majic22 (Hive Bee)
11-28-02 07:03
No 384172
      which is easier/betterhexamine or nitro reduction?  Bookmark   

Ive seen a lot of controversy on the two synths.  Both of them have their good points and theyre bad ones. I understand that hexamine has better yields but is harder. Which one would be the better synth for a first timer.  any thoughts on this? 

Theres nothing to be afraid of, just concentrate, and trust the music.
(Hive Bee)
11-28-02 07:46
No 384196
      Of course, Nitromethane is said to be easier  Bookmark   

Your friend doesn't want to use hexamine.  He wants to use methylamine or one of it's salts (usually hydrochloride).  Methylamine hydrochloride is made with hexamine and hydrochloric acid.  Many, SWIM included, have had trouble making good methylamine hydrochloride.  Of course, if he simply would have used paraformaldehyde rather than formaldehyde, or if he used the hexamine route or even just recrystallized the methylamine hydrochloride he most likely would have had no difficulties.

SWIM only has one experience with nitromethane and ketone together but his ketone was bad and poor yields followed.  He has made methylamine with nitromethane using an Al/Hg amalgamation and has to believe that the first time chemist should probably use nitromethane and then start making methylamine after nitromethane amalgamations have been mastered, as using methylamine instead of nitromethane typically gets better yields if done correctly.  That is SWIM's advice but he only has his experiences to compare and limited experience with both.  Maybe some more experienced bee will instruct you differently.  If so, I'd follow that advice but nitromethane seems to be the easiest method, if based only on SWIM's ease of making methylamine from it.  Let other bees weigh in on this one before making a choice.

El_Zorro: I think you might be right.  I probably didn't read the question very thoroughly and have done that (not read questions thoroughly enough or thought about my answer) in the past, which has gotten me in trouble from time to time.  Still, for the first time chemist (assuming now we're talking about making methylamine) I recommend nitromethane.

Who wants to play cops and dope fiends?
(Hive Addict)
11-28-02 08:30
No 384212
      I think he isn't talking about any aminations ...  Bookmark   

I think he isn't talking about any aminations just yet, just a method of getting methylamine.  I think he's wondering whether the Al/Hg reduction of nitro alone to get methylamine is better than the hydrolysis of hexamine or not, but he wasn't really all that specific.

It is seductive, way too seductive.             -Eleusis
(Hive Bee)
11-28-02 09:08
No 384218
      sorry  Bookmark   

Sorry........Yes El Zorro you are correct that is exactly what swim was asking.  thanks for clarifying.  hey swims still learning.  thankscool

Theres nothing to be afraid of, just concentrate, and trust the music.
(Hive Addict)
11-28-02 09:14
No 384220
      Don't worry about it, dude, just take it all in ...  Bookmark   

Don't worry about it, dude, just take it all in stride.

But it's really just a matter of opinion, precursors, and skill.  Terbium stands by the formaldehyde/ammonium chloride synth, abacus is partial to the Al/Hg, and Chromic seems to fancy the hexamine route.

There's no real right or wrong answer there, just UTFSE, find out other's opinions on the subject, and then decide what you can do with the precursors you have available.

It is seductive, way too seductive.             -Eleusis
(Hive Bee)
11-28-02 10:38
No 384245
      Its a question of how much time you have  Bookmark   

I found the formaldehyde route and Hexamine with hcl method work very well, but the yields are low.

However I found the fishy stink that those synths somehow created was the problem for me, stinking my lab and clothes out for weeks, so much so that the neighbours started complaining.

Thats why I switched to using Al/hg to make a methylamine/methanol solution which was a lot faster and less stinky.


BTW  Eleusis was right.
(Hive Bee)
11-28-02 10:53
No 384252
      Time and labor intensive  Bookmark   

I first used the formaldehyde and ammonium chloride at 104 degrees celcius route and did it several times.  The temp has to remain constant, in my experience, meaning your equipment (stirrer with hotplate combination) must not fluxuate.  This is my guess as to why SWIM had so much trouble.

