posted 06-08-99 09:03 PM         

Now on to the fuckups:

tBOC was using 90% H2SO4 to hydrate the olefin to make his alcohol, and kept ending up with a purple gunk that just sat there when he tried to hydrolyze it. At most 10% of the olefin converted to the alcohol. After a couple failures, tBOC thought it just might have been caused by the fact that his acid was old and impure since it was slightly discolored, but decided to dilute down to 80% and try once more. Even though his now 80% acid had a slight pink tinge to it, when he added it to his olefin cold, he got a quantitative yield. Actually 100% (+/- 1%) conversion to the alcohol. So from the several 90% acid attempts that failed, and the two 80% attempts that got 100% yields, tBOC concludes that 80% H2SO4 is the ideal concentration of the acid. 90% seems to be too harsh too our precious MD-ring.

So, quick review: 90%- bad 80%- good .

Now on to the oxidation. tBOC, once he FINALLY got some alcohol made, weighs out 10g (not bothering to wash or purify in any way) and weighs out 10g of NH4NO3 (a rather large molar excess, about 2 mol NH4NO3/mol alcohol) and combines these two in a RBF in an ice bath. tBOC adds a pinch of Cu(AcO)2 and 30ml glacial acetic acid (aldrich, guaranteed 99+%) and 5mL water straight from the sink. The alcohol is now sitting on top of the acid and not much is happening, so tBOC starts with the gentle heating. After about 10 minutes there is a definite yellow tint to the top layer and acid phase which had initially turned slightly brown is now entirely bluish-green. tBOC decides to let it run for an hour or so and see what happens while he goes off to get laid.

When he comes back 1.5h later, tBOC cuts the power, cools down the mixture and throws it into a sep funnel. After the layers have been sitting for a while (two bong bowls and a cigarette) tBOC separates the two and does TLC analysis on the top layer. THE SHIT COMES OUT AS ONE SPOT ON THE TLC. tBOC weighs it (10g, qualitative... nice!!!) chucks it into the freezer (set to -10C, and it DID NOT FREEZE, btw) and takes the acid layer, which is now the color of dirty pennies, and tries to use it on a second batch of alcohol.

10g of alcohol and 10g NH4NO3 are added to the old acid solution, and the flask is heated again. After 0.5h the whole thing is one dirty black color. FUCK!! tBOC thinks this shit is screwed and tBOC is right. No pretty yellow layer on top and tBOC has to resort to extractions with CCl4 to get out his yellow ketone. Stripping off the solvent tBOC is left with that yellow solid everyone almost had tBOC convinced he made the LAST time he tried this. (Maybe I'll aminate this and feed the result to people I don't really like... nah, that's be bad for karma.)

So, once with the acid in excess, and excess NH4O3: good . Second time: bad . Got it?
Good.

Now on to the fuckups with reductive aminations. tBOC sets up two simultaneous reactions, both with n-BuOH as the solvent using nitromethane reduced as the in-situ amine source. Same scales with both, 0.25mol ketone with 0.40mol nitromethane added to 40gAl/Hg in 650mL n-BuOH, only one is with 5g ketone, the other with 15g. (tBOC forgets the actual weight amounts but knows he calculated and weighed out these same proportions in each batch.)

The 5g batch runs smooth and clean, no problems. Adding 300ml 50%NaOH and washing with water results in a nice clear top layer that spits out 4.6g white crystals when acidified to pH 4 with 30% HCl. The 15g batch, however, instead of having the yellow color of the ketone disappearing as the reaction proceeds, starts to turn red and when the 50%NaOH is added after it cools, turns into a black mess. No amount of washing, A/B extractions, etc, yields any product at all. tBOC thinks for a minute, reads Shulgin's add-the-amine-in-yourself method and notices one little phrase: Keep the reaction below 60C....

Well, goddamn. Maybe the 15g batch got a tad too toasty, thinks tBOC. So tBOC takes another 10g ketone and instead of using straight nBuOH, he mixes it 50/50 with MeOH (with a much lower boiling point, should keep it cool enough, thinks tBOC....)

