod of converting bromosafrole to MDA via ammonia and isopropylalcohol or ammonia hydroxide gives poor yields (20%) and doesn't

smelltoo good to the neighbors.

In another post, Pugsley discusses iodosafrole. This method usesDMSO,NaI, and H2SO4 to yield anhydrous HI. NaI is easily diverted fromsaltlicks. I believe that the recipe is 100ml chilled DMSO + 7.8mlH2SO4 +43g NaI. Although this can be used for making speed without havingtopurchase red phos or iodine, can it be used for MDA? If one were to

usethe HI to convert sassafras oil to Iodosafrole, could it beconverted toMDA via the Delepine reaction? How? Let's use the example of 5mlSassafras oil + 100ml DMSO + 7.8ml H2SO4 + 43g NaI. After it hasreactedfor a day or so, there should be iodosafrole - right? Now, wouldaddinga 5g Hexamine camping fuel tablet start the delepine reaction? Whatarethe times and methods - reflux, bomb, let sit? How do the yieldscompare

to the bromosafrole methods?


22/46

Finally, in their amazing post about pseudonitrosites, the authorsstatethat the method can be used on various propenyl benzenes. Thiswould

allow isosafrole to be easily converted to MDA. Howver, in Fester'sPractical LSD Manufacture, he states that it will work on allpropenylbenzenes EXCEPT isosafrole. Howver, the two procedures aredifferent.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.Ican be reached at:

[email protected]

Thanks,HI Guy

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

From: Secret SquirrelSubject: COME MOCK MY DMSO FAILURE

Date: 1997/06/03

Let me first apologize for the outburst. After investing so muchtimeand energy into the project, to have it fail miserably at the endwasfrustrating, to say the least. I greatly appreciate Pugsley's andWednesday'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 postis pure fiction :).

The DMSO was purchased anhydrous at the local homeopathy shack (iteven says "for use as solvent only" *grin*). It would freeze solidwhen put in the fridge (a good sign). Kodak anh. KBr (from darkroomsupply) 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 relativequalityof the essential oil I have no idea nor reference for, all that canbesaid is that it was expensive.

175ml DMSO was chilled(frozen) in an acetone-rinsed 500ml round-


23/46

bottomand the flask placed in an ice-water bath. There was then added30.6gH2S04 drain cleaner with some evolution of heat. The drain cleanerwas

slightly discolored brown even though it came from a sealedcontainer(although the container is probably a year old). Looking at thecontainernow, the acid is dark brown-red with chunks, disgusting; evidently Ihaddrawn off the undisturbed clearer top part when doing this, butstillundoubtedly introduced impurities. I hadn't realized it at thetime, oreven much later.

69.3g KBr was then added. The initial granules falling into theflaskproduced a fine mist, much like ammonium chloride forming above abottleof muriatic and a bottle of ammonia placed next to each other,whichshot up a bit and gave me a bit of a gag. Perhaps the additionordershould be reversed. The soln turned orange, and began to stink.Thestench is a lot like garlic, and exactly like the smell of thesweaty

guy who had the locker next to mine in high-school gym class (ugh).A lot of KBr remained undissolved despite repeated stirring with aglassrod, as expected.

10ml sassafras oil was pipetted in. The stink changed from garlic/sweatto garlic/sweat/bandaids. The soln turned brownish-red with a sortofmobile greenish band on top. The flask was tightly stoppered, thenentirely enclosed in a ziplock bag, which still didn't keep in allthe 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 uponstirring.

My notes are missing for the next part, but around 600 ml ofdistilledwater was added in two portions, the entire thing getting dumpedinto aliquor bottle. A dark red, clear oil settled to the bottom; theaqeuouslayer turned cloudy tan as the solids dissolved into it. The aq

layer


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was poured off, and the oil washed with a bit more H2O. Yield ofoil was(guessing) maybe 7 or 8 ml.

To the oil was added 400ml denatured alcohol and 10.2g crushed

campingfuel, which was used straight but was nice and white crystalline. Afew small pieces of fuel didn't dissolve right away, but had afterthe soln sat one day. The soln was left alone until the 3rd day,whenheating was attempted, but aborted due to pesky interlopers. The4thday the soln was finally refluxed on steam bath for about 6 hrs. Itsat 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, fillingthe500ml flask halfway and nearly giving me a heart attack for the fewsecondsuntil my brain realized there were just too many and they wereprobablyammonium chloride and unreacted hexamine. As the rest of the HClwas added,the crystals all dissolved, but then gradually a white ppt formed,snowy andunlike the needles. The flask was refluxed on steam bath about 4

hrs andthen sat for a day. The ppt did not dissolve with heat.

