Author Topic: Perhaps you may have a look here....  (Read 2278 times)

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Organikum

  • Guest
Perhaps you may have a look here....
« on: June 09, 2004, 01:59:00 AM »

Post 511869

(Barium: "You can make the alkoxides by dissolving e.g.", Newbee Forum)

and followups.

in special:

Post 511982

(Organikum: "Process without distillation", Newbee Forum)

Post 512000

(gsus: "precipitation with acetone, alleged", Newbee Forum)

and prove of principle:

Post 512006

(Nicodem: "The patents work", Newbee Forum)


Nevertheless very good psyloxy, I like the "example 2" most as it answers the second of my questions asked here:

Post 511960

(Organikum: "Barium, do you know the composition and bp of...", Newbee Forum)


ORG  ;)


psyloxy

  • Guest
Yep, I've already read this when I checked...
« Reply #1 on: June 09, 2004, 06:33:00 AM »
Yep, I've already read this when I checked TFSE to see whether I'd post anything redundant - still great to see it work, though. On the other hand, fluffy precipitate like Nicodem describes can look massive in solution, while it weights next to nothing, well you may all know this  ;D

--psyloxy--

gsus

  • Guest
not next to nothing
« Reply #2 on: June 09, 2004, 09:04:00 AM »
the yield of whatever it is was high with the KOH/MeOH, even with the lost product that was too fine for the filters. didn't weigh the KOH flakes so i cant say how much. ended up cream colored. storage under the wash solvent should be fine for many applications-no need for the vacuum desiccator, though i dried it and felt the heaviness in the baggie. the problem is the amount of acetone, and the fineness. why not try it with a couple grams yourself?


Nicodem

  • Guest
A coment on Patent US1978647
« Reply #3 on: June 09, 2004, 01:30:00 PM »
Psyloxy: I didn't filtered and weighted the presumed NaOEt but I don't think it was in bad yield. 12ml of ethanol can hold utmost ~1.5g of NaOH so the there should bee produced ~2g of the sodium ethoxyde in my test. Judging by eye it was near that. The problem is only the amount of acetone needed (though it can bee recycled if one wants so).

BTW: Silicium carbide is an incredibly inert ceramic. It does not react with water.


psyloxy

  • Guest
thanks a lot !
« Reply #4 on: June 09, 2004, 07:01:00 PM »
That's really encouraging news, would be the way to go then. I would feel like a thief if it was that easy, though  ;) .

Just think of the possibilities:  CHCl3 + NaOMe __> HC(OMe)3 - 87% ;  HC(OMe)3 + p-TsOH __> p-TsOMe - 99%

OTC methylating agent there you are.  Details in

Post 466982 (missing)

(psyloxy: "practical alkyl tosylate synth - new approaches", Novel Discourse)


--psyloxy--
Summer of love, anyone ?

ning

  • Guest
ummm
« Reply #5 on: June 11, 2004, 05:21:00 AM »
psyloxy, why not just use that trimethyl orthoformate to directly methylate the phenol again?


psyloxy

  • Guest
that possible ?
« Reply #6 on: June 11, 2004, 06:53:00 AM »
I've been feeding beilstein with phenol and HC(OMe)3, turned up 2 hits, that have nothing to do with alkylation. Would you know how that art is performed ?

--psyloxy--

psyloxy

  • Guest
physical chemistry
« Reply #7 on: June 15, 2004, 11:25:00 PM »
Mol sieves! Here's the latest thoughts my brain generated on sodium methylate production:

Mix: 202ml MeOH, 40g NaOH, 100g mol sieves, stir for an appropriate amount of time with heating.Filter off the mol sieves. Theorethically you should be left with a 30% NaOMe solution in MeOH.

Now that I look at it, it's just like in

Patent US2451945

, only regenerate-able mol sieves are substituted for acetylene producing calcium carbide.

Suggestions ?

The ponderings that started it all are documented below for historical reasons:



Uhm, BTW: here's the $1 . 106 answer: methanol doesn't form an azeotrope with water. Here's the boiling-chart:



If we consider

Patent DE628023

I think it can be taken for granted that the percentage of water in the vapor-phase is low because the equilibrium lies heavily on the left (little water is generated by NaOH + MeOH __> NaOMe + H2O)  thus the difference in boiling points of MeOH and MeOH/H2O is small, a few °C  if you're lucky. What big ass fractionation column did those crazy Germans think of ?

I think a much better approach would be to use a Soxhlet where you would be trying to extract the hell out of BaO/CaO or even better: mol sieves (3Å).


Dynamic drying: solvent is filtered thru a chromatography column. 250g mol sieves are sufficient to dry 10L of solvent to a water content of 0.002% (20ppm). Column: 2.5 x 60cm (~1"x23"). Throughput: 3L/h. (transl from : www-oc.chemie.uni-regensburg.de/OCP/methoden/kap9.PDF )




Mol sieves have a capacity of ~20% their own weight, so you would  need ~ 100g mol sieves for every 54g NaOMe.

Any objections ?

--psyloxy--


Osmium

  • Guest
> Mix: 202ml MeOH, 40g NaOH, 100g mol ...
« Reply #8 on: June 16, 2004, 06:37:00 PM »
> Mix: 202ml MeOH, 40g NaOH, 100g mol sieves, stir for an appropriate amount
> of time with heating.Filter off the mol sieves. Theorethically you should
> be left with a 30% NaOMe solution in MeOH.

I doubt you can simply stir (or even filter) that mixture since it should have the consistency of wet concrete. Kneading and sieving would be more appropriate terms for those operations.  ;)


psyloxy

  • Guest
Re: it should have the consistency of wet...
« Reply #9 on: June 16, 2004, 08:38:00 PM »

it should have the consistency of wet concrete.




Because of the mol sieves or the NaOMe ? After all 30% NaOMe/MeOH is commonly referred to as 'solution' - that's what I took it for being.

However, using a Soxhlet, or more MeOH for that matter, should solve that problem.  ;)  

--psyloxy--


psyloxy

  • Guest
my last word on alkali alkoxyde production
« Reply #10 on: October 27, 2004, 03:52:00 PM »
The principle of KOH trapping water has been mentioned before in other patents found by you-know-who-you-are. Nonetheless I find this an extraordinarily beautiful example of the principle at work... so close to ultimate simplicity it fills my heart with joy. Have fun  ;D

Patent DE1043309



Example 2

In a procedure modeled after example 1 ethanol was used instead of 3-pentanol. The column was held at 68°C. The analysis of a sample taken from the top of the column showed 30.4% waterfree alcoholat.

Example 1

A glasscolumn of 25,40 mm diameter and 91 cm lenght is filled to one third with 8-mm glassrings and KOH (85%) in the form of pellets. 3-pentanol is filled into the column from the bottom with a speed of 5 mL / min. The column was kept at 120°C. A typical sample of what leaves the column from the top  was analysed as 40% waterfree alcoholat and 2.5% dissolved KOH.

--psyloxy--