dormouse (Member)
04-21-00 05:49
No 108470
      Aluminum amalgam and nitromethane -Feck  Bookmark   

Author  Topic:   Aluminum amalgam and nitromethane 
Feck
unregistered   posted 08-12-98 07:15 PM           
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There is an interesting reduction amination procedure using nitromethane and aluminum amalgam and substituted P2P's. I found this in "Amphetamine Syntheses" by Otto Snow, which Strike recommended a few weeks ago.
A mixture of substituted phenyl-2-propanone (0.25 moles), nitromethane (25 grams, 0.40 mole) and 150 mL ethanol are added dropwise while stirring to a mixture of 40 grams of aluminum amalgam in 650 mL ethanol. This mixture is refluxed for 3 hours and worked up as usual. The approximate yield is 0.21 moles (84%!) of substituted N-methylamphetamine. Supposedly, one can also use nitroethane to give the N-ethyl derivative. They used 2-methoxyphenyl-2-propanone and nitromethane.

The reference is "A New Synthetic Method for N-alpha-Dimethyl-2-methoxy-phenylethylamine"
Yakugaku Zasshi (1957) 77: 310-311 by Tanaka and Seki. Also the Chem abstracts listing is 1957 51: 11278-11279. I've never heard of nor seen the journal Yakugaku Zasshi, but I'm going to definitely find it. Osmium mentioned this in his Al/Hg variation.

Feck


quirks
Member   posted 08-12-98 07:34 PM          
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he mentioned alkyl nitrites didn't he?
Can you post any other good refs in that book?


quirks
Member   posted 08-12-98 07:44 PM          
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btw - I was checking around the other day and it is possible to get your hobby shops to order gallons of nitromethane feuls, 35% nitromethane, the rest methanol. That could almost be used as is in the above mentioned amalgamation...
Osimum where are you?? Tell us why this is too good too work!!


ketone
Member   posted 08-12-98 07:46 PM          
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quirks: make doubly sure it is just nitromethane and MeOH. Many of these model racings fuels also add a small amount of lubricant to the fuel (often castor oil!).

-ketone


Piglet
Member   posted 08-13-98 05:32 AM          
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On a related note. I have done a little reading about some slight twists on the amination game.
I noticed that Osmium's posting about Hg/Al reduction stated that the method was poor for making primary amines.
Then I noticed #114 in Pihkal where Hydroxyl Amine HCl is added to the ketone and then reduced wirth sodium cyanoborohydride. I wonder if Pd black and H2 will reduce this one? How about amalgam.
Also, CA 61,6953 (1963) (look in PC by Michael Valantine Smith p81 second edition).
This describes the formation of an oxime(?) using hydroxyl amine HCl with pottassium acetate in 70% ethanol.
The last line is 'hydrogenate'. No details! D'oh! This DOES lead to the amine rather than the hydroxyl amine.
is this more easily reduced than NH3? Will this allow production of MDA type things using a simpler reduction?

Thanks,
Piglet 


quirks
Member   posted 08-13-98 07:44 AM          
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bp: methanol = 70
bp: nitromethane = 100
bp: castor oil = 200+??
Shouldn't be very easy to seperate, it stated it was sans-lubricant anyways.


drone 342
Member   posted 08-13-98 12:54 PM          
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There's places around here that sell 80% nitromethane. In any case, all one would have to do would be to distill off the methanol and nitromethane -- the two form an azeotrope, meaning you're not going to get pure nitromethane no matter how hard you try. But you could account for the MeOH impurity when using the stuff (you have to mix it with alcohol anyways). This looks like a nice improvement.
Pd black and H2 will do the job great. Hydroxylamine doesn't really offer any advantages over NH3 in MDA production.

-drone #342


Piglet
Member   posted 08-14-98 04:20 AM          
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D342: I think that quirks (or was it ketone), tried using Pd black as a follow on to the #3 avec methanol. He said it only got him about 10% with methyl amine. Is is much better for NH3?
Thanks for your reply, Appreciated!

Piglet 

P.S. Being a dude of many interests, have you ever taken a look at the unexplored downers. Chlomethiazole is related to B6 I believe, and a great drug for beating comedowns. It was good enough for Keith Moon! Also Chlormezanone, Ecthlorvynol, Ethaniamate. All 1 off type drugs with fascinating structures. How pretty they look in CS by Sasha. Comment?


Rhodium
Administrator   posted 08-14-98 04:28 AM          
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How many times do I have to state that nitromethane and methanol can be separated by washing the MeNO2/MeOH azeotrope with the same volume of dH2O, drying with Na2SO4 or MgSO4, followed by another distillation, to yield pure, colorless nitromethane at 100-102C...
 
Piglet
Member   posted 08-16-98 10:34 AM          
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I know that I keep banging on about NH2OH, but could I ask one more thing?
In Pihkal, under FLEA (N-Methyl-N-Hydroxy MDA), Shulgin reacts the ketone with N-methyl Hydroxyl Amine to form an intermediate... Nitrone? What the...
Anyone?