125ml H2O was added, which dissolved the ppt and turned the solnopaquetan. A dark clear red oil settled out (I assumed it to be unreactedbromosaf).The pH at this point was less than 3, determined by indicator paper.Theoil was seperated and the aq soln extracted with 3x20ml 1,1,1-TCE.The TCEextracts were combined w/ the oil and set aside.

80ml 25% NaOH (lye) in water was added to make the aq soln stronglybasic.After shaking, a (small amount of) red-brown oil settles to thebottom.The oil was sep'd and the aq layer extracted with 3x20ml 1,1,1-TCE.TheTCE extracts were orange-ish. The remaining aq soln looks like icedtea.Post-mortem dissection of my notes reveals the combined TCE extractsandoil did not get an additional water wash. The TCE was distilled off

in a


25/46

flask I finally remembered to tare beforehand, leaving 7.4g of adarkblack-red oily goo, which was dissolved in 12.5ml anh. isopropanolandtreated with a couple ml of HCl, then evaporated on steam (ala

ZWITTERION,remember him?) to give a disgusting orange tar (which had to bescraped offwith acetone), a few grains of probably NaCl, and a whole lottastink.I would guess the stink was from methylamine HCl (from unreactedhexaminehydrolyzed during the second part of the Delepine) subliming withthe 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, withsoftcrying.

For my next attempt, I'm considering (among other things) doing thefirst part of the Delepine in TCE instead of alcohol, which wouldallowme to see the progress of the rxn, harvesting the pptd hexaminesaltand returning the rest to the heat. The salt could then behydrolyzedin a separate reaction. I'm also considering use of the bomb.

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

Date: Fri, 19 Sep 1997 17:37:07 -0600From: [email protected]: The Real Info - Please Read

HI can be made by reacting phosphoric acid (it can be purchased atHOMEDEPOT in the bldg supply section) and NaI or KI. NaI can be found

at saltlicks. HI can also be made by reacting dilute sulfuric (it's notspelledwith a ph bookworm) with NaI or KI. Now this produces HI gas. So,using avariation of Tom Kasper's push pull bullshit, in jug have 5L ofphosphoricacid connected by neoprene automotive feul tubing to a champagnebottlecontaining NaI, Ephedrine or pseudoephedrine, and H2O. Supposedly HIgasbubbled through a solution of 1 part ephedrine to 2 or 3 parts water

under


26/46

25 psi will make meth without the need for red phos.

The best quench for the Birch is ammonium chloride. Bubble some ofthe gasthrough 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:15gTripleSuperPhophate(might be tri-sodium phosphate):10g Al. If it works, which I doubt,the10g of Al should be AlCl because it is hygroscopic. This is all inonejug which is connected to another jug containing phophoric acid. Heclaimsthat 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 SantaBarbara.

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

Subject: Re: HBr + Safrole = ??????From: [email protected] (Eleusis)Date: 1995/10/15

In article , [email protected]

wrote:> So Fester is a Puss Face? Is the HBr route to MDA a total waist oftime?> The reaction appears feasable on paper. Does it work at all? Orare the> yeilds just pathetic? What modifications would one need to make tothis> 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 beenthoroughly

hashed over. In fact, I just posted a synopsis answer to thisquestionabout 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.Carterarticle, where I would find the following corrections to Fester'squestionable chemistry deviations:

1) Anhydrous HBr gas is dissolved in glacial acetic acid, notHydrobromic Acid, and definitely not the azeotropic acid.


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2) 100g of allylbenzene was used in Carter's, 100g of safrole isspecified by Fester, but allylbenzene has a mol. weight of 118, whilesafrole is 162. That means that Carter was brominating .85 moles, while

Fester is attempting to brominate 0.62. Fester didn't even botherconverting molar quantities!

Etc... Otherwise, the process seems facile.

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

Subject: Re: MDA from MDP2PFrom: [email protected] (Eleusis)

Date: 1995/11/01

Bromination of Safrole at the secondary carbon of the double bondproceedsat less than 5% yield if 48% HBr is substituted for 66% underpressure, atwhich 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 ofbromosafrole.

Same source paragraph f - 4.7g bromosafrole + MeNH2 in alcoholheated 3hours at 130C, clean-up and treatment with HCl yields 1.4g MDMA and1.9g

unchanged bromosafrole recovered.

