Author Topic: bromosafrole (Read 15324 times)

serodronin · « **on:** November 16, 2000, 08:00:00 AM »

AFOAF was intending to make some Bromosafrole, but she believes that an aquatic solution of HBr will not produce good yields. what other solvent can she use to hold HBr in approx. `+ soln?

Osmium · « **Reply #1 on:** November 16, 2000, 10:58:00 AM »

Post 22772

(Osmium: "Bromosafrole breakthrough?", Serious Chemistry)

startinout · « **Reply #2 on:** November 16, 2000, 04:14:00 PM »

Osmium is correct, it works as such, but in reply to your concern regarding yields one needs to weigh up benefits, even a 10% yield would be favourable when weighed against the benefits of purchasing and/or cost of materials.

'Isn't society irrational'

blue always
except for at the start

serodronin · « **Reply #3 on:** November 16, 2000, 10:09:00 PM »

10% yields would work for the amount of feed material ,my friend has, but she has read journals from chem. abstracts, JOC, JBC, JACS, JCs, etc. that all say 95-100% yields are possible if water is not contained in the reaction. She likes the sound of this a lot more. I think she will go with safrole dissolved in chloroform and then gas it with anhydrous HBr.

psychokitty · « **Reply #4 on:** November 17, 2000, 05:51:00 AM »

Kitty has never done it, but Ritter claims SWIM has performed the hydrobromination of safrole using Fester's method: 1 part acetic acid to 1 part safrole are mixed with an amount of 48% HBr (don't remember exactly how much but I do have Fester's book to refer to if need be). This is cooled in an ice bath to about 10 deg C and cooling maintained while anhydrous HCl is gassed into the stirred mixture over a period of one hour. The container is stoppered and allowed to stir for about 2 days or so. Then, the whole sheebag is dumped into ice cold dH2O, and the rest of the work-up is standard. BTW, the HCl dehydrates the HBr, liberating it to react with the safrole to form the desired bromosafrole. Yields are about 75% at a starting scale of about 100 g of safrole.

Although no one here really trusts most Fester methods, Ritter swears that this one is gold. Good ventillation would be the only obstacle that I can think of as this method seems incredibly easy. If you want the actual details, they MIGHT be on Rhodium's page. If not, I can get the information for you.

Good luck.

--PK

serodronin · « **Reply #5 on:** November 17, 2000, 06:40:00 AM »

I think UF is confused about a lot of org. chem. I read the articles that his information came from, and it claims that acidifying in AcOH with aqueous hydrohalogens causes polymerization.

homunculus · « **Reply #6 on:** November 20, 2000, 11:45:00 AM »

48% WILL work, HCl gassing does improve yields, but the tricky part is aminating.

Stonium · « **Reply #7 on:** November 20, 2000, 11:50:00 AM »

Osmium is correct

As usual.

Biased...who, ME?

I think UF is confused about a lot of org. chem.

Think YOU might bee RIGHT about THAT.

Stonium

On time is when I get there

improv_chem · « **Reply #8 on:** November 20, 2000, 10:51:00 PM »

Where was your friend gonna get the gaseous HBr?
Any good ways to make HBr(g) from NaBr?

If it doesn't work, smash it and start over

psychokitty · « **Reply #9 on:** November 21, 2000, 05:18:00 AM »

I've heard that reacting the distilled bromosafrole with aqueous sodium azide in a biphasic mixture using PTC is a good way to get the intermediate azidosafrole, which then is reacted directly (after separation of the previous two phases) with an aqueous solution of sodium borohydride. Separatation of phases followed by standard work-up yields VERY PURE MDA in about 50% yield as the free base.

No, kitty has not performed this reaction. But some other bee has guaranteed kitty that SWIM has.

--PK

serodronin · « **Reply #10 on:** November 21, 2000, 09:19:00 AM »

NaBR or KBr in sulfuric acid will produce HBr gas. if your sulfuric acid is anhydrous, your HBr will be anhydrous also.