Piglet
Member   posted 08-17-98 04:21 AM          
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On, and another thing. The oxime is a LOT more stable than the imine, isn't it? The oxime also has different solubility characteristics to the ketone. Could this be used as a purification step?
eg:

Take your crude ketone extract in DCM. Put it in a flask and add an equal volume of water. Stir and shove some NH2OH through the DCM layer. The Hydroxyl amine will migrate to the water layer? (Does the oxime form salts, I do'nt think so but if it did, dilute HCl rather than water would bee better).
I think only ketones & aldehydes form oximes so it SHOULD remove the junk without use of bisulphite or vacuum.

Comment?

Piglet 

P.S. I also read in Quirks Hydrogenation post that forming the imine/oxime beforehand will increase yields. Coupled with the fact that the oxime is more stable, I am wondering why it hasn't been used more...


Piglet
Member   posted 08-17-98 10:07 AM          
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Actually, Vogal's 5th Ed. 5.16.2 'Reduction of Nitro Compounds & Oximes'. Page 774
The general thrust is to say that both may be reduced to amines in a similar manner. Vogal cites Sodium dihydrobis (2-methoxy,ethoxy) aluminate ('Red Al') as the best agent.
Examples of a sodium reduction (not sodium amalgam) are given.
Other methods mentioned are metal/acid systems, catalytic hydrogenation with Raney Nickel or Palladium-on-charcoal.

Metal/Acid? Could this mean Fe/HCl? That would bee a stroke of luck...


drone 342
Member   posted 08-17-98 02:15 PM          
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Piglet,
My, you have been busy hitting the books!To start backwards:

1. Fe/HCl will reduce nitroalkenes into ketones, but I couldn't speculate regarding its use in reductive amination. I've looked at a lot of sources, and as far as I can see, I cannot find any examples in the literature. That doesn't mean it wouldn't work, just that people have been inclined in the past to resort to other means of reduction. This looks like the kind of nice, cheap, and easy research that the typical armchair chemist could research at home.

2.My guess the reluctance to forming the oxime stems from two sources. The first is that hydroxylamine isn't as readily available. The second is simply that people don't seem as interested in N-hydroxyphenethylamines -- market forces at work; people want to go with a brand name.

3.Hypnotics have never appealed to me personally as a source of recreation, but their chemistry looks mildly entertaining. Unfortunately, my copy of Controlled Substances was STOLEN (!), and the Merck doesn't seem to list any of the compounds you listed. Would it be possible for you to send me a picture of their structures, or at least their CAS #'s?

drone #342


Piglet
Member   posted 08-18-98 04:05 AM          
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D342:
1. I think I will try making an oxime from acetone and NH2OH.HCl and then run some different metal/acids on it.

2. I think hydroxyl amine is pretty easy to get and is easier to handle than NH3. Also, who says it result's in the hydroxyl amphetamines. The Vogal's entry refered to amine production (although hydroxyl amines can be produced with sodium cyanoborohydride a la Sasha).

3. I will do some posting 4 U soon.

Another thing about oximes over imines:

'Mechanism in Organic Chemistry' 6thEd by Peter Sykes: 'Nucleophilic Addition to C=O' Page 220.

...

'NH3 itself yields imines R2C=NH with carbonyl compounds but these derivitives
are unstable & react with each other to form polymers of varying size. The classical 'aldehyde ammonias' are found to bee hydrated cyclic trimers'.

Does this explain why NH3 gives such inferior results over CH3NH2 for SO MANY of the reduction routes?
Now, NH2OH! It will yield the amine and sounds like it might be as amenable to reduction as methyl amine...

Thanks for your response,
Piglet 

P.S. What do you think of Pd black for NH2OH and ketone? I'm hearing mixed things. Or is it just my tinnitus, sweetie?


Piglet
Member   posted 08-18-98 04:52 AM          
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I see from R's site that Pd/H2 on nitroalkenes yields mostly hydroxyl amine, which is more like a methyl amine in it's pharmacological action. Cheap alternative for MDMA? MDOH sounds good to me. Most of the 'Pills' in the UK are from The Netherlands and they certainly DID go through a phase of making MDOH after MDMA was made illegal and while MDOH was still legal...
Smiles,
Piglet 


Labrat
Member   posted 08-18-98 10:06 AM          
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Pig: you're right. Most of the UK pills come from Holland. Only, have you never tasted a pill containing MDOH??? I don't think so, cuz you would have known that it's more like taking MDA then taking MDMA. In Holland we even call those things "trip-pills" for obvious reasons.
But if you insist, you can use MDOH as an alternative for MDA. The hydroxylamine is alot less stable then the amine, so I'd consume my product as fast as I could. But I don't think this will pose a problem. Lr/