Journal of the Chemistry Society, part 2 1938, page 2008, 4thcompleteparagraph titled Addition of Hydrogen Bromide to Safrole (K.H.Lin &R.Robinson) - Safrole in solution of perbenzoic acid in benzene wassaturated with hydrogen bromide. On each of next 7 days 1ml ofperbenzoicacid solution added. [CH: to keep it in solution?] The mixtureshaken andkept for 17 days. Water washed, treated with sodium carbonate,washed

again, dried, and distilled giving unspecified yield of colourless


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mobileliquid identified as safrole hydrobromide.

Journal of the American Chemical Society, Vol 68, page 1806, Sept.1946,

3rd complete paragraph (B.Riegel & H.Wittcoff) - Hydrogen Bromidegasbubbled into solution of glacial acetic acid and allylbenzene led toformation of 2 layers which were dispelled by adding more acid. Rxnkeptcold overnight, poured into icewater yielding heavy bromide taken upinEtOH, aqueous layer extracted and extracts pooled. Washed withdilutebicarb then with water then dried over sodium sulfate then distilledtoyield 71% colorless B-Bromopropylbenzene.

Journal of Biological Chemistry, Vol 108, page 623, 1934/5?, firstcompleteparagraph (H.E.Carter) - 200g glacial acetic acid containing 150ghydrogenbromide in bottle in ice bath. 100g allylbenzene added, stoppered,andallowed to come to room temp slowly with occasional shaking. Twolayersmerged into clear red solution after 10 to 12 hours. After 24hourscontentspoured onto crushed ice, bromide separated, water extracted with pet

ether.Extracts pooled, washed with water and sodium carbonate, dried oversodiumsulfate. Distilled bromide was 90-95% pure and total yield was 92%oftheoretical.

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

From: The Journal of the Chemistry Society, part 2 1938 page 2005.

379. Experiments on the Synthesis of Substances related to theSterols. 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 manyexperimentsmade is here described. A mixture of freshly distilled safrole (8.1g.), a

solution of perbenzoic acid in benzene (2 cc of 0.3N), and benzene


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(100 cc)was saturated with hydrogen bromide (2 hours). On each of the next7 daysperbenzoic acid solution (1 cc) was added, and the mixture shakenand kept

for 17 days. The mixture was then washed with water, dilute aqueoussodiumcarbonate, and again water and the benzene layer was separated,dried, anddistilled. The fraction (6.5 g), b.p. 145.5-153C at 9.5mm, was acolourless,mobile liquid and was identified as the known safrole hydrobromide;Robinsonand 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 ofanhydrous ferric cloride. The same beta-bromdihydrosafrole wasobtained inboth cases.

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

This procedure calls for reactions under high pressure, this ispotentiallyvery dangerous. See ANALOG, Vol 9, No. 3, Nov 1987, pp. 1-10, byR.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 andDL-1-(3,4-dimethoxyphenyl)-2-(methylamino)propane. StanislawBiniecki andEdmund Krajewski.

Safrole (5.3 g.) added dropwise at 0C to 21 g. 70% HBr, the mixt.

left14hrs. at 0C, poured on ice, extd. with Et20, and the ext. distd. invacuoyielded 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, thesolventand excess amine distd., the residue acidified with HCl to Congo

red, extd.


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with 30 ml. Et2O to remove unchanged (I), the aq. layer treated with10 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) wasrecovered;hydrochloride m. 148-149C.

[Similarly, 7.2g. (II) and 22.5 g. MeNH2 after 10 hrs. at 140C andsimilar working up (NaOH used instead of K2CO3 and CHCl3 substitued forEt2O in the last extn.) gave 2.35 g. 3,4-(MeO)2C6H3CH2CHMeNHMe, n D-221.5265; prepn. of the hydrocloride, m. 114-119C, was not successful unlessthe base was purified via the perchlorate, m. 180-181C.]

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

=========

From: The Journal of the American Chemical Society, volume 68, page1805

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 preparedpreviously by Carter by the addition of aqueous hydrobromic acid to

allylbenzene, it was decided to employ an alternative procedure.Theinduction of a rapid stream of hydrogen bromide into a solution of10g.of allylbenzene in 25 ml. of glacial acetic acid over a period oftwohours led to the formation of two layers which were subsequentlydispelled by the addition of 20 ml. more of solvent. The reactionmixture, having been subjected to low temperatures overnight, waspouredinto ice water to yield a heavy bromide which was taken up in etherand

combined with the solution which resulted from the ether and benzeneextraction of the aqueous layer. The solution, having been washedwithdilute bicarbonate and with water, was dried over sodium sulfate.Thereupon, the solvent was evaporated to obtain a reddish oil whichonfractionation yielded 12g.(71%) of a colorless liquid whichdistilled at77-80C at 1mm.

