Author Topic: MDA using LiAlH4 and oxime. NEED HELP!!! (Read 253 times)

Oerlikon · « **on:** November 14, 2011, 09:33:55 PM »

Look...
I know this is s generally against this forum rules,but I am desperate,very short on time,very busy and need someone to help me with search this reaction ASAP!

As you know I failed MISERABLY to reduce ketoxime using Al/GAA multiple times and i won't spent any single mg on this foul reaction!
(Costed me 50g+ of the finest ketone/ketoxime!)
I solved this by ordering super expensive and hard to get LiAlH4 and it will be in my hands in just few days. (have Et2O as solvent)

I don't have a free time (exams and shit) to search all the books and web-pages for appropriate methods (writeups) so I need your help.
So,any good written,reproducible paper or writeup on reducing oxime to amine using LiAlH4 or NaBH4 will do.
(preferably isosafrole ketoxime to MDA or anything that will follow the same pattern)

I promise to submit my report on reaction IN DETAILS as soon as I get more time.
Thanks in advance!

lugh · « **Reply #1 on:** November 14, 2011, 11:07:15 PM »

Reductions using sodium borohydride are on Rhodium's page:

http://www.erowid.org/archive/rhodium/chemistry/redamin.zirconium.html

http://www.erowid.org/archive/rhodium/chemistry/oxime.txt

and a working procedure using LAH:

http://www.lycaeum.org/leda/Documents/2C-B_Synthesis.11171.shtml

Aa far as LAH, theoretically one would use one half of a molar equivalent to reduce the oxime to the amine just as one would need the same amount of LAH to reduce the nitro compound to the oxime

In the attached article, Journal of Organic Chemistry 17 294-7 (1952) DOI: 10.1021/jo01136a018 the authors state that optimal yields are obtained using about 1.5 moles oxime to one mole of LAH

Oerlikon · « **Reply #2 on:** November 15, 2011, 01:24:01 AM »

Thanks! Will read it completly tommorow and tell you more.
Stoichiometry is not a problem,I am more concerned with whole procedure:,adding reactants,extraction,eliminating dangers etc.
and even more with reaction parameters,like temperature,how long to react etc.
LiAlH4 is a nasty stuff and i never worked with it before (only NaBH4)

I will get it in pallets/prills.
Is it an good idea to crush them in powder or use straight as it is!?

lugh · « **Reply #3 on:** November 15, 2011, 01:36:45 AM »

A pictorial of how to crush LAH had already been provided in another thread:

http://127.0.0.1/talk/index.php/topic,2133.msg22364.html#msg22364

solvents should be dried in the same manner as for a Grignard reaction, a dust mask can be helpful and gloves are mandatory

As was stated in the other thread, LAH is pyrophoric so special measures are needed

Wizard X · « **Reply #4 on:** November 15, 2011, 01:54:20 AM »

LAH is soluble in many etheral solutions. However, it may spontaneously decompose due to the presence of catalytic impurities, though, it appears to be more stable in tetrahydrofuran (THF). Thus, THF is preferred over, e.g., diethyl ether, despite the lower solubility.[9] http://en.wikipedia.org/wiki/Lithium_aluminium_hydride#Solubility_data

Purify and dry all solvents accordingly.

Sol Invictus · « **Reply #5 on:** November 15, 2011, 03:08:38 AM »

While we're talking about LAH, I've heard that using methyl tert-butyl ether aka MTBE allows for both a greater solubility than THF as well as possessing a higher boiling temperature than diethyl ether. Thus a similar reaction to diethyl ether is achieved while avoiding the risk for peroxide issues, and with the greater BP a more vigorous reaction can take place. There is however the issue of it being an environmental groundwater pollutant if improperly disposed of.

I also remember reading in I believe 'The Synthetic Organic Chemist's Companion' (an excellent book mostly concerning lab technique) a really cool way to do a work-up of a post-LAH reaction so that the typically huge metal salt emulsion could be avoided by conducting a series of simple washes with different aq. solutions of a few salts. Wish I could recall the details here but I think you can find that title pretty easily for free online.

Hope some of this helps. Best of luck!