And he was right. 10g ketone, same proportions of other reagants (with the alcohol called for being 50/50 MeOH/nBuOH), dumped in shitloads 50% NaOH after the reaction was done and it had returned to room temperature, washed with water, titrated to pH 4 with 30%HCl and out drops 8.2g product.

So, tBOC has learned that once he has his safrole pure, he can put in about 3h of work and get out up at least 8.2g (likely more) sweet honey crystals as long as he keeps the following in mind:

At least 1.2 mol NH4NO3/mol alcohol and as much as an equal w/w amount. This oxidation is actually a catalytic dehydrogenation with CuO as the active reagant being generated in situ on demand by the NH4NO3.

Excess of AcOH: about 35mL of around 80% AcOH works great for 10g not-MDP2Pol. Ya just gotta love the generosity of this reaction towards lazy people who hate measuring shit out .

Keep final reaction cool. Use 50/50 mix MeOH/nBuOH and you should be fine. tBOC SHOULD have known this, it's been repeated over and over again on this board. But tBOC has a tendency to make the same stupid mistakes over and over again without learning from them.

So tBOC sits back and waits for the masses to start tearing his horrendous lab-skills and general lack of chemistry knowledge to shreds. And he laughs, 'cuz he's sitting on 12+g honey and can make more anytime he has an afternoon to spare.

In your face, crusaders for the war on drugs. You have LOST!!!

posted 06-09-99 03:55 AM         

Just a few questions:

With the H2SO4. Do you dilute down with water afterwards or do you seperate directly from the 80% H2SO4? Also is the H2SO4 added dropwise or faster?

posted 06-10-99 08:03 PM         

In the top of this thread tBOC says to combine the alcohol and ammonium nitrate in a ice bath, then starts heating(???)...

Also for a 10g size is 0.1g a good sized "pinch"?

Also noted that one doesn't add any 50% NaOH this time, was that the case or does one add it in the sep funnel?

I need to know the weight of ketone(pre-honey) or the chemical formula if anyone can help.

tBOC, do you think that MeOH alone would work in the Al/Hg that you describe? I notice that you xtalize in the alcohol with aquious HCl, not worried about losses in the water content? If MeOH cannot be used alone what about the tert BuOH from the Palladium acetate fiasco?

posted 06-11-99 03:49 AM         

During the oxidation, was 'a vigerous evolution of N2 observed'? or is this a different pathway to the benzoin oxidation? I would like to know the temperature to run this oxidation at, maybe too much heat could be damaging/dangerous.

Methanol is generally held to be the best alcohol when making the not-MA compounds, but I still shout and wave at the Zn/Ni couple for making simple not-A's (such as those from other essential oils). DIY NH3 in methanol is simple! Zn & Ni2+ salts are easy to get as well
Have you done a bisulphite yet?

Respect,
Piglet

posted 06-23-99 06:06 PM         

Now for some questions. Confusion is running rampant here, I think there are a few areas that need some clarification. Now when SWIM did as tBOC's original post said, what resulted was cardamon smelling tapioca type of stuff, oh well no harm done. Next when SWIM did as tBOC's updated proceedure said (i.e. 30ml GAA/5ml water) SWIM got appropreate yeild of presumed ketone, but since basification is not stated in the updated proceedure it was not done. Which resulted in a final product which smelled of acetic(read vinagar) and not of cardamon. Due to complicating factors this NOT-Ketone was not tested to see if it was indeed NOT-Ketone. I think clarification is needed in this area, and I also don't think it appropreate to ask tBOC to write it all out, so how about this, I will offer a hypothetical proceedure outlining what I understand of tBOC's notes and anyone who has NOT-Knowledge of this, please comment, ok? I just don't think it fair to ask this of tBOC as he/she has already done so much concerning this...

Here goes...

