10-13-02 22:08
No 368088
swim dreamed 20g of double-distilled asarone yields 24.5g of nice yellow glycol/glycol acetate strictly following chromic's peracetic oxidation (with NaHCO3 buffer and NaOH washes). so far so good.
however, 30ml MeOH and 120ml 15% h2so4 refluxed for 1.5h turned everything deep brown at which time the mixture was cooled, and extracted w/ 120ml dcm.
3x 100ml 5% NaOH washes looked progressively less dirty but were not continued as it was thought the NaOH was decomposing something and would always wash light brown. 6x 100ml nearly-saturated NaCl washes all looked kind of orange/brown.
at this time the dcm looked white and milky, 3/4 of it was partitioned and stripped off yielding 7.75g brown viscous oil.
in swim's dream he was unable to distil this, but got it up to about 200C and then added 1.75g NaI (sodium iodide, 1/3 molar eq. to 7.75g ketone) slowly with stirring. some yellowish iodine gas was liberated, probably only a little NaI decomposed. upon cooling, 1/4 of the oil turned to grayish crud at the bottom. looked like too much to be elemental Na (will see after filtering, adding h2o!).
it has been stoppered in the freezer 2 days and small clear crystals have appeared on the sides of the flask. soon will see if these do not melt (ie not ice crystals) and how much (if any) sweet sweet ketone is recovered.
anyway, after UTFSE ppl say any lewis acid will rearrange the glycol...
swim has seen formic acid suggested, and acetic with h2so4 as a catalyst.
however swim has not seen actual procedures with yields for any glycol...
for 100mmol glycol, would 30ml MeOH + 119ml GAA + 1ml 93% h2so4 be good?
what about 120ml 15% formic, or 20ml 90% formic?
does h2o play an important role the rearrangment?
would a longer reflux be suggested with these acids as long as color is good?
swim is getting pretty sleepy...
(Chief Bee)
10-13-02 23:01
No 368099
Chromic's buffered peracetic oxidation should yield asarone epoxide. Here are two epoxide -> ketone tales:
It seems like the distillation of asarone glycol (and possibly also the distillaion of the epoxide, if water is present) forms a crystalline by-product,
which is a glycol dimer, and not solely 2,4,5-trimethoxyphenyl-2-propanone.
Asarone 1,2-glycol
Distillation of asarone 1,2-glycol (an oil) at 170-230°C/4 mmHg gives a red oil, which solidifies on standing. Through crushing the crystals under ether, a solid was left undissolved, which after recrystallization from alcohol melted at at 204-205°C, and had the molecular formula C24H32O8 [Could possibly be the 2,5-dimethyl-3,6-(2,4,5-trimethoxyphenyl
Reference: J. Chem. Soc. 1338 (1937)
Here is an anonymous contribution too:
Laugh at SWIM's yield, go ahead. But should she embark on a more sensible quarter-mole run, starting with 52 g asarone, in sizes where she can see what's going on, she'll expect me to put that in Novel discourse, when it's done. (I'll try to keep it down to novella length, though.) smile The point I wanted to establish in this post, is that thermal rearrangement of the epoxide works with asarone.
Using: Chromic's 100 mmole scale verbatim with 20.8 g asarone, 72.7 g oxone buffered with 24.4 g Na bicarbonate, in 500 ml water/200 ml methanol. The solution turned red about an hour into the reflux. For the workup, SWIM added 20 g Na bicarb, bringing the pH up to 8 before she distilled off the methanol. During the distillation, the flask contents were strongly black-red. She filtered with aspirator suction. With the methanol and solids out, she botched the extraction. With DCM, she was still pulling color on the sixth 40-ml separation, but discarded the solution. Undoubtedly she tossed some of her epoxide there. She may go back to ether extraction, more used to it.
