Author Topic: OTC way to amphs, F.C w/ Al?  (Read 8193 times)

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Ganesha

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OTC way to amphs, F.C w/ Al?
« on: May 06, 2004, 05:09:00 PM »
I appologize, following is purely hypothetical and written in hurry.

I don't remember where, but I have read that the original Friedel-Crafts reaction was carried out with aluminium and not AlCl3. Friedel and Crafts inncorrectly assumed that the aluminium was the catalyst, this was later on proved to be AlCl3, which was formed in situ. AlCl3 could be substituted for another L.A, such as AlBr31.

I was thinking about the possibility of preparing 4-methylamphetamine OTC. Reaction of benzene, chloroacetone w/ AlCl3 to yield P2P is a known reaction2. What about toluene + AlX3 (or even plain Al powder) and chlororacetone --> 4-methyl-P2P?

Chloroacetone is pretty nasty to handle, it could however be prepared in several ways3. An OTC approach would be to simple generate chlorine, (by dripping HCl over KMnO4 or sodiumhypochlorite) and passing thru acetone, the yields are bad and some polychlorinated ketone is formed but it works. Aceton to be chlorinated should be very dry, this minimises the formation of byproducts according to a patent that I've unfortunately lost.

When finally the 4-methyl-P2P is formed a good old Leuckart would work for amine. Ammonium formate is not OTC, nor is formic acid. Formic acid could be prepared from oxalic acid (OTC)4. Ammonium formate could then, of course be prepared by treating ammonia (OTC) with formic acid.

Even if this worked out fine, it would nedless to say be low yielding prep. But considering the price of starting materials and OTCness it would be worth investigating for those interested in stimulants.

_____


1:

Post 413291

(Mountain_Girl: "Preparation of Aluminium Bromide, AlBr3", Methods Discourse)

2:

J. Am. Chem. Soc.; 1940; 62(6); 1622-1622.
3:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/haloacetone.html


4:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/formic.acid.html



Thoughts?


Organikum

  • Guest
On the formation of AlCl3 "in situ"...
« Reply #1 on: May 06, 2004, 06:46:00 PM »
On the formation of AlCl3 "in situ" see

Patent US2057306

, courtesy Sam.
Unfortunatly a small amount of AlCl3 is necessary to get the reaction going, but if one can get hands on some gram AlCl3, this is a superp way to produce endless amounts of this.

The patent which tells that acetone and Cl2 have to be VERY dry refers to gasphase chlorination. (cant find it now either, sorry)

If acetone is chlorinated in the liquid phase it is necessary to add at least 1% HCl or the reaction will proceed VERY violently after an induction period of some minutes where nothing happens at all.
The related

Patent US2204135



For substituted benzenes AlCl3 is a unnecessary strong FC catalyst, the addition of some iron filings will break the power of AlCl3 and suppress side-reactions this way.
(to enhance the power of AlCl3 tin might be added. In toluene disproportionation for example)

The actual drawback in the FC was the insane amount AlCl3 needed. The first patent discovered by Sam solves this problem in a very elegant way. Chloroacetone is nasty but can be handled without problems when kept cold. Its synthesis wont be possible without shedding some tears, at least in the experimental phase though.  :)


ORG


Ganesha

  • Guest
US20057306 - Document or database inaccessible
« Reply #2 on: May 06, 2004, 07:14:00 PM »

Patent US20057306

- Document or database inaccessible

Do you possibly have this patent saved on your HD, if so, could you upload it?

Thanks!


Organikum

  • Guest
Was a typo, I corrected it. Sorry. ORG
« Reply #3 on: May 06, 2004, 07:22:00 PM »
Was a typo, I corrected it. Sorry.

ORG


Nicodem

  • Guest
Vapor phase chlorination of acetone
« Reply #4 on: May 06, 2004, 07:53:00 PM »
Vapor phase chlorination of acetone:

Patent US2235562


Patent US2243484


The schemes in these two patents are more like for industrial production, but simply introducing Cl2 to acetone under reflux should work perfectly. Like Org. mentioned, the liquid phase is a little trickier and can produce more of the dichlorinated product. Once long ago I tried to chlorinate acetone during the winter (outside of course, Cl2 is nasty) and it yielded almost no product since the temperature was ~5°C. But then again I didn’t add HCl. I hopped it could bee avoided to ease the purification by distillation. Seams like not. Maybe gassing just a little with HCl gas would be better?
BTW, there are cheaper ways to produce Cl2. I guess the cheapest is by dropping sodium hypochlorite (~10% bleach) in conc. HCl. At the end some heating to ~50°C is required or you will not get all the Cl2 out. Or maybe HCl + H2O2 is even better but haven’t tried that one yet.