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


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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 trioctylmethylammoniumchloride(Aliquat 336), and the two-phase mixture was heated at 115!C (bathtemp)with magnetic stirring for two hours. The solution was extractedwith1x20ml and 2x10ml CH2Cl2, and the pooled extracts was freed fromsolventby evaporation. The dark residue was distilled under aspiratorvacuumwhich gave two fractions:

113-135!C - 10.1 grams - Clear, safrole + chlorosafrole135-165!C - 4.8 grams - Cloudy, chlorosafrole + something.

Chlorosafrole II

16.2 grams (0.1 mole) of safrole was added to a mixture of 150 ml37% HCl(1.5 mole) and 4.0 grams (0.01 mole) of trioctylmethylammoniumchloride(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 mlDCM. Thepooled organic extracts was washed with a little dilute Na2CO3,dried overMgSO4, and the solvent removed by evaporation. The black residue wasvacuum distilled at 3 mmHg to yield 10.2 grams of clear 2-chlorosafroleat 130-150!C. There was also quite a lot of deep red residue in thedistillation flask, probably consisting of the PTC and variouspolymerization products.

Using the first procedure, but with 0.5 moles 48% HBr only producedtar.

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

US Pat 3,864,115

Preparation of Bromosafrole

65 grams of safrole was dissolved in 100 ml of glacial acetic acid.

At 20!C,


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there was added, with stirring, a solution of 100g HBr in glacialaceticacid. Stirring was continued for a further 12 hours at roomtemperature andthe acetic acid was distilled off under vacuum. The residue was

taken up in200 ml of benzene and washing was effected several times with, ineach case100 ml of water. The benzene solution was dried over sodium sulfate.Whenfractionation was effected, 43 grams of bromosafrole of the bp 90!Cat0.05 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-PhaseSystems in the Presence of Catalytic Amounts of Onium Salts."

The PTC used in this reaction can be replaced withtetraoctylammonium bromide or

the much cheaper are more easily obtained trioctylmethylammoniumchloride(Aliquat 336). Other PTCs such as tetrabutylammonium bromide andtriethylbenzyl-ammonium chloride serve as very poor PTC catalysts due to theirappreciablesolubility in water.

Also, any hydrohalogenic acid solution (HCl, HBr, HI) can be used.Don't knowabout HF though. A mixture of 16.8g of 1-dodecene (0.1 mol) (Note1), 55.5mL

of 48% hydrobromic acid (0.5 mol), and 5.1g ofhexadecyltributylphosphoniumbromide (0.01) is heated at 115degC (bath temperature) with magneticstirringfor 2hr (Note 2). The organic layer is separated (Note 3), theaqueous phasewas extracted with dichloromethane (Note 4), and the solvent isevaporated.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


33/46

furtherpurification (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 sealedround-bottomedflask surrounded by an oil bath with the temperature monitored by athermometorimmersed in the two-phase mixture held in place by a stopper. Afterabout thirtyminutes, pressure within the vessel increased and the stopper wasblown off thetop of the flask. Thermometor was recovered unbroken. The set-up wasquicklymodified through the addition of a reflux condensor with thethermometer

relocated to the oil bath to monitor reaction temperature. Noproblems wereexperienced again and the process continued smoothly. The reactionmixture wasthen stirred for 4 hrs at the required temperature. Although therehad been somegas evolution before, no reflux of the standard kind was observed.The 4 hourreaction was unintended (I lost track of the time). As the reactionprogressed,the substrate darkened in color and became considerably morevoluminous. A quick

sniff from the top of the reflux condensor indicated a verysignificant changein odor. Smell was consistent with other published reports. At thecompletion ofthe reaction, the stirring was stopped, and the flask was removed tocool down.

Note 3: Separation was not too difficult.