--Sol

atara · « **Reply #6 on:** November 15, 2011, 04:43:33 AM »

Why didn't you ask before you ruined your ketone? Acidic methods for reducing oximes never work. u.u

http://www.erowid.org/archive/rhodium/chemistry/oxime2amine.zn-af.html

RoidRage · « **Reply #7 on:** November 15, 2011, 04:51:20 AM »

Quote from: atara on November 15, 2011, 04:43:33 AM

Why didn't you ask before you ruined your ketone? Acidic methods for reducing oximes never work. u.u

http://www.erowid.org/archive/rhodium/chemistry/oxime2amine.zn-af.html

Haven't tried others substrates, but Acidic Al/Hg works like a charm with Isosafrole Ketoxime

lugh · « **Reply #8 on:** November 15, 2011, 03:59:46 PM »

An old thread from the Hive in which the LAH workup is discussed:

Chemistry Discourse

Posts 1 - 4 of 4 Subject: Nice way to quench LAH rxns.

beagle boy
( )
11-03-98 16:50
No 100225
Nice way to quench LAH rxns.

I haven't seen this covered here, so I am posting it in the hope that it may prevent someone from having a nightmare.
LAH reductions may be quenched in several ways. Sometimes ethyl acetate is used, because hydrogen is not evolved, lowering danger of fire/explosion.
This method should not be used with amine products, however, because of side reactions. Another method often used is to simply add H2O, ice chips, or wet solvent till bubbling ceases. The problem with this method is that if too much H2O is added, the resulting inorganic salts become gel-like, causing problems in filtration and washing. Only a slight XS amt of H2O is necessary to cause problems. When the proper amount of H2O is used, the salts form a granular consistency, which is easily filtered. A good solution to this problem is to add n mL of H2O, n mL of 15% NaOH, then 3n mL of H2O for every n g. of LAH used. A properly quenched rxn can make the difference between an 80% yield and a 95% yield, so I hope this may be of use to someone.

Scooby Doo
(Member)
11-05-98 07:03
No 100226
Re: Nice way to quench LAH rxns.

Sure is beagle, Thanks!!!

beagle boy
( )
11-07-98 03:23
No 100228
Re: Nice way to quench LAH rxns.

Either sat. Na2SO4 or sat. NaCl at the end is a very good modification of this quench.

assholium
(Member)
11-07-98 11:46
No 100227
Re: Nice way to quench LAH rxns.

Beagle Boy:
>n mL of H2O, n mL of
>15% NaOH, then 3n mL of H2O for every n g. >of LAH used.
ok, but I usually used satd. soln. of Na2SO4 at final quenching - and always got beautiful results - granular & easy filterable... i.e. n ml of H2O, n ml of 15% NaOH and then 3n ml of satd. Na2SO4.

Posts 1 - 4 of 4 (Intrinsicality)

Oerlikon · « **Reply #9 on:** November 15, 2011, 06:12:30 PM »

Thanks guys! As I thought,post LiAlH4 workup is not a joke.
Every link and idea is welcomed!

BTW I can get Et2O ONLY as the solvent now and there is no need to mention environmental issue since I dispose all of my crap professionally.

antibody2 · « **Reply #10 on:** November 15, 2011, 08:45:52 PM »

Quote from: atara on November 15, 2011, 04:43:33 AM

Acidic methods for reducing oximes never work. u.u

Atara - That simply is not true.

As Roid rage mentioned and hundreds of bees can attest.

lugh · « **Reply #11 on:** November 16, 2011, 12:57:07 AM »

The first Hive thread on MDA via the oxime using the al-hg:

Methods Discourse

   All 16 posts         Subject: MDA via oxime



        Chromic
(Hive Addict)
07-11-01 11:29
No 189969
                  MDA via oxime

I've asked this at the Zonez, and I'm looking for other input. Can anyone enlighten me if my friend can use Hg/Al to reduce mdp2p oxime? Would that give MDOH, MDA or nothing at all? Also, he's assuming hydroxylamine sulfate can be used interchangably with the hydrochloride... in which case, is Na2CO3 or NaOH in methanol or ethanol a better route for the oxime's preparation?



