Author Topic: Ludes from phthalimide - The saga continues  (Read 2888 times)

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Methaco_s_mic

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Ludes from phthalimide - The saga continues
« on: May 28, 2000, 07:52:00 PM »
The validity of the following synthesis has been debated here for quite some time now:

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



So Dr. Dream picked up those small glass jars he had in the fridge and begun to play. The crappy product from “Test #2” was soon discarded, that run was fucked up good. The second runner up product from “Test #1” was another story. First a simple recrystallization from a dH2O/EtOH mixture, then recrystallization from the same type off mixture but with decolorizing carbon present (about 300mg). This was messy; Dr. Dream has not been working with carbon in quite some time.

The result from “Test #1” was 6.24g nice glistering flake-like crystals, even though they looked nice the colour was not so nice, like “brown sugar” (not heroin ;). Sloppy carbon usage technique, I believe. More correctly the individual crystals were a bit like needles, but they formed flakes by grouping side-by-side.

The product from “Test #3” was worked up in similar manner, but the first recrystallization was omitted. The result was 6.83g of product that looked exactly as the one described above. No doubt it was the same thing.

In both cases the product was allowed to dry for 24 hours on a glass dish in room temperature, prior to weighting and further procedures. 

In retrospect, knowing more than the reader does so far, I think the best thing is to; perform the Step-by-step in my “last paper”, when the non reacted phthalimide precipitates add some (2-300mg) decolorizing carbon and see what happens. Then filter and proceed, use the product for The Next Step without yield lowering post synthesis purification.

The Next Step:

The first 6.24gs was placed in a 100ml RB flask. 5.0ml Acetic Anhydride was added, 4.7ml would have been 1:1, but it was an old bottle, the air is not dry this season and so on. Just after the entire dry material had turned damp, things went really hot, there was a reaction going on for sure! I “stirred” with a glass rod; no external heat was applied, after half an hour of doing this, things had cooled down. The slightly gray product looked dry but the smell of Acetic Acid was strong. Left it in room temperature for 24 hours, after this most of the Acetic Acid smell was gone.

In a similar manner the 6.83gs with origin from “Test #3” was put into another 100ml RB flask ~5.5ml Acetic Anhydride was added; again this was more than enough. Things went hot, and this time external heat was applied. Everything was wetter in this run, compared to the previous one. The lightly grayish product was left overnight, but was not dry (free from Acetic Acid) when The Last Step was performed.

If the modification I proposed above is used, I assume this product will not be very pure. To make The Last Step more foolproof, recrystallization from dH20/EtOH (50/50 as invented by Cheapskate) could probably be worth the extra time and work. Anyhow, I did not purify my suspected N-acetyl-anthranilic acid after this step.

The Last Step:

To the first of the two RB flasks above was added 6.0ml o-Toluidine. As soon as this was done the RB flask was emerged in an oil bath preheated to 190°C. The reaction begun after just a few minutes, after only an hour (with the temperature held between 189-193°C) the reaction died. Another 1.0ml o-Toluidine was added and the mixture held at about 190°C for another 30 minutes. Now the mixture was poured into a 250ml beaker with 100ml 0.2% NaOH (200mg NaOH added) solution. After some hours in the fridge “the mess” was almost solid and the water was poured off. 50ml Acetone was added, and it was slightly heated to make “the mess” dissolve. 2.0ml 37% HCl was added. After a night in the fridge, no crystals, added another 1.0ml 37% HCl and about 15ml Acetone and put the beaker in the freezer (-10°C). Crystals precipitated in the same manner as I have seen before using this method. Left it there for 24 hours to ensure complete precipitation. Filtered and boiled in Acetone to get 4.34g Methaqualone that was pure enough for consumption.

To the second RB flask 6.5ml o-Toluidine was added, everything got wet (the powder was damp already, remember?). After ~10 minutes at room temperature it had solidified (!?). After this delay it was emerged in a 190°C oil bath. The temperature was about 195°C, after 30 minutes it was 220°C, by mistake (my corn-oil smoked ;). Brought it back down to 200°C and kept it there until the total time was 90 minutes. At the one hour point the reaction was dead though. The mixture was dumped into a weak NaOH solution in the same manner as above. This time “the mess” was a bit browner and not so much the usual purple tint, that 220°C top sure was overkill. I might add that I use a Claisen adapter on the RB flask as some kind of condenser, the water leaves just fine even with it on. It almost solidified in the fridge as above and the same method was used. Off with the NaOH solution, mixed with ~60ml Acetone and added 3ml 37% HCl, put in the freezer for 24 hours. Just as before, crystals appeared after many hours in the freezer. Again I filtered and boiled in Acetone to get 4.80g rather pure Methaqualone.

The yield in the last step was rather low (this has been the case for Dr. Dream when using N-acetyl anthranilic acid made using the KMnO4 oxidizing method too). I think the best thing to do is to recrystallize the N-acetyl anthranilic acid using EtOH/dH2O then grind the crystals to a very fine powder. After this, the powder is placed in a RB flask and 1.20mol% o-Toluidine is added and the flask swirled until all the powder is wet. Then emerge in preheated oil (~170°C), when the reaction dies at this temperature raise it fast to 190°C and keep it there until the reaction again dies.  