Note 4: Solvent was added (toluene) as was dH2O and the phasesseparatedcleanly. The solvent layer was then washed with saturated solution

of sodiumcarbonate. The evolved carbon dioxide made separation somewhatdifficult makingbasification with NaOH probably more desirable. Approximately onehour wasneeded for the separation of phases. The solvent layer was bluish-black. Thewater layer was slightly cloudy. Separation of the organic layer wascommencedfollowed by two dH2O washes. Solvent was evaporated to yield amarkedly viscousblack oil that seemed to have a tarry appearance. Smell was pleasant

and NOTHING


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like the starting alkene. Assumed the reaction to be successful asthere was aquantitative change with no apparant cleavage of the ether ring. Hadthere beenany ring cleavage, the sodium catecholate would have formed during

the basicwashes and been carried away in the subsequent water washes. Butthen again,sodium carbonate and bicarbonate solutions when mixed with phenolinhibite theformation of sodium phenolate. This suggests that the sodiumcatecholateformation may have been retarded due to the sodium carbonate insolution. In anycase, however, the presence of such a large amount of end-productsubstantiantesthe assumption that the reaction did indeed effect some kind of

change in the1-alkene structure.

Note 5: Distillation was attemted but due to an undetected leak inthe vacuumsystem, the process ended in failure. Heat was applied in ever-increasingamounts with the assumption that the 2-bromoalkane must necessarilyhave a veryhigh bp. When the attempt was finally abandoned, it was too late.There wasnothing left in the distilling flask except carbonized material and

tar. OnlyDCM was able to remove it after letting it soak for a day. About 1/4ml of oildistilled over into the receiving flask. It was deep red, and had apleasantsmell to it and was assumed to be the 2-bromoalkane. Being uselessin such anamount, 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 was30 min. This modification was made due to the information found inthe articleregarding the more facile and quick brominations of styrenes whencompared totypical aliphatic alkenes. End product was less viscous and not asdark. Not asvoluminous either. Significant odor of starting alkene was detected.Made theassumption that in order to be successful, reaction time must be inthe order oftwo to four hours.


35/46

An attempt at substitution of the bromide atom for that of an azidewas made.Two phase aqueous azide solution and 2-bromoalkene were reactedtogether in amanner identical to that of a published proceedure (I'll get the

article for youguys soon). Even when using a very powerful stirrer, mixing of thetwo phaseswas virtually impossible due to the viscosity of the unpurifiedundistilled2-bromoalkane.

At the end of the reaction, an attempt was made to try reducing theazideproduct (it was assumed that there probably was no 2-azidoalkaneformed due tothe crappy lab technique applied to the previous step, but oh, well,

what thehell.) Proper proportions of the suspected 2-azidoalkane MeOH and Cametal werereacted the manner detailed in TSI and II. There was the fear thatthe PTC(hexadecyltributylphosphonium bromide) still dissolved in thesuspected2-azidoalkane would somehow undesirably react with the Ca metal,thus redardingthe scheme of the reaction. Fears were abated as just a littlebubblingoccurred. In fact, practically nothing happened. The reaction was

assumed to bea failure. Money was scarce, as was the need to have a workingmethod. The1-alkene to 2-bromoalkane to 2-azidoalkane to the final 2-amineroute wasabandoned as there was no detailed established proceedure to followprintedanywhere in the literature. The process was immediately substitutedwith the1-alkene to 2-ketone to 2-amine strategy. Have had no regretswhatsoever.

An attemt was once made to synthesize the 2-amine via the 2-bromoalkane a longtime ago using the proceedure published in Journal ofChromatographic ScienceVol. 29, April 1991 pp.168-173 and Vol. 29, June 1991, pp.267-271.Although the2-bromoalkane seemed to be (just seemed to be, mind you) produced inabout 50%yield, the amine did not form. The process was deemed to suck big-time, and ofcourse, was abandoned.

Here are some promising references describing newer and better ways


36/46

toeffect 2-bromoalkane formation from 1-alkenes using hydrohalogensthemselves or in their place, hydrohalogen precursors, reacted oversilicaor 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 comesover as the125:128.5 fraction.

2) HBr in GAA:440g of 48%Hbr is placed in a flask and setup for gassing. Over (notin) the endof the gas bubbling tube is placed a single section of glass wool(nod toPiglet) which is held in place by tethlon tape. Add a pile of NaCl

just so inpeaks on the surface. H2SO4 is slowly dripped in over many hours andthe gaseousHBr channeled into 253g of slightly chilled GAA. The solution is anice orangecolor. Then GAA is weighed again and %age calculated. 28% (w/w) inthis case.

3) BromoSafrole:352g of 28%GAA is placed in a quart jar sitting in a cold waterbath. 91g ofSafrole (single distilled) are added in 4 portions over ~1 hour.

