PrimoPyro (Hive Prodigy)
01-13-02 15:06
No 255913
      Yet Another Classic PP Idea + Question Thread  Bookmark   

Hi, I just had an idea, and I need to know the answer to one specific question to make me either jump with excitement or cry with disapointment. Thank you for reading, and hopefully for answering as well.

Will a sodium amalgam (Na/Hg) react with anhydrous alcohols, specifically isopropanol, to form the sodium alkoxide derivative of the alcohol? (specifically, sodium isopropoxide)

If this will work on the surface line between the amalgam and the anhydrous alcohol, then I have a cool idea to share. If not, then I guess I don't. laugh

Thanx for your help everyone.


Vivent Longtemps la Ruche!
(Stoni's sexual toy)
01-13-02 16:00
No 255917
      Re: Yet Another Classic PP Idea + Question Thread  Bookmark   

Yes, the alkoxides will be formed.
(Hive Prodigy)
01-13-02 16:24
No 255923
      Re: Yet Another Classic PP Idea + Question Thread  Bookmark   


Now I realize that this does not mean that the following idea will work, but fuck yea anyway! That is so cool. cool

Why thank you, Osmium. smile

I was thinking about possible indirect electrosynthesis of alkalai alkoxides via an amalgam intermediate phase.

Here's a major example relevant to the idea, the exact one that gave me the concept:

Picture a cross-section diagram of a "square" reaction vessel. The vessel has two verticle levels of floor depth, the lower being toward the center, slightly off to one side, and being only a small degree lower than the rest of the floor (say maybe ~2cm deeper.) The vessel has a verticle partition at the first third across mark, which extends below the upper floor, into the depression, but not to the lower floor.

The basin is filled with liquid metallic mercury. Now we have an effective bisection of our reaction chamber, the bisecting wall being comprised of the verticle wall dipped into the mercury basin, giving rise to two seperate chambers on either side of the mercury.

One chamber contains an electrode. The other chamber is barren. A second electrode is intoduced into the mercury, not extending into either chamber itself.

The chamber with the electrode is charged with concentrated aqueous sodium hydroxide. The barren chamber is charged with anhydrous alcohol, specifically isopropanol in the brainstorm.

Electrolysis is begun, with the mercury acting as the negative cathode, and the aquatic electrode acting as the positive anode. Oxygen gas is produced at the aquatic anode.

The cationic/positive sodium ions attract to the negative mercury, and one of two things happens:

1.The sodium free radical is absorbed into the mercury, forming what is called an amalgam (a solution with Hg as solvent/an alloy with mercury) and the sodium diffuses throughout the mercury.

2.The sodium radical reacts with water first, regenerating sodium hydroxide, and evolving hydrogen gas. The starting hydroxide has been recycled, and is subjected to the process again.

On the other side of the partition, the sodium dissolved into the mercury diffuses to the surface, in contact with the alcohol, and reacts with the alcohol, isopropanol, to procure the alkoxide, in this case sodium isopropoxide, and to evolve hydrogen gas.

The mercury, being severely "hydro-hostile" effectively prevents hydrolysis of the alkoxide by preventing the diffusion of water across the metallic partition.

Very interesting isn't it?

There are a few catches, and unknowns, but hey give me a little break here, I just thought of this an hour ago ago. laugh


Vivent Longtemps la Ruche!
(Ubiquitous Precursor Medal Winner)
01-14-02 01:12
No 256057
      Re: Yet Another Classic PP Idea + Question Thread  Bookmark   

I like that apparatus for producing alkoxides. It gets the Neothermal Engineering Seal of Approval.

A reagent to bee alkoxidated, if resident in the anhydrous solvent of the nonelectrified side, could convert the device into an alkoxidifying machine. Not for bromovanillin nor others requiring heat in their processing, for heat can't be applied until the solvent is clear of the mercury.

Oh, wait --- Na methoxide will methoxylate bromovanillin without heating, won't it? My mind's been on magnesium methoxide too much lately. Well, there would possibly be a safety issue in conducting a methoxylation in the presence of mercury, with a halogenated reagent. Bear with me, I'm working it out as I go. The haloacid produced as by-product would make the mercury labile, producing a salt which may not all precipitate from anhydrous alcohol. A complex might get formed --- uh, Pyro? Your idea was good, mine wasn't.

turning science fact into <<science fiction>>
(Hive Prodigy)
01-14-02 11:33
No 256191
      Re: Yet Another Classic PP Idea + Question Thread  Bookmark   

No halo-acid is produced in those reactions. The alkalai halide is produced via the reaction ArX + NaOR --> ArOR + NaX.

True that there is a tradeoff however. The alkoxylation proceeds faster with better leaving groups, i.e. I>Br>Cl>F so one would rather use ArBr or perhaps even ArI to increase yields, but:

The better the leaving group, the more dissociation there is between it and the Ar (we have already established this) therefore, if any side reactions do occur between the amalgam (and there will be) the reactions will occur faster and there will be more if them, with each successively better leaving group.

One reaction that would be certain to occur with the amalgam is Ar* + X* + Na/Hg --> NaX + Ar** + Hg**

* = dissociation
** = some unknown complex that I cannot describe with formulae, as I do not know what would happen on that end.

I think this would effectively poison the amalgam, thus ceasing production of the alkoxide and causing the reaction to halt. But, as we all know, engineering can overcome this. I am going to be thinking a lot about this for a few days, I can already tell.

What I am truly interested in is the isolation of the alkoxide from the active reaction mixture. I'm fairly sure that one main problem will be that the formed alkoxide will clutter the surface line between the alcohol and the amalgam, preventing further reaction. There needs to be a way to remove the product from the reaction site effectively.