Osmium · « **Reply #11 on:** November 21, 2000, 11:29:00 AM »

Sulfuric acid is an oxidiser and will probably oxidise some of the bromide to Br2.
What about phosphoric acid?

psychokitty · « **Reply #12 on:** November 22, 2000, 03:22:00 AM »

I have an old chemistry book that says that both NaBr and NaI can be dehydrated into the respective anhydrous hydrohalogenic acids but that the reaction is too slow for practical use.

--PK

PolytheneSam · « **Reply #13 on:** November 22, 2000, 05:07:00 AM »

What about this link on Rhodium's page?

http://rhodium.lycaeum.org/chemistry/halosafrole.txt

serodronin · « **Reply #14 on:** November 22, 2000, 10:54:00 AM »

UF mentions making halosafrole from isosafrole instead of safrole. wouldn't using isosafrole as precursor attach the halogen at the first carbon from the ring instead of the second(where you want it)?

Osmium · « **Reply #15 on:** November 23, 2000, 12:10:00 AM »

I think it depends on the reaction mode, either you do it by forming radical intermediates or ionic. Could be wrong though.

improv_chem · « **Reply #16 on:** November 23, 2000, 02:21:00 AM »

Ok, there is obviously a number of bromosaf compounds that could be made. What about that DMSO Method that SWIM tried? I think that is what PolytheneSam is asking about... It certainly DID NOT form the desired amine when swaped with Iodine and reacted in the delephine rxn!! (Could have been the delephine's fault though) Someone said it was a DiBromo compound? Has anyone tried reacting the product of the DMSO rxn with NH3 or MeAm in a bomb?? If it is the real thing then you should get some product, right? I think we need some kind of table of possible reactions of Safrole and isosafrole with HBr in various solvents so Bees can figure out what they are going to get from a rxn.
Are you sure about the HBr not being oxidized to Br2? SWIM thought he saw some bromine when he dripped in the Sulfuric.
SWIM is going to investigate making HBr using various methods as soon as he is a little less busy with other matters....
SWIM will post anything interesting if nobody else does by then.

If it doesn't work, smash it and start over

PolytheneSam · « **Reply #17 on:** November 23, 2000, 03:37:00 AM »

Here's two patents on the subject: 2456316 and 3864115 (see example 1 on 2nd page).

The_Animal · « **Reply #18 on:** November 23, 2000, 01:55:00 PM »

Can DMSO be substituted for anything else?

Insert signature of your choice here

improv_chem · « **Reply #19 on:** November 23, 2000, 03:26:00 PM »

PolytheneSam: put those patent #'s into Rodium's search engine--> Gonna check it out tonight when i print it.

Animal: Do you mean what can you use instead of DMSO in the Bromo procedure or do you mean what else can you use DMSO for?

Just a thought: The only problem i can see with the DMSO procedure is that there might be a side rxn because of the NaHSO4 present.
The product that SWIM got smelt nice and looked good after washes even though SWIM used washed saf oil and not distilled stuff. SWIM found that the oil looses about 20% of its weight after washing, does that mean that it's fairly pure safrole? The oil is supposed to be about 80% safrole right?
The Bromo product smelt kinda sweet and was a suripy, translucent pink/yellow/orange liquid at room temp.
Who was it that reported a similar failure with the DMSO method.., mabe YelloJacket?? I can't remember, but if anyone made this stuff and tried to aminate with some method other than the delephine i would be very interested to hear your story.
SWIM tried this procedure a long time ago with NaI instead of NaBr, and got shit all.
Made more stink too. SWIM thought he fucked up the delephine, that's why he tried it a second time with NaBr.
SWIM thinks that the DMSO method doesn't work well with the NaI since a lot of I2 seemed to be produced..
Anyone else got any stories on this procedure???
Sweat dreams............