Note: recycledSafrole from wacker / halogenation are not appropriate as isoS willnot convert.Jar covered and stirred for 2d 19h (way overkill). Color progressionis darkorange to green to deep bright red. The solution is dumped into~450g of crusheddIce/dH2O in a sep funnel. Heavy BromoS goes to bottom and isseperated. Theremainder is extracted with 86mls of pet ether and added to theBromoS. Thesolution should (but wasn't) be washed with a couple portions of

dilute NaBiCarb


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solution and best sit overnight with the BiCarb where substantlecrap goes intothe BiCarb water (thank gyro). The pet ether is distilled off. Theremainder isdistilled under vac (~~~28", big 3.9amp fridge pump). 11g of

(iso)Safrole arecollected from the 130:177 fraction. 64g of BromoSafrole arecollected from thetight 178:181 fraction. Safrole normally comes over at ~140 withsame pump.Suddenly black polymerized crap comes shooting through the condenserplugging upthe entire apparatus which is exactly why crude solution must bewashed withNaBiCarb.

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

=========Chem Guy:

From "Analysis of 1-(3-methoxy-4,5-methylenedioxyphenyl)-2-propanamine (MMDA) DerivativesSynthesized from Nutmeg Oil and 3-methoxy-4,5-Methylenedioxybenzaldhyde"

It is inThe 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 roomtempature for 7 days. The reaction was then quenched with theadditionof crushed ice and extracted with ether. The ether extracts werecombined, washed with water, and evaporated to dryness under reducedpresure , and the resultant product oil was analyzed directly by GC-MS.

AMINATION REACTIONS

The crude bromination product was disolved in methanol containingmethylamine and stirred for several days. The reaction mixture wasevaporated 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 solutionwasextracted with ether, then the combined ether extracts wereevaporated

to dryness under reduced pressure. The resulting oil was analyzed


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directly. "

In another arctile concerning this same topic except the oil wassafrole. (Journal of Chromatographic Science, Vol. 29, april 1991,page

169) It says

"... analysis showed the bromination occured slowly and requiredapproximately 7 days to consume most of the Safrole.... The resultsofthe present study clearly shows that MDMA and related designer drugsanalogues of MDA can be prepared by amine displacement ofbromosafroleobtained via bromination of the organic steam distillate of therootsof the sassafrs plant."

That same article gives the same reaction method:

"Bromination Reactions. Samples of sassafras oil or alkenes (5.0 gofsafrole, isosafrole, eugenol, isoeugenol, etc.) in 48% HBr (25 mL)werestirred at room tempature for 7 days. The reactions were thenquenchedwith the addition of crushed ice (25 mL) and extracted with ether(2 x 50 mL). The ether extracts were evaporated to dryness underreduced 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 reactionmixture was evaporated to dryness and the resultant oil dissolvedin 10% HCl (50 mL). The aqueous acidic solution was waqshed withether (2 x 50 mL) and then made basic (pH 12) by the addition ofNaOHpellets. The aqueous base solution was extracted with ether(2 x 50 mL) and the comgined ether extracts evaporated to drynessunderreduced 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 bothsay 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, andone refernece says "... especially HI" (as we already knew) and itshows the equation:

"ArOR + HI, concentrated, heat --> ArOH + RI"

Now my question is, how concentrated do HBr and HCl have to be and


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howmuch heat is required for this? It seems that room tempature may notbe 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 haveall this trouble?

Next,...

Found this in Journal of Organic Chemistry, 1980, Vol 45, 3527-3530."Addition of hydrohalogenic acids to alkenes in aqueuos-Organic, twophase systems in the presence of catalyitic amounts of onium saltsIn previous works we reported that lipophillic quarternary ammoniumand phosphonium salts show a high catalyitic activity in reactionspromoted by hydrohalogenic acids in aqueuos-Organic two phasesystemssuch as the conversion of alcohols to the corresponding halides andthe cleavage of ethers. Recently quartenary ammonium salts were

shownto extract hydrohalogenic acids from their aqueuos solutions intolowpolarity organic solvents."