Piglet
Member   posted 08-18-98 10:56 AM          
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LR: I saw this trend by watching the results of pills tested by many of the UK dance magazines. For a period 95-96, quite a few samples of MDOH and MDEA were turning up. I think this was the point that MDMA was made illegal?
Remember, the pills in the UK are, in many cases, far more unsafe than the ones that the Nederlanders make for themselves. I think the best pill I ever had was in Amsterdam. Someone went to a squat (can't remember the name, but it's famous).
It was a Sunshine, and wow, I danced for about 5 hours at The Mazzo (is that how you spell it?) followed by extensive unwinding in the Greenhouse Effect. I love that place...
You can convert it to MDA afterwards. I'm just proporting this as an easier reduction route as you can form the oxime intermediate, purify it, and feed it into a nice reduction. Easier than messing with NH3.


Piglet
Member   posted 08-18-98 11:00 AM          
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Oh, and I should think that it would bee stable enough once it has been pilled up with some appropriate preservatives. How do U Dutch guys get your pill presses? I have always wondered...
Piglet 


Osmium
Member   posted 08-19-98 03:10 AM          
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German companies sell lab equipment and pill presses to everybody. Unscrupulous (?) bastards.
 
Labrat
Member   posted 08-19-98 09:27 AM          
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Pig: you're very well informed. And yes, you're right, MDOH has been launched as a legal substitute for MDMA. But soon people who used these pills started to discover that MDOH is absolutely NOT MDMA, but more like MDA. That is, it's not too good a party-drug, it's better used during a very relaxed trippy evening with some friends.
I don't think Dutch drug-manufacturers give Dutch people the best pills. They usually contain a variety of vague psycho-active substances, no matter where they go.

You've been at the Mazzo?? That must have been awhile ago, since this joint has been closed for awhile because of the extensive dealing in this place.

So you're interested in MDA oxime reduction to MDA, eh? Have you considered electrolytic reduction? I can't give you any exact references, but you need a strong reducing agent to convert the oxime into an amine.

You're right about the pills, the hydroxylamine COULD be stable if you add the right preservatives. But do you have any idea which preservatives to use? From experience I know that simply changing the colorant of the pill can change the degradation rate of the substance very much. Don't forget there's always degradation by light and oxygen.


 
Labrat
Member   posted 08-19-98 09:29 AM          
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Osmium: do those Germans sells chemicals too without asking questions? Lr/
 
Osmium
Member   posted 08-19-98 12:56 PM          
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Labrat: Last time I was in Germany (last week ;-), I had no problem getting chems. Don't ask for things like formamide, methylamine, phenylacetic acid, LAH etc. (the obvious things, you know). Basic chems are no problem at all for me, but I have an exceptional good relationship with my supplier, I usually pay less than regular prices on chems and much less on equipment. When they refuse to supply you, it's usually not because they can't legally sell you anything, it's because they don't want to. Using industrial sources, I even bought Et2O, MeNH2, solvents, sassafras in huge drum quantities for cash 3 years ago. It's probably still possible. There's a big difference between industrial and lab suppliers (Fluka, Merck, Aldrich). Industrial suppliers usually don't care very much, lab suppliers do much more often.
Sassafras is not available anymore, it's controlled since end of last year/beginning of this year.
Equipment is absolutely no problem, too. You can buy ANYTHING you want, rotovaps, pumps, glassware, cap-filling machines etc.
 
Labrat
Member   posted 08-20-98 09:39 AM          
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Osmium: Great! This is very valuable news for me, since getting chems in Holland is pretty tough. I'll start looking for German yellow pages or something alike...
Do you know the answer to this question? When I buy chems in my home country, I have to pay environmental taxes,etc. on top of the catalogue price. This means the chems become 2 times as expensive as the prices in the catalogue. Can I avoid these taxes when getting the chems in another country? Thanks for your help! Lr/


Osmium
Member   posted 08-21-98 07:58 AM          
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Environmetal taxes? Never paid anything like that. Usually I don't even have to pay regular sales tax (16% in Germany, I guess).
My supplier earns his money with bigger companies and the local university, which means he doesn't need my money that badly (that's what he said!). Students and hobby-types don't have to pay the taxes and handling charges. It also means a good, cheap used equipment supply. It's a good idea to build up some sort of relationship, and don't order chems for 2000$ the first time. Start small, make him happy, buy some of his glass, too.


Labrat
Member   posted 08-21-98 10:56 AM          
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Osmium: I hope all these German chemical suppliers are as nice as yours! I usually have to pay environmental taxes and sales taxes, making the chems 2 times as expensive as in the catalogue! In some cases, this can amount to 10 times the catalogue price! But if students and hobby-types don't have to pay the taxes, I'm VERY happy!
If making the chem supplier happy is the key, I'll try to do the best I can! Ofcourse I won't start with a $2000 order, maybe I'll buy a nice vacuum pump first, then some regular chems and build up a contact with the company. Thanks for the advice and the good help! Lr/