If it doesn't work, smash it and start over

The_Animal · « **Reply #20 on:** November 23, 2000, 06:09:00 PM »

improv_chem - I meant what can be used instead of DMSO. Its just a solvent -right?.And what happened on your 2nd attempt with NaBr??

Insert signature of your choice here

homunculus · « **Reply #21 on:** November 24, 2000, 08:11:00 AM »

DMSO is pretty easy to get, there are lots of places besides chem companies that will sell it. If you don't mind putting up with lower yields and more side reactions, an aqueous solution will work- just not as fast.

improv_chem · « **Reply #22 on:** November 24, 2000, 04:11:00 PM »

DMSO could probably be substituted with acetonitrile, DMF, mabe something else?? These solvents have similar properties i think. I believe DMSO would be the most accessible for most bees. The product from the second run with the NaBr is what i described in the last post. At first it stank like DMSO (bandaid nastinesss) but after a number of washes with dilute NaOH sol. and DW, the product was as described above. The first trial was with NaI a long time ago when SWIM was a lot sloppier than today and SWIM could not conclude too much from that trial because of sloppy technique. The NaI is really about 10 times more messy, nasty to work with than the NaBr. And SWIM thinks that some HI is converted to I2 which SWIM finds to be one of the nastiest chemicals SWIM has ever used in terms of ruining clothes, staining stuff, and stinking the fuck out of the labspace when in the DMSO.
homunculus: Has your friend tried this? I would really like to hear from anyone who tried to aminate this stuff because SWIM found this rxn nice and neat with the NaBr and got a nice looking/smelling product. Very little work involved. SWIM still has no idea if it is a usable product because SWIM has doubts about the delephine working for these molecules after his experiment. People seem hesitant to comment on this DMSO rxn as to actual notes and similar. Some people have just said "it doesn't work" and start bashing the adams family but don't explain exactly why they think it doesn't work or they don't tell about actual trials. If you can make bromosafrole with GAA and HBr, why the fuck can't you make it in DMSO and HBr?

? This DMSO rxn can be done with a small amount of safrole so mabe some bee out there with the chems and a little safrole could try this and mabe cook it in a bomb with some NH3 or MeAm and get the final judgement??
If you don't feel like posting your results just PM me and it might help my dreams be a little nicer.
I hope you can sleep with this constant buzzing......

If it doesn't work, smash it and start over

PolytheneSam · « **Reply #23 on:** November 24, 2000, 05:42:00 PM »

Here's another thread. Biscuit2 mentions something about using NMR. I remember reading something about someone using NMR or something like that when he tried using DMSO and HBr. He said DMSO doesn't work. I'll keep looking for the thread.

Post 61606 (missing)

(improv_chem: "Bromosafrole prep.", Methods Discourse)

PolytheneSam · « **Reply #24 on:** November 24, 2000, 05:48:00 PM »

This looks like it.

Post 9150 (missing)

(Biscuit2: "Halosaf via DMSO not working, NMR data to proove", Methods Discourse)

startinout · « **Reply #25 on:** November 24, 2000, 10:29:00 PM »

dimethyl suphoxide is what is known as a polar aprotic solvent, it and DMF are really the only two solvents that will dissolve many organic compounds as well as anions/cations without leaving the cations/anions with huge solvent spheres around them making them less active. the reason GAA is used is to homogenise the HBr and safrole but as it is an acid and therefore a 'protic' solvent it will protect the anions/cations rendering them less active. DMSO/DMF are in many ways the dream solvents for these types of reactions, the problem with them and the reason they are not used more in chemistry/industry is simply because you can't remove them on a rotary evaporator and this makes them annoying. This in turn means there is less demand for making them therefore less is produced pushing up the economies of scale and making them more expensive.
i would assert, even though i haven't tried it, that if you subsitute the DMSO with any solvent except DMF you will get squat.
Please note that does not mean don't try, but in the course of rational discussion i think most chemists would be forced to agree with this.
The bigger picture is the amination though, has anyone had any pipe bomb success from bromo/iodo safrole to MDMA, using me-amine??, I can't remeber the last time someone actually claimed to get this to work.