With the DCM distilled under ambient pressure, she refluxed the epoxide 1 hour, with no companionship in the flask except the stir bar. She then rigged a short-path setup by attaching her thermometer adapter directly to the vacuum adapter (hose fitting plugged with a twist of tissue paper), like a straight distillation setup minus the condenser. When the distillation got busy, with a lot of drops of throughput, damp tissue laid over the adapters gave cooling. She got only 11.3 g crystal clear ketone, a 50% yield from asarone. Tale of woe: the heating mantle there is dead. She can see 10 ml undistilled limpid black oil left. To get it at ambient pressure, though, she'll have to go to the camp stove with open flame. Her hotplate/stirrer with mineral oil bath is left behind in the dust, just won't cut it. She even used foil, still not enough heat.
So there's no doubt at all, you can get over 50% crystal clear ketone from asarone, better than her. She aminated by Sonson's (MDP2P) hydroxylamine route to the oxime, using 10.8 g Na acetate and 5 g hydroxylamine HCl, in 10 ml water/40 ml MeOH. For the reduction of the oxime, she dissolved it in 100 ml denatured alcohol and 40 ml water, and added 7.0 g potassium hydroxide. The "unactivated" stage Urushibara nickel catalyst, 10% Ni deposited on 40-60 mesh aluminum granules, was then added, 2 grams of it, to this basic solution. Hydrogen generation was extended on 3 occasions by addition of 0.5 g aluminum flake, 50-80 mesh, at about 90 minute intervals. She used a microwave heating technique, a 30 second cycle whenever the tiny H2 bubbles slowed, or after adding more aluminum. Finally, though, she set the flask on the stirrer. Never mind the etching effect on glassware, of tiny nickel granules. For the last hour, she stirred @ 40°-50°. (If warmed and stirred the whole time, the reduction would bee complete in 4 hours. No help from microwaves in this case, but cheap entertainment to watch.)
The TMA-2*HCl is the real McCoy, bioassay by my buddy SWIM shows. (She took a preview taste test.) Got 9.3 g wet weight.
(Stranger)
10-13-02 23:28
No 368108
possibly not all the dcm came off, but aspirator vacuum was applied at the end and and bubbling ceased.
asarone = 208g/mol
epoxide = 224g/mol
glycol = 242g/mol
g.acetate = 284g/mol
so swim doesn't think 24.5g from 20g asarone can be the epoxide (or just glycol). will re-dream and re-check.
thanks much Rh for the oxone tale, but swim's dreams lack a heating mantle...
no suggestions on an alternate acid rearrangement?
details on "purification of the glycol through its semicarbazone yielded tmp2p"?
(Chief Bee)
10-14-02 00:52
No 368149
As long as you haven't purified the product by distillation or chromatography, you cannot ID the product bt weighing it like that. It can be a mixture of things.
An alternate rearrangement of the epoxide uses Lithium iodide. UTFSE for "LiI" or "Lithium iodide".
The glycol cannot be purified through the semicarbazone, but the ketone can. Most ketones form crystalline addition products with semicarbazide, just like bisulfite does, and can be used for purification.
(Stranger)
10-14-02 01:23
No 368168
swim could dream of thermal rearrangement of the epoxide/whatever on the stove with a safflower oil bath and crushed ceramic boiling chips...
this will probably only reach 300C without smoking, the atmospheric bp of asarone.
is there a verdict on brake fluid for higher temps? </Edit> DOT 5 smokes at 180C <Edit>
swim takes it 345-350C will actually bee necessary?
short-path is used instead of a water-cooled condensor so less heat is needed?
normally a 100mm claisen would be used with boiling chips, but this is a bad idea here?