-Methaco(s)mic

methaco_s_mic@hotmail.com (send PGP key or no reply)



Methaco_s_mic

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Re: Ludes from phthalimide - The saga continues
« Reply #1 on: May 28, 2000, 07:53:00 PM »
Rhodium > I think it would be a good idea if you put my post on your site as a follow up to the Anthranilic Acid synthesis. Do you agree or is it not enough Step-by-Step? (Rhetorical question, answer; “NO, it’s just fine as is”) 

Cheapskate > This sure is strange don’t you think? I don’t remember if you also tried to make a 3.5% NaOCl solution using NaOCl(s). Anyway your NaOCl solution must differ in some critical aspect from the Alclorite that Dr. Dream used. But now we know that the conversion of phthalimide into anthranilic acid doesn’t have to be more involved than my original write-up, which is nice I think.

Others > Sure there must be more Lude cooks out there; I request more rapports of successful conversions using my method. It obviously CAN BE DONE.

-Methaco(s)mic



Rhodium

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Re: Ludes from phthalimide - The saga continues
« Reply #2 on: May 28, 2000, 09:15:00 PM »
I'll add it to the file at my page. Good work!

http://rhodium.lycaeum.org


Cheapskate

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Re: Ludes from phthalimide - The saga continues
« Reply #3 on: May 31, 2000, 06:58:00 AM »
I believe you.  Now what the heck is wrong with the hypobromite I can get??  As I said, I can get the anthranilic, but not reliably and not at all with the description of your reaction.  I have another 3 wks or so to wait for arrival of stuff to try again.  I did try the 3.5 percent solution, I also tried lower concentrations.  I will refine my techniques and try it again.

We have got to find an easy way of getting o-toluidine!


Rhodium

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Re: Ludes from phthalimide - The saga continues
« Reply #4 on: May 31, 2000, 01:17:00 PM »
Cheapskate: Do you want me to send you a bottle of Alclorite? :)

http://rhodium.lycaeum.org


Methaco_s_mic

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Re: Ludes from phthalimide - The saga continues
« Reply #5 on: June 04, 2000, 08:54:00 PM »
Cheapskate > Good to hear that you don't question my success. I also believe that the problem is that you don't use the same hypochlorite solution as me. I could try to make my own 3.5% solution using solid NaOCl, but I don't have any right now, so I will not do this soon anyway. Let us all hear about your future adventures!

o-Toluidine is still easy to obtain in my area, but you are smart when planning ahead... However I'am not to fond  playing with it repetedly due to it being toxic.    

-Methaco(s)mic


Cheapskate

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Re: Ludes from phthalimide - The saga continues
« Reply #6 on: June 05, 2000, 06:08:00 AM »
Twice now I've ran across references that say that solutions of sodium hypochlorite are unreliable in their concentrations and have to titrated into reactions.  Could it be that I'm getting varying concentrations??  I tend to use the same bottle until empty and then switch, and gotten the varying reactions, but maybe there's something here.

Is there a way to test the concentration of this stuff?  Maybe I'm just being messed up by my source.  I could try some reagent grade material, but this won't help the garage mechanic.  Maybe Clorox bleach would be better after all!!


Methaco_s_mic

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Re: Ludes from phthalimide - The saga continues
« Reply #7 on: June 10, 2000, 03:10:00 PM »
Cheapskate - Yes, those bulk solutions you buy is probably of rather low quality. But yet, if you made your OWN 3.5% solution using NaOCl(s) this could not have been the problem that time. 

The concentration should be possible to determine using some kind of titration, ehh, well, read up on it. Something smelling of Cl2 could be used I guess :)

-Methaco(s)mic



Rhodium

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Re: Ludes from phthalimide - The saga continues
« Reply #8 on: June 10, 2000, 11:04:00 PM »
To titrate a NaOCl solution:

Add KI until no more iodine precipitates. Titrate this iodine slurry with good stirring with a well defined concentration of sodium thiosulfate until all the iodine color disappears.

The number of moles of thiosulfate needed, exactly equals the number of moles NaOCl present in the solution you began with. Correct for the volume and you'll get the concentration.

http://rhodium.lycaeum.org


Cheapskate

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Re: Ludes from phthalimide - The saga continues
« Reply #9 on: June 14, 2000, 02:47:00 AM »
Rhodium, is this for real?  I can try this a see what I get but I expect to have trouble with precipitating the iodine.  My experience has been that one can't tell when the iodine quits precipitating and one could easily have too much KI in the solution.  Hmmm or would this even matter?


Rhodium

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Re: Ludes from phthalimide - The saga continues
« Reply #10 on: June 14, 2000, 05:27:00 AM »
Too much KI doesn't matter.

The hypochlorite converts KI to I2 until it runs out itself.

The brown I2 is reduced to colorless I- by the thiosulfate, so when the color disappears, you have added the right amount of thiosulfate.

The tricky part is to make a very EXACT solution of thiosulfate to titrate with, and to use a very EXACT amount of hypochlorite solution to begin with.

And then it is a lot of math. Ask someone else than me to help you with that, as my chem math sux...

 

http://rhodium.lycaeum.org


Methaco_s_mic

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Re: Ludes from phthalimide - The saga continues
« Reply #11 on: June 18, 2000, 07:15:00 PM »
Cheap - As long as you tell me WHAT you do and HOW MUCH chemicals as used I will be able to help you with the math, if you run into problems. I'm sure Rhodium can too, he is just lazy :) 

-Methaco(s)mic


Rhodium

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Re: Ludes from phthalimide - The saga continues
« Reply #12 on: June 18, 2000, 08:00:00 PM »
[Technical reference for the aspiring matemathician:]

ClO- + H2O + 2 I- => I2 + 2 OH- + Cl-

hypochlorite + water + iodide => iodine + hydroxide + chloride

I2 + 2 S2O3(2-) => 2 I(-) + S4O6(2-)

Iodine + thiosulfate => iodide + tetrathionate



http://rhodium.lycaeum.org