        Antibody2
( )
07-11-01 15:31
No 189985
                  Re: MDA via oxime

Chromic - Yes, it will give a mixture of both MDOH and MDA. I'll have to check the dream log, but as i recall (microscale) yields were

10% aqueous THF less than 10%
10% aqueous MeOH 17%
10% aqeous MeOH with 4 equiv 31% HCl (w/ lewis acid*) near 25%
10% aqueous MeOH with 8 equiv HOAc (w/ lewis acid*) 25%**
10% aqeous MeOH with 4 equiv HOAc (w/ lewis acid *) 62%!!!smile

in all the above 10 equiv of Al was used. it is not at all exothermic like reductive amination, so there is no reason other than volumetric consideration when choosing foil thickness.

average rxn time was 8-12 hours and hot water baths were used occasionally to prevent the rxn becoming sluggish.

* there were concerns that the acid would be consumed by the Al and that the freebase would eventually turn the suspension basic, so for this reason silica gel (flower driing type) was added to rxn. Was reading somewhere that hydrogenation of oximes in acidic media inhibits coupling rxns and favour the production of primary amines.

** this rxn accidentally evaporated dry while forgotten on watyer bath, so is possible the yeild could be greater.

For what it is worth acording to Hata oximes can also be reduced using Urushibara Catalyst activated with NH2

hope that helps Chromic



        Rhodium
(Chief Bee)
07-11-01 15:40
No 189987
                  Re: MDA via oxime

What lewis acid did you use, and how much? If you say 10% aqueous MeOH is that 1 part water in 9 parts MeOH or the other way around? And I don't really understand what you are using the silica gel for?

https://www.rhodium.ws



        Antibody2
( )
07-11-01 16:09
No 189991
                  inspiration?

in a rxn with 2g (10mmol )oxime (the 3,4-MDP-2-P variety) 1g of silica gel (the lewis acid) was used. in scale ups it was reduced to half that ratio.(using too much complicates work-up). the following was where the acidic solvent inspiration came from.

Acidic solvents or solvent systems are recommended to minimize reaction rate inhibition caused by the amine product(s). Primary amine formation is favoured by the use of acidic solvents or ammonia to minimize reductive coupling reactions

h**p://www.chemicals.matthey.com/catalysts/viewnarrative.asp?ProcessID=23

i realize the above ref is not strictly relavent and i am not convinced that the silica gel(lewis acid) was actually neccessary, it was more of an insurance policy to keep everything protonated in the event that the all the HOAc reacted with the Al making aluminum acetate or the HCl making AlCl3 (don't know if possible) but figured it couldn't hurt. that's all. the chemist could have kept adding acid but this would complicate the work-up and the dream chemist is colourblind so PH is difficult to accurately determine.

what do you think? was it necessary, i'm not sure, just know it worked so was not motivated to try and make it not work. easy to get carried away with variations and loose sight of the goal. and up there we definately have a winner.

and yes - 1 part H2O, 9 part MeOH.



        hypo
(Hive Bee)
07-16-01 12:36
No 190895
                  Re: inspiration?

ab2!! this _is_ a definite winner!

6g Al (thin foil, folded, cut into small pieces and nuggetized) was amalgamated in around 200ml IPA. 4.8ml AcOH, and 3g ketoxime (from anethole) were added. the reaction was stirred for 12h. it was exothermic but the IPA never started boiling. usual workup (basify, extract with toluene, wash, gas) yielded 2g of white powder (not dried, so maybe less).

my friends lab technique sucks and the used glassware was not suited for small scale reactions.

fantastic!

edit: forgot to mention that some water was added with the ketoxime and the AcOH

Man was not born to work.



        LaBTop
(Daddy)
07-16-01 18:19
No 190946
                  Re: inspiration?

(not dried, so maybe less).

Dry it, and it will be a lot less, more than you think.
Be precise, first rule here. LT/

WISDOMwillWIN



        Chromic
(Hive Addict)
07-16-01 21:52
No 190990
                  Re: inspiration?

AWESOME NEWS!!!! Thanx hypo, you have just given me enough faith to try this again... even a 50% yield would make me happy. Maybe I'll even do a run with PMP2P ketoxime just for the heck of it. I've never tried PMA. How did the bioassay go?