Good luck and don’t cry  :)


Novice

  • Guest
Acetone (l) + Cl2 (g)
« Reply #5 on: May 07, 2004, 02:18:00 AM »
I've made chloroacetone from liquid acetone and gaseous chlorine with violent magnetic stirring. There was a slight increase in temperature (25-35 °C), and upon distillation it yielded 25 ml of chloroacetone (b.p. 119-121 °C) from approximately 150 ml of acetone.

The boiling range suggests either the clean formation of chloroacetone or a mixture of 1,1-dichloroaceton and chloroacetone, as 1,3-dichloroacetone has a boiling point about 50 °C higher than that of chloroacetone.

How does one go about to separate di- and mono-chloroacetone? Ideas?

Ganesha

  • Guest
Properties
« Reply #6 on: May 07, 2004, 02:29:00 AM »
1,3-dichloropropanone - Melting point 40 celsius, Boiling point 173 celsius

1,1-dichloropropanone - Boils at 117 C

Chloroacetone - Boils at 120, melts at ~-45 celsius

This also includes bonus hits such as: Baby cry no tears, Cry with me, Tears of perl and Big boys don't cry...  ;)


Vitus_Verdegast

  • Guest
as a sidenote :-)
« Reply #7 on: May 07, 2004, 02:50:00 AM »
If you close your left nostril and hold a tissue moistened with a bit of chloroacetone under your right nostril, only your right eye will tear (and vice versa).

I actually enjoy doing this when I'm bored  :) .


Barium

  • Guest
Oh my!
« Reply #8 on: May 07, 2004, 03:39:00 AM »
You really should get a girlfriend Vitus.  ;)  Cleaning his nasal cavities with chloroacetone just because he's bored. We need to get him laid quick! Hey GC do you have anyone to spare for old Vitus?
Anyway, chloroacetone isn't that bad if you handle it as a solid. But rest assure all hell is broken lose if a refluxing solution containing chloroacetone it spilled.


Organikum

  • Guest
Aqueous mixtures containing chloroacetone at...
« Reply #9 on: May 07, 2004, 09:49:00 AM »
Aqueous mixtures containing chloroacetone at RT do utmost nothing when spilled - but once you start to wipe it up.... oh my god.

Vitus: So you suggest to fill ones nostrils with activated charcoal whilst working with chloroacetone?  ;)


armageddon

  • Guest
chloroacetone?
« Reply #10 on: May 18, 2004, 07:18:00 PM »

Nicodem

  • Guest
Chloroacetone is OK
« Reply #11 on: May 18, 2004, 08:18:00 PM »
Oh please! What’s the big deal about chloroacetone? In my experience it is nothing special. Sure, it can make you cry a little but it is just as nasty to work with as with benzylchloride or benzylbromide. And I rarely hear anybee complaining about these. It seems to me that most of this chloroacetone myth is simply based on exaggerations and fears of those who did not even experienced the beautiful lacrimogenic properties of this compound.  :)


ning

  • Guest
I think the words "war gas" put...
« Reply #12 on: May 18, 2004, 09:29:00 PM »
I think the words "war gas" put people off.

Really, though, lachrymators are often added to war gas formulations, not because they are deadly but rather to warn you that you are breathing poison gas before it's too late (or, more nefariously, to disguise the smell of the real toxic agent).

Thus, I would say to take the merck index's words with a grain of salt or two.

Someday, I want to see if the P2P from benzene alkylation with chloroacetone can bee improved by using a gentler catalyst--it would probably work best for things like dimethoxybenzene --> DOH p2p because overalkylation would be less of an issue.


armageddon

  • Guest
insignificancy *lol*
« Reply #13 on: May 18, 2004, 09:33:00 PM »
Ehmmm, of course I don't want to criticize anyone, especially no such competent bee as vitus: but I really don't see why his proposal of sniffing chloroacetone through one nostril could in any way be more significant than my suggestion to synth bromoacetone for having the same "fun", and therefore I really don't know why my last post was downrated. But that's OK. Just wanted to mention it.  >:(

BTW 1,3-dichloroacetone is nice, too!!  ;)

ning: you mean "denatured" chemical warfare agents? *lol*

Greetz A


Rhodium

  • Guest
Bullshit treshold
« Reply #14 on: May 18, 2004, 10:00:00 PM »
Other users posting useless information is not an invitation for you to do the same. It should rather be construed as an alert that any further posts in the thread should be really factual and informative as a counterweight to whatever was posted above.