blue always
except for at the start

improv_chem · « **Reply #26 on:** November 24, 2000, 10:34:00 PM »

Ok, just read that thread. Hmmm...SWIM thinks that HBr in GAA would have less variables that could cause things to fuck up than a DMSO/NaBr/H2SO4 synth.
Question to anyone who knows:
-->if one had a solution of GAA/HBr/H2O, could some kind of drying agent be added to romove some of the water???
Would this even be necessary??
What drying agent would be suitable? need something not soluable but capable of absorbing the water but not the GAA or HBr.
If some or all of the water could be removed this way, improv thinks that the resulting GAA/HBr solution would definately brominate safrole to the bromocompound we are looking for.
Has anyone used silica gel for drying??
Will this stuff absorb GAA or HBr? H2O is a smaller molecule than both...
If not SWIM might be going to the flower shop....
Other than that improv thinks that if HBr(g) could be obtained, bubble it into some GAA with a fish tank airator and add the saf....THAT would be the way improv would do it if improv played with these sort of thing... But improv doesn't do these kind of things, that's left up to my friend SWIM to play with......
I think that the only concern would be to not get any Br2(g) with the HBr(g) for the bubbling.
hmmm...mabe that old acid distillation aparatus to make some HBr(aq)....
we shall see...
ps: SWIM used Dr. StrangeGlove's(sp?) revised DMSO recipe when he did the rxn with NaBr, that synth uses less NaBr and Sulfuric than pugsley's version........you can find it on the old board..

If it doesn't work, smash it and start over

startinout · « **Reply #27 on:** November 25, 2000, 10:21:00 AM »

to see if the water can be dried off just throw some drying agent into conc HBr and se if any gas evolves, ie as the drying agent adsorbs the water the solubility limit of the Hbr/water mix will be exceeded and gas should form on the drying agent surface. this might also be an easy way to generate HBr gas, do i get the credit if it works even though i can't be fucked trying it. Seems to easy though, i figure vogel or someother book would have quoted this method if it had worked.

blue always
except for at the start

serodronin · « **Reply #28 on:** November 25, 2000, 11:42:00 AM »

improv_chem, try using sassafras oil instead of safrole in your reaction. It should give you the product you're looking for, while the pure safrole will give you something different.

I try to take my reactions on one at a time, but lately several reactions have attacked me at once.

improv_chem · « **Reply #29 on:** November 26, 2000, 12:59:00 AM »

serodronin--> SWIM used washed sassafras with the NaBr/DMSO trial. How do you know it will work with raw oil? Has your friend tried it and got a product after amination??
SWIM used washed stuff because he couldn't distill because of small size of oil. Wouldn't using strait oil give a lot of garbage after the rxn is drowned with water?
THat 20% garbage in the sass gotta go somewhere. SWIM doesn't have a very good vaccume so he is hesitant to try to distill the Brsaf after the rxn. SWIM would like to do the rxn then wash product and put it in a bomb in the good old pressure cooker.
SWIM wasted all his sass oil on trying this before as well as some other bullshit synth that i'm not gonna mention.
Mabe that extra 20% of stuff that SWIM washed out would have saved the rxn by making it follow the right path. Pugsley specified using undistilled....
Fuck, I guess SWIM will have to try this again when he gets some more sass oil.
Thanks for the tip serodronin.......
we shall see, we shall see.....

If it doesn't work, smash it and start over

serodronin · « **Reply #30 on:** November 26, 2000, 09:02:00 AM »

there are two pathways for HBr to react. Via an ionic mechanism generates the desirable compound. Via a free-radical route forms terminal bromo compound. The crude
sassafrass oil contains eugenol, a phenolic compound which inhibits free radical reaction. Thus you will get better product if you don't purify out safrole. Also keep reaction mixture away from air and UV light, both generate free radicals.

this is a clip from an article I found. UV light wouldn't be a problem if the reaction is carried out in pyrex, and air won't be a problem due to the HBr atmosphere.