Abacus: Good post on this subject just a few days ago.  I've recommended he follow it.  SWIM's goin' MM Nitro but plans to make his methylamine your way in the future and abandon nitromethane reductions in a one pot reduction using amalgamation.

Who wants to play cops and dope fiends?
(Hive Addict)
11-28-02 10:56
No 384254
      wrong temp?  Bookmark   

i believe it's 104°C, no?

Now with 12% more Bottom!
Nymphomania is not a disease, its a goal! (Methadist)
(Hive Bee)
11-28-02 11:02
No 384259
      Yep!  Bookmark   

It is 104 degrees celcius.  I was using a fahrenheit thermometer at the time and converting.  That got me confused.  Thanks for the correction.  I'll edit it above and only posted here so that your post would make sense to other bees reading.

BTW, still a big Pixies fanatic?  I am!  I can't stop listening to them and that's like, been goin' on for 6 months.

Who wants to play cops and dope fiends?
(Hive Bee)
11-28-02 17:49
No 384334
      ok thanks  Bookmark   

ok thanks

Molecule: MDMA (" CNC(C)Cc2ccc1OCOc1c2 ")

Theres nothing to be afraid of, just concentrate, and trust the music.
(Hive Bee)
11-28-02 19:41
No 384347
      Beuatiful picture!  Bookmark   

However, your aromatic ring shows too many double bonds (6 rather than 3), unless that's a way of showing the C6H5 ring section of which I am currently unaware.  Remember, also, that the MDMA molecule you drew or found is lacking in hydrogen.  Maybe there's no rule regarding including hydrogen in it's nomenclature.  It's assumed in drawing "short hand" that available spaces for bonds are hydrogen filled but this doesn't look like short hand.  Regardless, pictures are nice.

I wanted to draw it myself but every attempt I made to draw it myself came out looking confused.  I don't draw those very well.  Sorryblush!  I just wanted to acount for all the atoms in the compound or at least clear up confusion.  I should probably of said nothing at all but that model looked confused to me. 

Who wants to play cops and dope fiends?
(Synaptic Self-Mutilator)
11-28-02 20:38
No 384355
      There is almost no smell  Bookmark   

There is almost no smell to the HCHO/ammonium chloride or hexamine/hydrochloric acid synth if you vent the gases produced from the reaction to the outside. I have no idea what you guys are doing wrong? You should only have stink for a couple hours when you're working with the chems. Don't be sloppy and the smell isn't any worse than distilling any of the oils.

I have also found that no reaction happens when the internal temperature stays at 104C. It's only until the vapor temp reaches 104C that I see a reaction happening (yes, I've tried holding it at 104C for hours...)

If you were following Eleusis' write-up you were following the wrong synthesis.

But yeah, the yields are kind of low (you're lucky to get a 40% molar yield after recrystallization)... but the synthesis scales very easily.

I'd definitely recommend the nitromethane to any bee who just wants to make a bit of mdma. If you want to mass produce, you want previously prepared methylamine (either made from hex/HCl, HCHO/AmCl or catalytic hydrogenation of MeNO2).
(Hive Bee)
11-28-02 21:35
No 384362
      thanks  Bookmark   

actually i got the picture from the FAQ page on the hive.

Theres nothing to be afraid of, just concentrate, and trust the music.
(Hive Bee)
11-28-02 22:17
No 384370
      Okay  Bookmark   

I'll accept thatwink!

Who wants to play cops and dope fiends?
(Hive Bee)
11-29-02 00:05
No 384404
      I hope people arent doing the ...  Bookmark   

I hope people arent doing the p-formaldehyde/nh4cl synth without a distillation apparatus!

Sink or SWIM
(Hive Addict)
11-29-02 00:26
No 384414
      Moriarty- I think that pic was showing the ...  Bookmark   

Moriarty-  I think that pic was showing the resonance structure of the aromatic ring, with what I think is supposed to be a dotted line all the way around the inside of the ring.  Am I right?