Organikums post contained the useful advice that aqueous mixtures of chloroacetone was relatively innocent, while the dry substance was not (and therefore his off-topic comment could be excused). Your post added nothing of value to the thread.


armageddon

  • Guest
idividual bullshit thresholds
« Reply #15 on: May 18, 2004, 11:16:00 PM »
OK rhodium I don't want to offend you, but I gave information in my "insignificant" post, too (bromoacetone=war gas).. And the only info orgk gave was that it starts to hurt only when you go down to the floor and wipe it up - he didn't say anything bout dry substances. And why do you downrate only the second insignificant post, not the first you come across?
but as I said already, it's allright. I don't care. Really.  >:(

 And now some information to justify my post  ;) :

chloroacetone and 1,3-dichloroacetone are considered lacrimatoric, whereas 1,1-dichloroacetone is not... (at least according to merck index, which isn't the last word according to ning, and I think he's right about that)

So if this was the case, could 1,1-dichloropropanone be used in a AlCl3 catalysed benzene/toluene->(4-methyl-)p2p rxn? If not, why? Is some chlorinated phenylpropanone being formed? (which could surely be dehalogenated, ask nicodem  :) )

Here are some preparations of chloroacetone:

Patent US2209683


Patent US2235562

(this one is the chlorination of acetone)

Patent US2243484



and two more about stabilizing it (for storage maybe):

Patent US2229651


Patent US2263010




Hope that's useful enough to pass your threshold indicator, rhod!  ;D

Peace A


Organikum

  • Guest
Bah! Merck patents....
« Reply #16 on: May 19, 2004, 12:43:00 AM »
Nope, I at least am not satisfied armageddon, just typing out the patents from the Merck index (and those referred to in these patents) is cheap. No,no,no!

Answer the question how to separate mono and polychlorinated acetone in a conveniant way and I may forgive you!
I heard about azeotropic distillation with water being a possible way, but I never found details on this.
Extra bonuspoints will be given if the separation avoids distilling the lachrymators at all.

ORG  ;D
(the question is serious - the way it was expressed is meant to be a friendly tease, so please nobody may take offense.... thanks)

for ning: The reference on TCCA as chlorination/oxidation agent on Rhodiums page mentions the production of monochloroacteone by means of acetone and TCCA with BF3-etherate as catalyst.
Produces the wrong isomer though - alpha-monochloroacetone  :(

This one:
Trichloroisocyanuric Acid:   A Safe and Efficient Oxidant

Organic Process Research & Development 2002, 6, 384-393
Ulf Tilstam and Hilmar Weinmann
Process Research, Schering AG-Berlin, D-13342 Berlin, Germany



armageddon

  • Guest
next try ;^)
« Reply #17 on: May 19, 2004, 02:52:00 AM »
OK, here is what I've found:

1. chloro/bromoacetone WERE used as an aerosol in WW1 for eyewatering purposes. But they weren't real war gasses (the germans used nasty things like organic As-compounds or things like "S-Lost" which are absorbed through the skin and are deathly poisonous). Bromoacetone? - to hell with merck... :)

2. Chloroacetone can be prepared by electrolysis of HCl (or NaCl soln.) in acetone with carbon electrodes. If acetone is used in excess, the monochlorinated product is dominant...

This is what I found:

"The reaction of the acetone with the chlorine takes place directly at the electrode, The nascent Cl (NOT Cl2!) couples directly to the acetone, the so formed chloroacetone sinking to the bottom as it is much heavier than the acetone/HCl mixture.
If bubbles are visible you use much to much current.
Try 5V to 10V - chlorine bubbles = time to reduce the voltage!
But placing the anode below the cathode seems a good idea to me so no diaphragm is used. Placing the anode at the bottom of the cell is a bad idea as there the chlorinated compound will be after some time and you may get polychlorinated stuff this way.
So - in the middle?
Or use a diaphragm, claypot, plastics..."


Do you know the text, organikum?  ;D  ;D  ;D

Sorry, but at the present time I haven't found a method for separating mono- and dichloropropanone other than distillation..   but I'm still searching!

BTW chlorination of acetone yields the alpha-chloro, too - at least I read it somewhere. What do you mean with "wrong isomer"?

Greetz A


Organikum

  • Guest
Re: BTW chlorination of acetone yields the...
« Reply #18 on: May 19, 2004, 03:33:00 AM »

BTW chlorination of acetone yields the alpha-chloro, too - at least I read it somewhere. What do you mean with "wrong isomer"?



You are right. The fucking article names 2-propanone aka acetone but the drawings show 2-butanone, aka MEK. And I being tired confused it somehow it seems.

Hey ning! It works!  ;D
Where to get some BF3 though?

i´ll better get some sleep.
good night
ORG




moo

  • Guest
Separation of chloroacetones
« Reply #19 on: May 19, 2004, 03:51:00 AM »
Unfortunately I haven't got the abstracts this time. :)  In

Patent US2260262

a mixture of chlorinated acetones is refluxed with ethylene glycol and a bit of hydrochloric acid in benzene (or maybe toluene instead?) with a Dean-Stark trap, forming the ethylene ketals of the chlorinated acetones. These ketals are then separated with vacuum distillation and hydrolysed to the ketones.

In

Patent US4067886

different ketones, acetone among them, are halogenated in the alcohol, so that the chloroacetone ketal of that alcohol is formed directly. It is also demonstrated that the ketals themselves can be halogenated. I don't know whether the ketals are lachrymators or not though.

Is this what you were looking for, Orgy? ;)