EDIT: Nevermind. It appears as though the alkoxides are soluble in their corresponding alcohols, so NaOiPr should solvate and thus be removed from the reaction site effectively.

Vivent Longtemps la Ruche!
(Hive Prodigy)
01-14-02 12:21
No 256193
      Re: Yet Another Classic PP Idea + Question Thread  Bookmark   

Halfapint: You wanna be crazy and invent a methamphetamine machine? SWIPP does. SWIPP has ideas for two now. The original, starting from toluene, and now this one, also applicable to MDMA (I'd rather see people make MDMA than MA)

1.Instead of electrolyzing sodium hydroxide, electrolyze sodium iodide, to precipitate I2 at the anode.

2.This will be incredibly difficult, but I know it can be done somehow. This will be very vague: Set up the machine so that the produced NaOiPr is led off, concentrated (through automated partitioned extraction) and led into iodobenzene and acetone mixture, in a 1:1.1 ratio or so.

Alkoxide forms the acetone enolate, enolate attacks iodobenzene, forming phenyl-2-propanone.

Ideally, instead of using iodobenzene, one uses iodobenzodioxole instead, to procure MDP2P.

The iodobenzodioxole is produced from the liberated iodine via electrolysis. Ideally, it is done in a continuous, realtime reaction, producing the two reactants and the main reaction mixture perfectly with no problems whatsoever in the perfect ratios and conditions and everything is just wonderful. tongue

Hey, it can happen.....wink


Vivent Longtemps la Ruche!
(Stoni's sexual toy)
01-14-02 12:59
No 256201
      Re: Yet Another Classic PP Idea + Question Thread  Bookmark   

You confuse me.
(Hive Prodigy)
01-14-02 13:40
No 256205
      Re: Yet Another Classic PP Idea + Question Thread  Bookmark   

Ehh? How so?

I realize that my last post was very vague, but that's because it was just an outline, not an actual device.

If you were confused before that, then how so?

As for the desire, what I was talking about was building a one single reaction vessel, with multiple chambers and such, that operated in such a way as to be able to take in raw materials, say acetone, IPA, NaI, Benzodioxole, Hg, H2O, and a variety of other solvents and such for the various not-yet-created apparatus, and take all that, and you plug in the juice, all the parts come to life, and it hypothetically makes P2P, or MDP2P. Its more of a joke really.

I have already covered the alkoxide idea, as far as producing it. But what about isolating it? There are so many things I do not know that it makes it incredibly difficult to design such a device that automates this type of reaction, where you fill the chambers, flip the switch, and moments later, remove your jar of isolated alkoxide. But I want the end to be no less than just that very idea.

So far, I like what I got: the sodium hydroxide forms the amalgam, and that reacts with IPA to form the alkoxide/IPA solution.

But that is where it ends. I still want to know:
a method for isolating the alkoxide from the IPA mixture while the device is still operating, i.e. a continuous cycle reaction of production and isolation.

I wonder about perhaps having another partition in the IPA chamber, extending from the floor toward the top. On the other side of the partition, a solvent that is immiscible with IPA resides, not actually reching the top of the partition. The IPA level however, is higher than the partition wall, so it "overflows" (initially) into the other side, forming a layer above the "other solvent."

If the isopropoxide was insoluble in this other solvent, when the NaOiPr dissolved in IPA diffused to that surface line, wouldn't it precipitate into that solvent, and crash out as crystals? This is where my knowledge falters majorly. I am just outright guessing on that, and want to know if that would work with this mystery solvent.


Vivent Longtemps la Ruche!
(Hive Bee)
01-14-02 18:23
No 256280
      Input from Rhodium  Bookmark   

SWIM COMMANDS YOU to keep working on this absoutley awesome
idea.  I wish I could contribute to this but that project is
a little outta swims reach.  I am definately entrigued by
this idea.  Where is Rhodium?  He knows all and sees all..
I think he uses a crystal ball in his reactions or either
he perfected the book to brain osmosis catalyst wink
Do you have any ideas (Rhodium)?  Well it's official you
get the Golden Bee star of the week for "most innovative
and potentially revolutionary idea"

Gott Mit Uns!
(Hive Prodigy)
01-14-02 20:27
No 256335
      Re: Input from Rhodium  Bookmark   

Here is a 2 minute attempt at what I am talking about here.

The blue is the water phase, the grey is your mercury, the yellow is the alcohol, and the green is the mystery solvent that is denser than the alcohol, and immisible with it, and the alkoxide is insoluble in it.

The mystery solvent needs to be as small a volume as possible, for efficiency in removing it from the extracted alkoxide. However, the surface area on contact with the alcohol should be significantly larger, to quicken the rate of extraction by increasing the transition site area. The same goes for the area of the reaction site between the alcohol and the mercury.

Ideally, the non-aqauatic chambers will be created as one chamber with a diagonal partition, maximizing both surface areas, while minimizing each's volume.

The aqueous electrode can simple be "dipped" into the water, which is open at the top, so that the oxygen gas just evaporates.

As the alcohol is consumed to create the alkoxide, more is simply introduced via careful toploading.

Simple exploitation of properties can eliminate the needs for certain exotic reagents and procedures.


Vivent Longtemps la Ruche!
(Stoni's sexual toy)
01-14-02 22:56
No 256407
      Re: Input from Rhodium  Bookmark   

Alcohols mix with pretty much every solvent there is.
Let's pretend there is a solvent heavier than the alkoxide solution. Then why should the NaOR salt move into that mystery solvent and precipitate? It has no reason to do so.

You have to take off some of the alcoholic solution, evaporate the alcohol, and return the distillate. That might work to isolate the NaOR.
You also have to move/pump the amalgam, because Na/Hg solidifies after only a few percent of sodium will be absorbed.