Btw, what procedure did you use for forming the oxime?



        hypo
(Hive Bee)
07-16-01 23:31
No 191007
                  Re: inspiration?

oh, this particular batch was not assayed. had a nice experience with another batch though. some visuals in the trees, general 'i dont give a fuck'-feeling. my advise if you like to try it: do it outside, drink a beer and waste your time. dont expect much psychedelic and dont fear the cardiovascular.

the ketoxime was made ala sonson, everything scaled up by 10 and replacing MeOH with EtOH. can take longer to crystalise, but works perfect.

lt: the thing was placed in dissicator. i dont believe it will loose much weight though (at least not enough to make a difference for my friends scale).

Man was not born to work.



        Antibody2
( )
07-17-01 15:23
No 191171
                  Re: inspiration?

cool hypo, thats great news. so it looks like maybe the silica gel isn't required after all. that settles that then.

"All those memories lost like rain..."



        Chromic
(Hive Addict)
07-17-01 22:27
No 191270
                  Re: inspiration?

So the conclusion is that it's mostly MDOH?



        Antibody2
( )
07-17-01 22:44
No 191276
                  Re: inspiration?

i think so Chromic, it was like doing x for the 1st time all over again, no tolerance laugh. it's not often one's virginity is restored.

if you are intent on MDA though, MDOH apparently decomposes to MDA at temperatures exceeding 100C

"All those memories lost like rain..."



        Rhodium
(Chief Bee)
07-17-01 22:52
No 191278
                  Re: inspiration?

Then a simple distillation of the freebase should do the trick.

https://www.rhodium.ws



        Osmium
(Stoni's sexual toy)
07-18-01 13:16
No 191437
                  Re: inspiration?

As far as I know heating MDOH will convert it into a mixture of MDP2P and MDA. So if you have MDOH better don't try to convert it.



        Antibody2
( )
07-18-01 15:01
No 191459
                  Re: inspiration?

shulgin states in pihkal that when a mixture of MDA and MDOH are distilled to separate the two freebases,

crystals, which weighed 1.4 g when air dried. If the temperature of distillation exceeded 100 ¡C, there was extensive decomposition during distillation, with the formation of 3,4 methylenedioxyamphetamine (MDA) and the oxime of the ketone. Under these circumstances, the only base isolated was MDA. The surest isolation procedure was to obtain MDOH as the free base, as a crystalline solid which could be recrystallized from 5 volumes ofboiling IPA.

you are right Os, far better to simply eat the stufftongue

"All those memories lost like rain..."



        hypo
(Hive Bee)
08-08-01 20:07
No 202574
                  exothermic!

addendum:

my friend tried this reaction with 10g of the oxime in EtOH and the thing nearly boiled over! so if someone wants to do this on a larger scale, he better uses thick foil or adds the oxime slowly. and has a waterbath prepared.

so much to the myth that only the MeNO2 reduction is exothermic...tongue
Man was not born to work.



        Osmium
(Stoni's sexual toy)
08-08-01 22:39
No 202603
                  Re: exothermic!

Somebody submit a detailed writeup please!


   All 16 posts

lugh · « **Reply #12 on:** November 16, 2011, 01:07:50 AM »

And the second such thread:

Methods Discourse


   Posts 1 - 18 of 18         Subject: Al/Hg/HOAc Oxime redxn



        Antibody2
(Rehabilitated)
04-18-02 04:01
No 298425
                  Al/Hg/HOAc Oxime redxn
(Rated as: excellent)

Al/Hg reduction of MDP-2-P oxime in acidic EtOH
by Antibody

For obvious reasons an alternative catalyst to sodium was sought for the reduction of the oxime of MDP-2-P to its amine
derivative. This investigation led to experimentaion with various solvent systems including THF, MeOH, EtOH [1], both aqueous and non-aqueous, acidic and neutral, with various acids being employed. Hazards and low yeild ruled out THF, and long reduction times and moderate yeilds led to the abandon of MeOH systems. Aqueous systems afforded superior yeilds with all solvents triied. Non acidic solvent-sytems failed altogather. HOAc provided higher yeilds than HCl. Different acid proprtions were triied with 10 equivalents producing the highest yeilds. The amount of Al used also impacted yeilds as well as the amount of MDOH by-product produced. With increases boosting overall yeild but lowering yeild of MDOH.