I try to take my reactions on one at a time, but lately several reactions have attacked me at once.

Osmium · « **Reply #31 on:** November 26, 2000, 08:00:00 PM »

I analysed sassafras oils by GC about a year ago, at least mine didn't contain eugenol.

PolytheneSam · « **Reply #32 on:** November 26, 2000, 08:49:00 PM »

Here's something from the old board.

Post 108044 (missing)

(beeach: "Methylamine in Methanol for the bromosafrole route", Novel Discourse)

serodronin · « **Reply #33 on:** November 26, 2000, 08:54:00 PM »

what did it contain? phenol and camphor?

I try to take my reactions on one at a time, but lately several reactions have attacked me at once.

PolytheneSam · « **Reply #34 on:** November 27, 2000, 01:14:00 AM »

The Ninth edition of the Merck Index says under Oil of Sassafras: Constit. About 80% safrole; small amount of eugenol; pinene, phellandrene, sesquiterpene, d-camphor.

Osmium · « **Reply #35 on:** November 27, 2000, 11:38:00 AM »

Well, my oil contained about 94% safrole and no eugenol, so those unscrupulous Asian bastards must have sold FAKE sassafras oil to me. Bastards

improv_chem · « **Reply #36 on:** November 27, 2000, 03:54:00 PM »

It depends on what type of Sassafras tree and where it was growing. The oil i had was Sassafras albidum which i believe is the type of tree most common in the USA. It seemed to be about 80% safrole because it lost about 20% of its weight after washes. I know that isn't a very accurate way of telling but it's good enough for me.
Oh yeah, improv tried a little experiment last night:
Took some NaBr and dripped some Sulfuric acid on it, Started bubbling and produced a gas that didn't look brown/yellow like bromine vapour should. The NaBr turned kinda brown/yellow but my H2SO4 looks pretty nasty anyways (molassis coloured shit) so i don't know if any bromine was produced but if it was i think it stayed with the NaBr and not much was vapourized. Would it be better to moisten the NaBr with some HBr(aq) to reduce the chance of bromine formation??
Next HBr experiment will involve silica gel......
any thoughts/suggestions??

It's all just a dream, I hope i don't wake up because of that incessent buzzing sound...

Biscuit2 · « **Reply #37 on:** December 06, 2000, 07:23:00 AM »

In reply to the queries above:

what happened was that after 2 days of KBr/DMSO/H2SO4 and sassy the NMR showed that the double bond had been broken but there was not the right number of Hs. (one less than required)

Importantly there was no crucial CH3 group which would imply a 2-bromo compound.
While the NMR was complex, it was inferred based on Osmium's suggestion that Br2 would be formed by the H2SO4, that a 1,2-dibromo compound was formed.

What was interesting about this reaction that an NMR done after only one days reaction time showed an approx 50:50 mixture of the alleged dibromo and sassy; proving 2 days is required.
The methlyenedioxy bridge was also unharmed.

The suggestion that H3PO4 is used instead did NOTHING. What i have been asking for ages is whether heat is required for H3PO4 to make HBr from a salt?? anyone??

Additionally a NaI/H3PO4/DMSO and psuedo mixture also has some interesting applications.

Osmium · « **Reply #38 on:** December 06, 2000, 12:00:00 PM »

> what happened was that after 2 days of KBr/DMSO/H2SO4 and sassy the
> NMR showed that the double bond had been broken but there was not the
> right number of Hs. (one less than required)
>
> Importantly there was no crucial CH3 group which would imply a 2-bromo compound.

Sounds like allyl substitution to me, leading to a product like this:

R-CH=CH-CH2Br, or maybe even some R-CHBr-CH=CH2.

I'm not sure, but I would expect the allyl to show up at another shift than an alkene, especially when conjugated.
Could one of them explain your findings? Are you sure that the stuff you tested is not a mixture of several compounds?