But I would have put the hydrogen on the nitrogen atom, though.

It is seductive, way too seductive.             -Eleusis
(Hive Bee)
11-29-02 01:49
No 384436
      Totally right  Bookmark   

Youre 100% right. That's how you represent aromatic rings, after all the pi electrons are delocalised over the entire ring. Its just a sum of its resonnance contributors
By the way hydrogens arent usually represented, rather implied. A carbon with two bonds showing has 2 hydrogen bonds implied but not drawn(sp3 hybridized of course)
(Hive Addict)
11-29-02 02:54
No 384453
      Yeah, I know about hydrogens not being shown on ...  Bookmark   

Yeah, I know about hydrogens not being shown on carbons, but it's just a thing I have, I probably would have shown the hydrogen on the nitrogen atom.  Doesn't matter, they're both right either way.

It is seductive, way too seductive.             -Eleusis
(Hive Bee)
11-29-02 04:18
No 384486
      The rules for drawing shorthand structures  Bookmark   

In one of my Organic Chemistry textbooks I just finished reading the rules on shorthand.  Here they are:

1.   Carbon atoms aren't usually shown.  Instead, a carbon atom is assumed to be at the intersection of two lines (bonds) and at the open end of each line.  Occasionally, a carbon atom might be shown for emphasis or for clarity.

2.   Hydrogen atoms bonded to carbon aren't shown.  Since carbon always has a valence of four* (astrix and comment inserted by me, not the text), we mentally supply the correct number of hydrogen atoms for each carbon.

3.   All other atoms other than carbon and hydrogen are shown. (p. 42)

I have to admit to not knowing if the same rules apply to resonance structures, but if they do the hydrogen should have been shown on the nitrogen atom.  They give indole as one of the examples on the next page and the hydrogen atom on that nitrogen atom is represented.  Let me read up on resonance stuctures and think about the concept to make sure the same rules apply.

Okay, there should be a hydrogen on the nitrogen atom.  The rules are not similar but involve, as the bees above mentioned, shared pi elecrons.  This wouldn't apply to nitrogen.  In the resonance example given in my text hydrogen is represented on the nitrogen atom.  I would do a pretty pour job of explaining what I just read so I won't try to explain the theory.  The inner lines represent that the pi electrons move from one carbon to another fairly freely.  In other words,

 //  \
C     C
|     ||
C     C
 \\  /
is a fiction of sorts.  It would be some hybride between these two (2) forms:
   C                 C
  / \\              //\
C   C             C   C
 ||  |   <---->  |  ||
C   C             C   C
  \ //              \\ /
   C                  C
The idea is to emphasize the moving pi electrons from carbon to carbon.

My textbook's lists five (5) rules for drawing and interpreting resonance structures:

1.  Resonance forms are imaginary, not real.  The real structure is a composite hybride of the different forms.  Substances like allyic carbocation, the carbonate ion, and benzene are no different from any other substance in having single, unchanging structures.  The only difference is the way they must be represented on paper.

2.  Resonance forms differ from each other only in the placement of the pi electron.  Neither the position nor the hybridization of atoms changes from one resonance form to another.  In benzene, for example, the pi electrons in the double bonds move, but the six carbon atoms remain in place:  By contrast, structures like 1,3-cyclohexadiene and 1,4-cyclohexadiene are not resonance structures because their hydrogen atoms don't occupy the same positions.  Instead, the two dienes are constitutional isomers.
(look those up at because I can't draw them).

3.  Different resonance forms of a substance don't have to be equivalent.  For example, the allylic carbocation obtained by reaction of 1,3-butadiene with H[/sup]+[sup] is unsymmetrical.  One, end of the delocalized pi-electron system has a methyl substituent, and the other end is unsubstituted.  Even though the two resonance forms aren't equivalent, they both contribute to the overall resonance hybride.