It should also be noted that the following solvent/redxn system was sucessfully employed in the manufacture of MMDA and DMMDA but in lower yeilds, 10% and 50% respectively. It failed repeatedly with DMMDA-2 altogather.

Experimental
In a 4l beaker with mag stirring, 0.75 moles of activated Al (19.5g) [2] is added to 1l 95% EtOH and 100mls dH2O, followed by 0.33 moles oxime of MDP-2-P (65g) [3],and 3 moles HOAc (180g). The Rxn is heated to 60C and heat removed. There follow three additions of 0.75 moles of activated Al at 30 minutes, 1 hour, and two hours. Temperature was maintained at 60C by placing beaker in a cold water bath as necessary. There is a vigourous evolution of hydrogen as the rxn progresses, care must be taken the rxn vessel does not overflow. An additional 150mls 95% EtOH and 15mls dH2O is added at 2hours. At 3 hours the rxn is a viscous gel which has stopped the stir bar. An additional 300mls 95% EtOH and 30mls dH2O is added . The rxn was allowed to stir until it has returned to room temperature, during which time 1 l of 15M NaOH was prepared and cooled. The rxn vessel was placed in a cold water bath and the basic solution was added slowly over 20 minutes, with care being taken the tempertaure did not rise above 60C. 500g of NaCl was added, much of which precipitated after stirring. 500mls toluene is added with stirring. The toluene/EtOH/amine layer is separated and decanted into 750mls of dH2O, causing the EtOH to migrate to the aqueous layer. The toluene layer is separated and the aqueous/alcoholic layer is extracted 2 times with 250mls toluene. The pooled toluene extracts are washed once with 400mls dH20 and once with 400mls brine, then driied through MgSO4 and gassed w/ dry HCl gas.

yeild 0.267 moles MDA.HCl (54g)
81% molar yeild

1) see Post 189985 (Antibody2: "Re: MDA via oxime", Methods Discourse)
2) activated by refluxing in 19.5g Al in 800mls of 50/50 dH2O/MeOH, with 1g Hg2Cl2 for 15 minutes, the mercuric solution was decanted, and Al was washed once with 400mls 95% EtOH, which was also decanted. Same mercuric solution was
used for all four activations.
3) prepared according to Sonson, see Post 54080 (Sonson: "High-yielding synthesis of MDA from MDP2P", Methods Discourse)





        Chromic
(Hive Addict)
04-18-02 06:19
No 298493
                  Excellent writeup!

Let me be the first to say this is an excellent writeup which deserves to go on Rhodium's webpage asap! Kudos!

I also want to add that as variations on Sonson's oxime preparation that one can:

Mix:
(1) 7.9g Na2CO3 or 20.4g NaOAc.3H2O (150mmol)
(2) 15ml H2O
(3) 10.3g (NH2OH)2.H2SO4 or 8.7g NH2OH.HCl (125mmol)
(4) stir bar

Stir, then add:
(5) 100mmol phenylacetone (22.4g 2,4,5-tmp2p 16.4g pmp2p or 17.8g mdp2p)
(6) 75ml MeOH or 75mL EtOH

Then do the 1.5hr reflux, cool in fridge, and suction filter a la Sonson. The calculations were a pain, so I thought I'd include them here so other people don't have to repeat them.



        uemura
(Hive Photographer)
04-18-02 06:39
No 298498
                  Good to see you back...

Hello ab2,
Good to see you back! Uemura hopes you will again continue to provide such good posts as the above one in the future smile. And yes, this oxime reduction should be saved on Rhodiums site! Carpe Diem



        Chromic
(Hive Addict)
04-23-02 20:04
No 300495
                  One more thing

I also want to add that at the end of the oxime preparation (not the reduction), I always see a white solid sludge that settles to the bottom. This is not the oxime, but some sort of inorganic salt. I'm not sure if this is common or not (anyone else seen this?), anyways, after cooling the flask in the freezer (and adding 40ml of water! oops, sorry for the omission!) the oxime crystallizes and fills the alcohol solvent with crystals. Don't skip the cooling step...

