01-18-02 16:06
No 257912
From US Patent #4,267,396
…..In accordance with the present invention a reaction is provided wherein sodium hydroxide or potassium hydroxide is reacted with an alcohol of up to six carbon atoms and unhydrated lime, i.e., calcium oxide, in the presence of a suitable surfactant(possible w/out one, albeit much slower, at atmospheric pressure. The reaction results in excellent yields of the corresponding sodium or potassium alkoxide in solution with the formed calcium hydroxide precipitating from the solution. The reaction proceeds much more rapidly with the surfactant present, than without any surfactant and satisfactory yields are obtained with the reaction carried out at relatively low temperatures, e.g., temperatures of up to about 60.degree. C., and even at room temperature.
Without PTC:
EXAMPLE IA
150 parts of calcium oxide pebbles (about 1/2 inch in size), 40 parts caustic soda flakes, and 262 parts methanol were combined in a reaction vessel fitted with a reflux condenser and stirred with moderate speed at room temperature for 197 hours (8 days). The solid material in the reactor was allowed to settle and the supernatant liquid was carefully decanted away from the settled solids. The solution contained 11.76% NaOCH.sub.3, 5.33% NaOH, and 0.09% Na.sub.2 CO.sub.3, which constitutes a 61.8% yield of NaOCH.sub.3.
EXAMPLE IIIA
14 parts of commercial 90% KOH flake. 71 parts methanol, and 38 parts calcium oxide were combined in an apparatus and procedure similar to Example I and stirred at room temperature for 190 hours. The product was found to contain 14.7% KOCH.sub.3, 3.49% KOH, and 0.38% K.sub.2 CO.sub.3 which constitutes a 75.7% yield of KOCH.sub.3.
With PTC:
EXAMPLE IB
Example IA is repeated however with the addition of 1% cetyl trimethyl ammonium chloride (with respect to the weight of the NaOH). After a reaction time of only 24 hours, the resulting solution contained 13.5% NaOCH.sub.3.
EXAMPLE ID
Example IA is repeated however with 1% sodium lauryl sulfate. After 144 hours the solution contained 11.6% NaOCH.sub.3 is obtained.
EXAMPLE IIA
99 parts methanol, 20 parts caustic soda flakes, and 75 parts calcium oxide, powdered, were combined in an apparatus similar to that in Example I and maintained between 45.degree. C. and 60.degree. C. for 54 hours with mild agitation. The decanted products was found to contain: 13.04% NaOCH.sub.3, 8.36% NaOH, and 0.30% Na.sub.2 CO.sub.3 which constitutes a 53.0% yield of NaOCH.sub.3.
The amount of the surfactant is not critical. Very small amounts can be used. While relative large amounts can also be used, it is of course desirable to use as little as possible of the surfactant from the standpoint of economy. In general, amounts of 0.1-4.0% of surfactant, with respect to the amount of the sodium or potassium hydroxide, can be used. The amount is preferably between about 0.5 and 2% by weight.
It should furthermore be noted that the particle size of the unhydrated lime is comparatively unimportant in the process and it is possible to use, with equal success, either powdered or lump material. The only difference of course is the time required for the reaction since lump would require a longer reaction time to produce the same effects at in the case of the powdered starting material. Still further it should be noted that even impure calcium oxide can be used provided that proper adjustment is made with respect to the quantities used and furthermore provided that not too much silica is present. The process has been successfully carried out using as poor a quality as 70% calcium oxide.
Like it? See the patent for more details.
Antoncho
(Official Hive Translator)
01-18-02 16:28
No 257918
Well, oh my beloved friends, looks like the previous procedure was just a preface. Here is the real shit, and it is fucken awesome!
From US Patent #2,278,550:
There is a variation of this prep'n using continuous extraction w/Soxlet, too.
Think of it - potash and alcohol, can it get easier?!
I feel compelled to start brominating vanillin
Antoncho
(Hive Bee)
01-19-02 03:22
No 258162
Did n0body reply on this excellent piece of OTC'ness ?
Thanks, Antoncho, what a beautiful job!!
e109
(Chief Bee)
01-19-02 04:20
No 258185
I think it's perfect. It will make it onto my page soon.
(Hive Prodigy)
01-19-02 05:21
No 258201
Incredible find Antoncho! Start harvesting your mothballs now before they become a controlled substance!
When reading this, the very first thing that came to my mind was p-C6H4Cl2 + 2NaOCH3 ___> p-C6H4(OCH3)2 + 2NaCl
Completely OTC dimethoxybenzene!
For those who are not aware, para dichlorobenzene is one of two formulations for common mothballs. Furthermore, if one decided to iodinate instead of formylate the dimethoxybenzene, one could utilize this alkoxide procedure even further to produce sodium isopropoxide, the number one otc choice for preparing acetone enolate, which, when added to the iodo derivative above, will combine to produce the dimethoxy-phenyl-2-propanone directly, skipping the propenyl stage. It's just a quick reductive amination with hydroxylamine and Al/Hg to make the amphetamine. Tack on your Bromine atom, and voila! DOB with style! Did everyone notice the ethylene glycol example? Possible candidate for forming the difuranyl structure, eh, eh? [jabs you in the ribs as he winks at you]
Use this to replace step one in the procedure outlined in Post 185131 (hest: "New Amph. more potent than LSD", Serious Chemistry).