In general, when two resonance forms are not equivalent, the actual structure of the resonance hybride is closer to the more stable form than the less stable form.  Thus, we might expect the butenyl carbocation to look more like a secondary carbocation than a primary carbocation.

4.  All resonance forms must obay rules of valency.  Resonance forms are like any other structure: The octet rule still holds.  For example, one of the following structures for the carbonate ion is not a valid resonance form because the carbon atom has five bonds and ten electrons:
   O          O
   ||         ||
   C          C-
  / \        // \
-O   O-   O   O-

Carbonate    Not a
ion         resonance form

5.  The resonance hybride is more stable than any single resonance form.  In other words, resonance leads to stability  The greater the number of resonance forms possible, the more stable the substance.  We've already seen, for example, that an allyic carbocation is more stable than a normal carbocation.  In a similar manner, we'll see...that the benzene ring is more stable than a cyclic alkene. (p.110-111)

As for the hydrogen being shown on the nitrogen atom of the MDMA molecule I'd say that a double bond is not close enough to that atom to allow pi electrons to move to it.  I could have misinterpreted what is written above but I think the theory is clear about what types of molecules and at what points on them pi electrons are free to move.  Even if it were, it doesn't appear as if the rules for showing hydrogen bonded to nitrogen is in anyway different, not to mention that examples clearly showed them.  In another resonance structure given as an example in the book I have (the example is morphine) all double bonded carbons do not show a hydrogen atom but all singe bonds show them.  Maybe it might be more correct to show a few hydrogen atoms on carbon atoms that do not share a double bond with another carbon atom?  I truly can't say as I am no expert.  Regardless, it's assumed where a valence may be filled that hydrogen is what goes there.  Which is more correct?  They are probably both correct or at least accepted but I'm with the bee who advocated the showing of hydrogen on the nitrogen atom of MDMA. (p. 364)

All the rules came from an Organic Chemistry book entitled "Fundamentals of Organic Chemistry, 2nd Edition", John McMurry, Brooks/Cole Publishing Company, 1990.  I doubt that text is even locateable so referencing it was probably not necessary.

*Those rules are for Organic Chemistry.  The book I have that is not Organic, but more like a General Chemistry Text, notes that oxidation states of -4, +2 and +4 are possible for carbon atoms.  At the moment I can only think of carbon monoxide (CO) as an example.

Who wants to play cops and dope fiends?
(Hive Bee)
11-29-02 17:08
No 384602
      terbium vs. chromic  Bookmark   

and now?

Two bees I usually trust in their statements, Chromic and terbium heve posted experiences which seem to exclude each other:

- terbium says the reaction with ammoniumchloride and formaldehyde proceeds well with the temperature at 104°C. No boiling necessary.
- Chromic says he tried and there was no reaction (visible) at 104°C

The only solution I see by now is that Chromium didnīt see the reaction as their is nothing to see. (terbium tells something like this if I am right)
So I ask Chromium if he did proceed by applying more heat until he saw something happen or if he tried a workup after these hours of nothing seeming to happen? If he did so, I will be left in complete irritation, if he didnīt I assume that the expectation to see something happen ended in the opinion nothing had happened without verification.

A light in the darkness please

now or never
(Synaptic Self-Mutilator)
11-29-02 21:10
No 384654
      It bothers me too  Bookmark   

Terbium has run the AmCl/HCHO reaction. I have run the hex/HCl reaction. There might be slight differences in the temperatures between these two reactions because the hex/HCl variation has a bit more AmCl equivilant than the AmCl/HCHO version.

The way I ran this reaction to test out Terbium's suggestion was over the course of three days. As each day progressed, I would turn the heat up a bit more. After stirring at 104C for a day, nothing happened. I went up to ~104C vapor temp (this is 110-115C liquid temp) and the mixture started bubbling as I normally saw when hitting this temperature faster (mostly gas bubbles, some vapor bubbles).