The article goes on to state the effecivness of the PTC's for this.Butit also states that this can cleave ether groups as well. Thereference given to this is "Synthesis, 1978, page 771". I haven'thadtime 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 inthepresence of Phase]Transfer catalysts"Standard methods to hydrolyse ethers require particularly drasticconditions, e.g. the use of concentrated hydroiodic acid, or a largeexcess of concentrated hydrobromic acid in acetic acid or aceticanhydride at reflux or of pryridine hydrochloride at 200-220 C.""Reactions were carried out by heating at 115 C under vigorous

stirringa hetrogenous mixture of substrate (1 mol), 47% HBr (5-10 mol) andhexadecyltributylphosphonium bromide (.1 mol)""Indeed in phase-transfer conditions even aqueous HCl quantitativelyconverts alcohols into the corresponding chlorides.""Attempts to use concentrated HCl or HCl and NaBr failed [to cleavethe ethers]"

The basic reaction:

ArOR + HBr --> ArOH + RBr

I hope this sheds some more light onto this subject.


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1) NO HEAT!2)Cold is good3)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, page267-271

"Thus the conjugated bond in isosafrole does not add HBr under thesameconditions as safrole. Therefore, any isosafrole generated in viaHBrelimination would not under go readdition and should accumulate inthe reaction mixture."

The conditions were:

Bromination with 48% HBr (aqueuos). Stirred for 7 days @ roomtempature. 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 productdissolvedin methanol containing 40% aqueuos methylamine, 20 mL. It wasstirred

at room tempature for 4 days.

For the amination the crude bromo compound was dissolved in 100 mLofmethanol and 20 mL of aqueous methylamine.

"In summary, these experimants show that HBr treatment of thevarioussubstitued allylbenzenes found in sassafras oil yeild predomintlythe2-bromopropane intermedites. Methylamine displacement reactions withthese bromo intermedites yeilds the N-methyl-1-aryl-2-propaneamines

asthe major components."

-------------------------------------------------------------------------------Drone 342:

An idea of mine:

To 235 ml of 10% methylamine in MeNH2 is added 0.89 gbenzyltriethylammoniumchloride and 18.6 g of crushed NaOH. The mixture is stirred

magnetically at rt


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for 1 h. 24.5 g bromosafrole is added, and is allowed to reactovernight at roomtemperature with stirring. The next day, the solution is check edvia TLC todetermine completion of the reaction. Once completion is determined,

theinorganic material is filtered out, and the solution is washed withH2O. Thesolution is dried over MgSO4, and stripped in vacuo. The finalproduct issubsequently 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- andiodosafrole.However, I want to share with you all the magic of yet anotherphase-transfercatalylzed reaction: a variation of the Finkelstein reaction.

Yes, a little quaternary ammonium salt, a dash of CaBr2 (I've heardrumors NaBrworks too), and a person can readily convert alkyl chlorides to

bromides withoutbreaking 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 withsilica orAl2O3 as the catalyst. The yields are excellent from what Iremember, and reacttime quick. It seemed to me thatthe addition of water really fucked things up though.

--------------------------------------------------------------------


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------------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 themethylenedioxygroup under HBr-AcOH treatment. However, the methylenedioxy groupwas stable upto 2hr in the presence of dry HBr in non-polar solvents such asCHCl3.

Reaction of o-allylphenols with dry HBr a solution of theappropriate o-allyl-phenol (1mmol) in dry CHCl3 (15ml) at 0c was saturated with HBr.After keepingfor 2hr, the reaction mixture was poured into ice water (50ml), the

CHCl3 layerwashed with water until neutral, dried (Na2SO4) and evaporated tofurnish thecorresponding o-(2'-bromopropyl)phenol in >95% yield as a dark brownliquid.

The treatment of dillapiole with dry HBr gave a mixture of (I) and2-bromodill-apiole in CHCl3, it exclusively led to 2-bromodillapiole in DMFmedium.

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 withdry HBr at0!C. After keeping for 2hr, it was poured into ice-cold water(300ml), extractedwith CHCl3, the organic layer washed with H2O until neutral, dried

over anhydrousNa2SO4 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) solutionsin DMF,AcOH, DMSO, etc to make bromosafrole.


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This procedure works perfectly for smaller quantities of the 2-brompropane.The thermal decomposition isn't much fun to deal with in quantitiesgreaterthan 50g.

Synthesis of 1-(3,4 methylenedioxyphenyl)-1,2-dibromopropane

18ml 48%HBr(aq), 10ml dH2O and Isosafrol(4.2g, .0258mol)is dissolvedin 10mlethyl ether with vigorous mag stirring. Rxn is chilled to -10'C(salt/ice bath).N-bromosuccinimide (4.6g, .0258mol) is slowly added portionwise over10min andstirring is continued an additional 5min. Stirring is stopped andphases areseparated. Aqueous layer is re-extracted w/ 10ml additional ether.