What other cool things can be done with alkoxides? Great find Antoncho! Thank you!
PrimoPyro
Vivent Longtemps la Ruche!
(Hive Bee)
01-19-02 22:42
No 258426
i've never seriously considered using hydroquinone as a precurser until now
.very sweet7.10.01
(Hive Prodigy)
01-19-02 23:37
No 258443
How will an alkalai alkoxide alkylate hydroquinone?
Vivent Longtemps la Ruche!
(Hive Addict)
01-20-02 06:00
No 258550
Woudn't Ag2O catalyze the reaction of the free alcohol, MeOH, with p-dichlorobenzene? It is a surprising finding that NaOH will react to form NaOMe (and not just as an equilibrium rxn)... btw, alcohols don't react with NaOMe... (obviously, just try and draw a rxn mechanism)
However... I just can't think of any applications for NaOMe (or, better yet, KOMe).. does anyone have a working procedure to brominate vanillin with NaBr? <sigh> I wish someone could find a way to make a 4-bromo-2,5-dimethoxy benzaldehyde, then we'd be talking...
(Official Hive Translator)
01-20-02 08:52
No 258597
Thank you everyone for the positive feedback, guys.
I want to note a coupla things. Dear Primo! i'm afraid, p-dichlorobenzene won't methoxylate - chlorine is way too unreactive, i've seen many examples of his rxn. At best, the yields are low.
Then, dear Chromic, both these rxn ARE equilibrium, it is just a matter of it being shifted in the proper direction.
Then - brominations. I understand your loathing to work w/Br2, well what about making Br2 w/peroxide and xtracting it w/DCM and then using the soln straight for bromination?
>I wish someone could find a way to make a 4-bromo-2,5-dimethoxy benzaldehyde, then we'd be talking...
What do you mean?
Actually, what i intend to use the alkoxides for is for making interesting stuff from bromovanillin - there's such a wealth of potentially possible compounds here, many quite potent, too - and, depending on the order of alkylations, both 3,4,5 and 2,4,5 can bee produced. What of 4-iPr-2,5-diMeO-PEA, say? It's not even in PiHKAL
- should bee potent at 30-50 mg.So... Oh, yes, the main thing:
Calcium alkoxide can bee made by dissolving CaC2 in alcohol. If one reacts this soln. w/alcoholic NaOH, he'll get NaOAlk and p'p'tated Ca(OH)2.
Now, THIS is, IMO, the best method: it's shortest, cleanest and can produce a product free of NaOH (BTW, can anyone suggest a way to separate them?)
I don't know about you, bees, but in my country tech grade Ca carbide is widely available and cheap as shit - acetylene generators, y'know.
Can someone please tell me what impurities technical carbide has? (i know some Ca3P2, but what else?)
Well that's it for now, bye,
Antoncho
(Chief Bee)
01-20-02 19:06
No 258697
Chromic: Dissolve the aromatic and one equivalent each of NaBr and H2SO4 in acetic acid, and then add two equivalents of 30% H2O2 dropwise with good stirring - it brominates just as good as free bromine.
(Hive Prodigy)
01-21-02 02:51
No 258811
Antoncho: Just keep adding CaO, reacting, filtering, and repeating, until the Ca(OH)2 precipitation weight is calculated to mean ~100% conversion of solvated NaOH to NaOMe.
As you said, it is an equilibrium reaction, by adding the calcium oxide, you drive the reaction to the right through dehydration, and when you remove the calcium hydroxide, and replace with more calcium oxide, the equilibrium point keeps moving further to the right, towards total conversion.
As for the reactivity of p-DCB and NaOMe, I bet they will react when superheated in a pressure cooker. NaOMe is about as basic as NaOH, probably a slight bit stronger, and NaOH reacts with chlorobenzene ar 300C to form phenol and sodium chloride.
PrimoPyro
Vivent Longtemps la Ruche!
(Official Hive Translator)
01-21-02 03:43
No 258821
>Just keep adding CaO, reacting, filtering, and repeating, >until the Ca(OH)2 precipitation weight is calculated to >mean ~100% conversion of solvated NaOH to NaOMe.
Yep. Theoretically. Not practically feasible, though. You _must_ use xcess CaO and you _can't_ weigh them separately, y'know. Such means of control is essentially a failure when performed in kitchen conditions - sad but true.
Also - i believe that to aquire ~100% convertion you'll need not less than a month. With constant stirring, that is. Now, SWIM doesn't have such a stirrer, and he guesses that not many of us the winged creatures do. He just plans to seal it and shake once in a while for a month, maybee - that is, if the carbide route turns to bee somehow unsatisfactory.
>As for the reactivity of p-DCB and NaOMe, I bet they will >react when superheated in a pressure cooker. NaOMe is >about as basic as NaOH, probably a slight bit stronger, >and NaOH reacts with chlorobenzene ar 300C to form phenol >and sodium chloride.