Keep in mind that the "work up" of this reaction requires the distilling pot to be boiled dry, so except for time spend at each temperature, there was no difference in the overall method. There was also no difference in the approximate yields.

The odd thing is that both Terbium and I stand by our recommendations. I think the best piece of advice is to simply "go very slow" with heating.

Honestly, this is a pretty hard reaction to fuck up. Eleusis did it on a hotplate with a frying pan and still got some sort of product that could be used for amination. (*but do not do this, your product will contain significant amounts of inactive N,N-dimethyl- product*)
(Old P2P Cook)
11-29-02 22:02
No 384657
      As I have said before .  Bookmark   

The way I ran this reaction to test out Terbium's suggestion was over the course of three days. As each day progressed, I would turn the heat up a bit more. After stirring at 104C for a day, nothing happened. I went up to ~104C vapor temp (this is 110-115C liquid temp) and the mixture started bubbling as I normally saw when hitting this temperature faster (mostly gas bubbles, some vapor bubbles).
The reaction mixture is not supposed to bubble. The reaction happens at a liquid temperature of 104 C even though there is no overt indication that anything is happening.

Keep in mind that the "work up" of this reaction requires the distilling pot to be boiled dry, so except for time spend at each temperature, there was no difference in the overall method.
Which procedure calls for the pot to be boiled dry? The procedures in Vogel and Organic Syntheses certainly do not. The procedures given in Vogel and Organic Syntheses are nearly identical and it has been my experience that the procedures given in Vogel and Organic Syntheses are very reliable. I don't understand why anyone would follow some procedure that is materially different from the ones given in Vogel and Organic Syntheses.

Baseline Does Not Exist.
(Hive Bee)
11-30-02 08:46
No 384840
      I tried the hexamine/hcl synth  Bookmark   

I carried out the hexamine (700g) with HCL synth.  The flask temperature was held at around 104DegC for over 6 hours.

Small amount of gas was emitted and minimal bubbling noticed in the flask and was not refluxing.

Then reduced the volume under reduced pressure to half, filtered, further reduced liquid under reduced pressure.

The flask contents temperature was never allowed to exceed 110DegC except right at the end for a couple minutes at most.

Recrystalised 220g meam.hcl from 1L methanol.

(Synaptic Self-Mutilator)
11-30-02 09:09
No 384845
      "reduced as far as possible"  Bookmark   

Orgsyn say to reduce the volume as far as possible--until it becomes a thick paste. I just kept boiling until it was dry... it was easier.
(Old P2P Cook)
11-30-02 16:50
No 384921
      Yes, but there is a lot in between.  Bookmark   

Orgsyn say to reduce the volume as far as possible--until it becomes a thick paste. I just kept boiling until it was dry

This is only after several previous steps and much of the methylamine has already been recovered.

Organic Syntheses says the post 104°C reaction workup is:

1) Cool to room temperature and filter off precipitated ammonium chloride.
2) Heat on a steam bath until the volume has been reduced by half then cool and filter off more ammonium chloride.
3) Concentrate again using heat and reduced pressure (water aspirator) until a scum starts to form on the top of the liquid then cool to room temp and collect a first crop of methylamine.
4)Concentrate again with heat and reduced pressure to 2/3 of previous volume then cool to room temp to obtain a second crop of methylamine.
It is only now, after 4 previous steps of concentration and filtration, that the solution is concentrated to a thick syrup and extracted with chloroform to obtain a last little bit of methylamine. I never bothered with this fifth round of concentration for the small amount of methylamine that was recovered from this step.

Again I can't emphasize enough that the Organic Syntheses procedure should be followed as closely as possible. The specified temperatures should be maintained and each step should be followed. Shortcuts should not be taken. If the procedure calls for five stages of concentration and crytallization it should not be shortened to one. The five stages are there not by whim but for a precise reason.

Baseline Does Not Exist.