(I forgot to mention the addition of 40ml of water at the 100mmol ketone scale before putting the flask in the freezer, if one fails to do this, one won't see the oxime form as it needs that extra water to crash it out of the alcohol... and if you just add a ton of water and skip the freezing, the oxime will just "oil out"... I've made about every mistake possible with this very simple preparation, no need for other bees to repeat my mistakes...)



        Vibrating_Lights
(Hive Addict)
04-24-02 03:33
No 300612
                  In organic salts

Swim has also seen these salts, that chromic mentions, form after a Nitro reduction.
Vl_



        Antibody2
(Rehabilitated)
04-24-02 22:39
No 300884
                  yes chromic, i've seen it in virtually every ...

yes chromic, i've seen it in virtually every oximation i've ever done, but it disappears when you add the H2O. Its either the XS base or NaCl crashed out by the ketone or oxime i think



        psychokitty
(Her Majesty, Stoni's Kitty)
04-29-02 10:29
No 302926
                  Reduction of nitroalkenes to aldoximes

Here's a new one (I think) for reducing nitroalkenes to aldoximes:

General Proceedure for the Synthesis of Oximes.

The synthesis of 9-anthracenylacetaldoxime is representative of the proceedure employed. w-(Nitrovinyl)anthracene (1.25 g, 5 mmol; is this right? I can't read this part), SnCl2-2H2O (2.25 g, 10 mmol) and ethyl acetate (25 mL) were placed in a 50 mL Erlenmeyer flask and the mixture stirred at room temperature. A mildly exothermic reaction ensued which was accompanied by the gradual disappearance of the yellow coloration (nitroalkene). The reaction mixture was carefully poured into ice water--

Which presumably forms an acidic aqueous solution making the water soluble amine-HCl salt.

--and the solution made slightly basic (pH 7-8) by addition of 5% aqueous sodium bicarbonate. The product was extracted into ether, washed with brine, dried (Na2SO4) and the solvent removed under reduced pressure to yield essentially pure E/Z mixture of 9-anthracenylacetaldoxime.

For nitrostyrene and p-isopropyl nitrostyrene the length of the reaction was 6 hrs with a 94% and 92% yield. For p-bromo nitropropene, 5 hrs and 89%.




        Rhodium
(Chief Bee)
04-29-02 11:11
No 302932
                  oxime salt?

Which presumably forms an acidic aqueous solution making the water soluble amine-HCl salt.

The oxime HCl salt you mean? What is the ref for this?



        Antoncho
(Official Hive Translator)
04-29-02 13:09
No 302956
                  The method

This article was 1st posted by Yellium a while ago and interested me very much at the time. Rhodium said that Ritter witnessed the fact that it worked as described at that scale, but produced only tar on larger scale - but '...it may bee simply a matter of twitching the rxn conditions.'

Also - i am very interested in the possible reduction of oximes with zinc. Any successes with it yet? On Rhodium's page there is quite a collection of such reductions, all performed on complex, picky molecules, always with ~90% yields.

Antoncho



        psychokitty
(Her Majesty, Stoni's Kitty)
04-29-02 20:18
No 303060
                  Sorry. . .

Rhodium: I don't know what the hell I was thinking when I wrote that. I guess as a result of fatigue, I mistaked the end-product as an amine rather than an oxime even when I was staring right at the paper itself. It was late when I posted last. Sorry.

Here's the ref: Post 70459 (yellium: "Syn. Comm 18(7), 693-697 (1988)", Novel Discourse)



        Antibody2
(Rehabilitated)
04-29-02 21:59
No 303082
                  i heard the same thing from ritter, i did however ...

i heard the same thing from ritter, i did however see another nitro>oxime SnCl2 rdxn in acetone that looked promising, i'll see if it can be found

antoncho Zn/Ni Urishibara w/ NH3 as base should reduce the oxime to amine



        Starkas
(Newbee)
05-08-02 17:13
No 306260
                  HgCl2 substitute for Hg2Cl2

2) activated by refluxing in 19.5g Al in 800mls of 50/50 dH2O/MeOH, with 1g Hg2Cl2 for 15 minutes, the mercuric solution was decanted, and Al was washed once with 400mls 95% EtOH, which was also decanted. Same mercuric solution was used for all four activations.