- 20g single distilled olefin(I hear licorice smells nice)
- 20ml H2SO4(80%)
- 80ml water

- Chill Olefin and H2SO4 in freezer for a couple of hours, chill water in fidge for the same amount of time.
- Add H2SO4 1 drop/sec to olefin stirring in an ice/salt/water bath.
- Right after addition of acid, pour water into dropping funnel so that it is added at the same rate(no need to adjust stopcock).
- After addition of water add a spatula tip (0.2g) NaCl(salt) to stirring mixture.
- Let stir for a moment or so to mix the salt into the water layer.
- Pour this mixture into a sep funnel, wait till it seperates and keep the top layer.
- This should yeild the alcohol.

- Weigh the alcohol, and add an equal ammount of ground(important!) ammonium nitrate fertilizer, while flask is in an ice bath.
- For every 10g of alcohol add 30ml Glacial acetic acid and 5ml water and a pinch(0.1g???) of Cupric Acetate.
- Heat gently (stirring???) about 1/5 power on a regular hotplate or mantle for 10-20min.
- Cool under running water then in an ice bath for 5-10 mins.
- Vac filter off the soilds, keep the filtrate.
- Seperate filtrate in a sep funnel, keeping top layer.
- Vac Filter over silica sand to yeild not-ketone(???).

That is with out the basification, is the basification nessisary???

posted 06-23-99 06:30 PM         

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EMOTIONSwill always beFREE!

posted 06-26-99 03:56 AM         

Took 20g of Not-Safrole (Distilled) and 20g of 80% Sulfuric (puriss). Put htem both to freezer until they were like -3C. Not-safrole had frozen (strange, .. Merck Index says that the MP of not-safrole is 11C ???) Oh well. Let it thaw while sulfuric resided in cold. When everything was cold liquid again, sulfuric was put into dryice/EtOH/Water-bath. Temp was controlled and was -2C to -3C. Added cold Not-Safrole 1 drop/second. Liquid progressed from clear to yellowish-pink to orangy and from there to deep red --> purple --> Black. No visible sign of any kind of oil. Although he was stirring it all the time. Didn't look too bad. It WAS cold after all, it just coloration. Well, progressed to add water (80ml, 2C) the same way. Knew that adding water was going to increase temp, so he was ready with additional cooling if necessary. When first drops hit the mix, temp didn't rise (Steady -2C) but liquid went to solid immediately, not ice but tar. Continued adding water, but nothing changed. As a result he got approx 20 g of goo and purple dilute acid.

posted 06-26-99 05:07 PM         

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EMOTIONSwill always beFREE!

posted 06-26-99 05:14 PM         

aNy off you daring joung cientits <now ????? LT/

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EMOTIONSwill always beFREE!

posted 06-28-99 01:04 PM         

I don't think jumping to conclusions id going to help. The last thing you want to do is piss off a bee who's help we need.

If you added the olefin (NOT-SAFROLE) to your sulfuric, you did it wrong, add sulfuric to your olefin.

posted 06-29-99 06:19 AM         

Oh, and Semtex, the thread I was speaking of was Piglet's posted 06-02-99 06:24AM

posted 06-29-99 05:37 PM         

Some willing friends with more then normal interest in this procedure will contribute to this too. ( I heard a rumor they had a SHITTLOAD of Saffrole oil 98% laying around somewhere). They will also concentrate on this one.

IF positive, tBOC will get all the Fame he can carry!! I promise you personally!

F_CKIN SH_T D_MMN_TT MF'IN MORONS.........! LT/

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EMOTIONSwill always beFREE!

posted 06-29-99 05:54 PM         

You ever tried to put Water in conc H2SO4?
And NOT the other way round!
Saw or FEEL the EXOTHERMIC reaction?

MORONS

LT/ :abitpissytoseeagoodlookingprocedureendbad

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EMOTIONSwill always beFREE!

posted 06-30-99 09:37 AM         

Adding the acid to the alkene creates a lot of heat, reversing the addition obviates this problem and keeps polymerisation to a minimum. Thus, add your alkene slowly and dropwise to the acid. The color should progress from light/brown to deep red. Diluting the acid can be done in the same way (so add the acid/alkene mix to the water). The color change you'll see here is from deep red to pink and finally a whitish kind of milky mix.