Biscuit2 · « **Reply #39 on:** December 07, 2000, 02:08:00 PM »

Well from what i was told; there were no CH=CH hydrogens at all; that was clear.

No it cannot be said that there was nothing else in there but the integration for the Hs was just too exact.

Excluding the aromatic and methylene hydrogens, the integration was definitely 5 and not 6 or 4 Hs.

Plus the single hydrogen appeared to be split into 5 tiny peaks; hence 4 adjacent hydrogens.
The benzylic hydrogens were unmistakenly present also and unaltered expect a slight shift; 1,2-dibromo is the only thing i was told that it could be.

But whatever the case there was definitely NO CH3 group.

Basically all the signals were as expected EXCEPT the terminal methyl group; which if was a -CH2-Br group the Hs would be diastereotopic and complex right?

PolytheneSam · « **Reply #40 on:** December 17, 2000, 10:28:00 AM »

I got curious about the stability of HBr and methods of making it. I found these patents that look interesting:

1,267,638 discusses NaBr + NaHSO4 --> Na2SO4 + HBr

1,193,552 NaNO3 + H2SO4 --> NaHSO4 + HNO3
NaCl + NaHSO4 --> HCl +Na2SO4

1,379,731 NaBr + H2SO4 (78%) --> hydrobromic acid

2,705,670 HBr gas from NaBr and dilute H2SO4

3,445,188 HBr produced in organic solvent using NaBr and H2SO4. One example even uses acetic acid as a solvent.

Compare the last one to US patent 3,864,115 which gives an example (example 1) for making the bromosafrole derivative from safrole and HBr in acetic acid.

smiley_boy · « **Reply #41 on:** December 20, 2000, 09:23:00 PM »

I just wanted to nip this urban legend in the bud before anybody gets dissapointed: NaBr and H₂SO₄ do not yield any great amount of bromide gas. Yes, hydrobromic acid is prepared this way, but hydrobromic acid is a solution of hydrogen bromide gas in water - there is a difference here worth noting.

Incidentally, in case you're wondering, the original procedure for preparing hydrobromic acid can be found in Inor. Syn. 1, 155 (1939).

PolytheneSam · « **Reply #42 on:** December 22, 2000, 04:21:00 AM »

I borrowed this from Rhodium's chemistry page.

http://www.geocities.com/dritte123/PSPF.html

PolytheneSam · « **Reply #43 on:** January 14, 2001, 03:03:00 AM »

I don't know about the last reactions, iudexk, but anyway, I found some more interesting patents, available on the internet remember.

2307552 discusses Markonikoff mechanism in addition of HX to alkenes, and gasses containing O2 such as air which can form peroxides and the use of antioxidants to promote Markonikoff addition.

5866732 use of aqueous HBr and ZnBr in addition of HBr to alkenes

2058465 antioxidants

3683037 air activation

PolytheneSam · « **Reply #44 on:** April 23, 2001, 02:29:00 AM »

This thread has a lot of stuff in it relating to bromosafrole and someone's discussing it again (bubbly bubbly).

http://www.privacy.org/article.php?sid=620&mode=thread&order=0&thold=0

http://www.privacy.org

News:

Author Topic: bromosafrole (Read 15324 times)

serodronin

Osmium

startinout

serodronin

psychokitty

serodronin

homunculus

Stonium

improv_chem

psychokitty

serodronin

Osmium

psychokitty

PolytheneSam

serodronin

Osmium

improv_chem

PolytheneSam

The_Animal

improv_chem

The_Animal

homunculus

improv_chem

PolytheneSam

PolytheneSam

startinout

improv_chem

startinout

serodronin

improv_chem

serodronin

Osmium

PolytheneSam

serodronin

PolytheneSam

Osmium

improv_chem

Biscuit2

Osmium

Biscuit2

PolytheneSam

smiley_boy

PolytheneSam

PolytheneSam

PolytheneSam