Can I use HgCl2 instead of Hg2Cl2? Do I reflux for the same time with the same quantity (1g)?

This question probably belongs in the Newbee forum but I didn't want to start another thread.

Cheers...




        Antibody2
(Rehabilitated)
05-08-02 17:41
No 306276
                  HgCl2 is in fact preferable (although more ...

HgCl2 is in fact preferable (although more dangerous to handle), it will amalgamte much quicker, and you could get by with less, probably as little as 0.1g



        Antibody2
(Bee without a Title)
08-05-02 06:28
No 341463
                  MDOH

A recent batch of MDOH was prepared via Al/Hg redxn of the ketoxime using 5 equivalents of Al and HOAc, 150mls H2O, 200mls IPA and 1650mls MeOH using the above proceedure. (10x produces higher yeilds with a much higher MDA ratio) In an attempt to further isolate the MDOH, its lower solubility in alcohols was exploited, and was slowly recrystalized from an equivalent w/w of boiling MeOH. The crop of crystals that formed when the solution had cooled to RT were vacuum filtered. The balance refridgerated to produce a second crop. Then reduced and and refridgerated to yield a third. (yeild ca. 72% w/w from oxime)

The odour of the first and to a large extent the second crop was completely dissimilar to MDA. The odor could be characterized as sweet. If you are familiar with MDA there is no mistaking the two.

trip report Post 341465 (Antibody2: "MDOH - strong disassociative", General Discourse)



        madprosr
(Hive Bee)
03-25-03 17:21
No 421144
                  swim tried it out <grin>

he treated 9g of wet mdp2p oxime (it had been drying 5days as a paste, and was finally 'crumbly') as if it were 9g of dry oxime using antibody's reduction in EtOH.

it took a bit more EtOH than expected, like 200ml of 85% to start with and 3x 20ml more to keep it stirring over 5h. required intermittent cooling the first 1.5h to keep it at 60C.

anyway, swim used his head and added 28.5g NaOH (still overkill as pH was 14) instead of the 80g antibody reccomends, no NaCl, and enough h2o to make 1.5x the volume of EtOH in the reaction.

extracted with 100ml, 4x 50ml toluene, washed with 3x 100ml brine, dried, and gassed out 7g of bright white mda.hcl.

if you fail to add enough water to the alcoholic mother solution, it simply is not dense enough for the toluene to separate out on top. which complicates the workup and can cause emulsions that would never have otherwise occured...

anyway, the best part is that swim measured the MP at 186-188C.

from Phikal-
hydrochloride salt [of MDOH] had a mp of 149-150 °C (and should not be confused with the hydrochloride of MDA which has a mp of 185-186 °C since the mixed mp is depressed, mp 128-138 °C)

swim expected his MP to be 1-2C high, as he was measuring the temp of an oilbath containing a test tube with ~30mg mda at the bottom. so the MP is right on, no mdoh present here!



        Antibody2
(Hive Addict)
03-26-03 18:10
No 421463
                  use less Al and get more mdoh

use less Al and get more mdoh



        TheBlindGenius
(Hive Bee)
09-22-03 01:58
No 460293
                  What kind of Al
Have been studying this method, perhaps in the future would like to try it. What kind of aluminum should be used for this? It's not really specified anywhere Ive looked whether aluminum turnings, or sheet, or foil, or whatever are to be used.
The working man is a sucker



        Chromic
(Synaptic Self-Mutilator)
09-23-03 05:22
No 460488
                  Foil

Foil--any kind will work. I preferred Reynold's Heavy Duty.


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Author Topic: MDA using LiAlH4 and oxime. NEED HELP!!! (Read 253 times)

Oerlikon

MDA using LiAlH4 and oxime. NEED HELP!!!

lugh

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Oerlikon

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lugh

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Wizard X

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Sol Invictus

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atara

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RoidRage

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lugh

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Oerlikon

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antibody2

Re: MDA using LiAlH4 and oxime. NEED HELP!!!

lugh

Re: MDA using LiAlH4 and oxime. NEED HELP!!!

lugh

Re: MDA using LiAlH4 and oxime. NEED HELP!!!