Organicphases are combined, washed with 10ml 10% sodium bicarbonate then10ml saturatedNaCl soln and finally evaporated to yield 8g of title product as athickgreenish oil(90-96% yield). Product does not yield a solid crystalwith anyknown crystallization solvent and also decomposes upon heating/distillationtherefor is best characterized as the monobromocompound.

2-Bromosafrole

The above produced dibromo compound is carefully thermallydecomposed in astandard vacuum distillation rig using an oil bath. Since copiousquantitiesof HBr are produced as decomposition product it only make sense touse a wateraspirator as vacuum source. When pot contents reach approximately100!Cdehalogenation takes place and 2-bromosafrole starts to distil over.Dependingon vacuum, rxn. may start at lower temp. Do not allow pot contents

to excede130!C or glassware will rapidly fill with charcoal from uncontrolleddecomposition! Yield of water white 2-bromosafrole was found to bein the 80-90% range.

Another thing, I'm not much of a Uncle Fester fan however I mustgive him creditfor his bromosafrole rxn which uses HCl to dehydrate 48% HBr. Itreally doeswork exactly as he describes it! Yields are high with very littleunreactedsafrole to separate from product and it can be scaled to any size

imaginable.


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--------------------------------------------------------------------------------Easy Bromosafrole Synthesis by Berserker

This is a revolutionary new method to halogenate ketenes withMarkinokov selectivity,by reacting them with a phosphorus trihalogenide in the presence ofsilicon dioxidecatalyst. To make others, just substitute safrole with 10 mols ofanother alkene.

A suspension is made by stirring 5g of SiO2 (silicon dioxide) into asolution of10 mol safrole in 25ml dichloromethane. To this, add a solution of 4mol 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 (stillin suspension)is filtered out and then washed with 15ml DCM. The combined liquidis washed witha 10% sodium bicarbonate solution, until no more gas is liberated,then twice withbrine, and the organic extract is dried with sodium sulfate. Thesolvent is thenallowed 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 glassinto a finepowder, and washing it with acid. Both silicon dioxide andphosphorus tribromideare unsuspicious chemicals, and can be ordered with ease from well-stocked chemicalsuppliers.

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 ofperbenzoic acid inbenzene (2cc of 0.3N), and benzene (100ml) was saturated withhydrogen bromide(2 hours). On each of the next 7 days perbenzoic acid solution (1ml)

was added,


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and the mixture shaken and kept for 17 days. The mixture was thenwashed with water,dilute aqueous sodium carbonate, and again water and the benzenelayer 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 andZaki (J, 1937, 2489) give bp 160!C/16mmHg.

The same beta-bromodihydrosafrole was obtained in both cases. Theproduct wasidentical with the hydrobromide made under ordinary conditions andit did not reactwith potassium phthalimide, which is an indication of sec-bromidestructure.

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1-(3,5-dimethoxy-4-hydroxyphenyl)-2-bromopropane

a mixture of 4-allyl-2,6-dimethoxyphenol (2.5g, 13mmol), HBr (40%,inglacial acetic acid, 15 ml) was shaken and placed in a darkroom foraweek. Then the bulk of the acetic acid was removed under reducedpressureand the remaining acetic acid was removed by co-distillation with

ethanol.The residue was cooled in a ice-bath and slowly mixed with anhydrousK2CO3(1-2g), and the resultant mixture was purified by columnchromatography to obtain1-(3,5-Dimethoxy-4-hydroxyphenyl)-2-bromopropane as a colourless oil(3g, 84%)

Reference: J Chem Research (s) 1999 (2): 158-159

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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 daysat 0!, neutralized with NaHCO3, extd. with Et2O, and distd. to give73.3%1-(3,4-methylenedioxyphenyl)-2-bromopropane (I), b15 162-5!. nD161.5628.

Methyleugenol (II) brominated analogously gave 36.5%

1-(3,4-dimethoxyphenyl)-2-bromopropane (III), b10 171-2!nD18


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1.5614.

I (7.3 g.), 36 g. 10% alc. NH3, and 0.8 g. Cu2O heated 7 hrs. at160!, alkalised to pH 9with 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. at0!, hydrolyzed, extd.with Et2O, and the ext. distd. yielded 80.9% III. III (10 g.)treated similarly with NH3gave 3.4 g. 1-(3,4-dimethoxyphenyl)-2-aminopropane sulfate andrecovered 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 theresidue extd. withEt2O 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 onpumice yielded

30.8% 3,4-dimethoxyphenylacetone.

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secrets of manufacturer safrole

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