Your reasoning is quite correct, i have nothing to object
It's just the fact that one can make dimethoxybenzene from such simple things as hydroquinone, MeOH and H2SO4 () that makes this route somewhat less sexyAntoncho
P.S. Guys, let me ask this once again: can anyone suggest how to separate NaOMe from NaOH?
Does anyone know what impurities contains tech grade CaC2?
(Stranger)
01-22-02 08:36
No 259262
Antoncho,
Tech. grade CaC2 is ca. 80% CaC2, the rest is mainly CaO, with the remainder mostly SiO2 & Al2O3. Also small quantities of nitrides, sulfides and phosphides.
(source: Ullmann's Encyclopedia of Industrial Chemistry)
(Official Hive Translator)
01-22-02 09:29
No 259277
2 Mountain Girl: Excellent, thanks a lot!
Antoncho
(Hive Photographer)
01-28-02 13:10
No 261794
Antocho,
This is a very nice piece of OTC chemistry. Very nice find.
Uemura
Carpe Diem
(Hive Bee)
02-07-02 17:49
No 266468
Won't p-DCB + NaOCH3 react when a Cu(I) salt is added, or are the yields still too low?
Hey, i just read Rhod & Os "MMDA and Mescaline" paper again:
Brominate MDA --> 6-Br-MDA ,
6-Br-MDA + NaOCH3 --(CuBr)--> 6-MeO-MDA or MMDA-2 !
e109
(Chief Bee)
02-07-02 19:10
No 266510
I believe the yields are still low with aromatic chlorides, if there are no powerful electron-withdrawing substituents on the ring.
Yes, making MMDA-2 may be that simple, but there is always better to do harsh transformations as the first steps of a synthesis. I would suggest that you brominate piperonal to get 6-bromo-piperonal, and then react that with Cu(I) and methoxide until it is all 2-MeO-4,5-MD-benzaldehyde, and then follow one of the usal steps known for making a benzaldehyde into a phenethylamine/amphetamine.
(Hive Photographer)
02-07-02 22:27
No 266609
Rhod,
Chromic: Dissolve the aromatic and one equivalent each of NaBr and H2SO4 in acetic acid, and then add two equivalents of 30% H2O2 dropwise with good stirring - it brominates just as good as free bromine.
Indeed, indeed ... So no nasty bromine vapours, and Uemura gladly confirms you get 92% 5-bromovanillin out of vanillin!
Now go ahead with Antochos OTC MeONa preparation to syringaldehyde.
Very nice, indeed...
Carpe Diem
(Newbee)
02-07-02 23:15
No 266629
hi uemura,
this is very good news, you should start a new threat.
otto
(Chief Bee)
02-08-02 16:52
No 266929
Threatening people with in situ bromine?
(Stranger)
02-08-02 17:04
No 266938
the first article states that the method can be used on alcohols with up to 6 carbons. anybee want to speculate if this would would with tert- butyl alcohol to give potassium tert-butoxide or does the alcohol need to be a straight chain?
(Official Hive Translator)
03-18-02 17:52
No 284348
anybee want to speculate if this would would with tert- butyl alcohol to give potassium tert-butoxide or does the alcohol need to be a straight chain?
I dunno. But check out this. They say the method works on any alcohol w/chain length 2-6 which forms a lower-boiling azeotrope w/benzene and water. Specific examples aren't given, but tert-BuOH is listed among them in the patent:
From Patent US1712830:
IMHO, also quite cool.That would bee the procedure #5
Antoncho
(Newbee)
03-21-02 13:49
No 285843
Another nice find Antoncho!! - and thanks posting the image extract. i noted that t-butyl alcohol is specifically mentioned in the patent. k-t-butoxide is useful in a couple of codeine conversions, o-demethylation to morphine with n-propanethiol and also an Oppenauer oxidation + reduction to hydrocodone - so i was wondering about the otc possibilities of preparing this chem from t-butyl alcohol. thanks again.
(Official Hive Translator)
03-21-02 14:42
No 285861
Our outstanding SWI-Vitsh of HyperLab forum did some xperimentation and the results are:
1) Route via Na2S is not practically feasible as purification from residual sulphides isn't possible in kitchen.
2) Stirring ~30.5g K2CO3 in 200mls at RT for 7 hrs yielded 7,7 gr of KOMe, after evaporation the soln to 11 mls volume. all went excactly as described in the patent.
,Antoncho
(Distinctive Doe)
01-30-03 07:23
No 402589
Post 236749 (foxy2: "This is even better.", Chemistry Discourse)
Sorry, I had to.
(Hive Bee)
01-30-03 23:28
No 402777
Yes, SWIM remembers that post foxy. That last paragraph looks great too...
"Removal of hydroxide ion from alkoxide ion solutions
Abstract
The concentration of alkali metal hydroxide contaminants in solutions of alkali metal alkoxides in alcohols is reduced to below about 0.1 percent by adding an alkyl alkanoate ester. For example, a solution of sodium methoxide in methanol containing about 0.04 percent sodium hydroxide was obtained by adding a small amount of methyl acetate. The alkali metal alkanoate salt formed as a by-product does not deleteriously affect most uses of such solutions. "
Thanks for reminding us