</Edit> does anyone think swim can dream it with safflower oil on a stove using weak aspirator vacuum and ceramic chips and/or a capillary? is this a bad idea distilling to a short path? maybe with an uncooled liebig? <Edit>
(Stranger)
10-16-02 05:32
No 369086
swim found the obvious answer, a sandbath.
he dreamed of an even stranger creature last night 21.8g of clear golden oil from a 14.5g peracetic buffered with 5.7g Na2CO3. he distilled the dcm 5h with a hot water bath at atmospheric then 3h more under aspirator vacuum.
more oil than expected for asarone glycol acetate even,,
Rd's refs-
1) glycol rearrangment at 4mmHg, ketone dissolves and the dimer crystals don't
2) epoxide rearrangement at atmospheric with no weight of epoxide or temperature of distillation given.
the refs give swim some faint glimmer of hope, swim supposes he should
1) hit 230C with stirring under available refrigerator compressor vacuum.
2) hit 350C+ with a capillary under available vacuum.
3) hit 350C+ with ceramic boiling chips at atmospheric.
swim supposed boiling chips under vacuum is a bad idea and a capillary at atmospheric is just plain stupid, he is starting to feel smarter
someone tell swim if he will have a nightmare. he wishes he could skip 1) and keep the sand off his hotplate, but no-one likes a lazy hack.
strangely, swim has NaI, not bisulphite, has anyone actually used it with tmp2p?
swim dreams he feels like eleusis, can't believe no-one else does this. lol.
(Synaptic Self-Mutilator)
10-16-02 05:53
No 369099
Hey, I dreamed the peracetic dream with asarone many times before I finally realized it could work.
Other people do do it... we just don't have all the time in the world to experiment.
(Stranger)
10-16-02 20:33
No 369280
chromic, swim would've repeated your experiment exactly but lacks NH3OH...
his pump wouldn't distill the post-h2so4 crud, he wishes for your 48mmol (33%).
if this oil don't rearrange he will take a hint and dream of oxone.
swim has been here since the pseudonitrosite thread was kickin', still doesn't quite have the balls to distill ether. fukkin' gas stove pilot lights and all.
and 50% via oxone beats the pseudonitrosite.
swim swears he couldn't find 1 report of a successful NaI complex with tmp2p...
the crystals from the bottom of his flask seem to just be NaI spit back at him, after much toluene washing, he gets .6g from the ~1.75g he put in hot. bah.
swim is dreaming of distilling the oil under vacuum with a capillary.
with aspirator, first more dcm comes off, then as water comes off at 88C (ugh) the oil goes from gold to red to black. swim prays to the chem gods he has epoxide. if Rd says so, it's sure worth a shot. hawtin and aquaviva pound relentlessly. swim wishes he would dream of a more badass lab.
(Stranger)
10-16-02 21:41
No 369301
swim dreams the 88-82C distillate smells of acetic.
swim cleans the short distillation train and hooks up his compressor, the train fills up with smoke. yuck. he adds some wet rags on top, melts the tip of his capillary smaller. will wait and see, probably more burnt shit.
he forgot to dry the dcm. and can't figure out why it smelled of acetic after 2x75ml, 1x100ml 5% NaOH, 1x100ml h2o (added NaCl to break small emulsion) washes.
unless he had some glycol acetate...
anyone think epoxide from an oxone run is distillable with boiling chips?
this is one tough nut as in his dreams swim is always nearly broke.
(Chief Bee)
10-16-02 22:07
No 369306
You probably have some glycol acetate present, those washes should have removed all free acid.
Boiling chips are of no use under vacuum. You have no strong magnetic stirrer?
(Newbee)
10-16-02 23:03
No 369320
sure swim has a hotplate/stirrer...
but an oilbath will only hit 205C and sand directly on the hotplate 230C, hence his motivation for using a pot of sand on a gas stove which the stirrer will not stir through (no surprise). he is lucky if his pump pulls 45mmHg...
thank god swim's friend held on to 30ml sassy from a few years ago so soon he can stop pounding his head on a brick wall and have some fun, at least temporarily. its a shame the 20kg of sassy rootbark he collected sat 2 weeks before a 3-stage steam extractor was working. 20kg => 1g. don't let that rootbark sit!!!
swim really would love to confirm that 50% yielding oxone epoxide thermal rearrangement. wait and see
(Synaptic Self-Mutilator)
10-17-02 03:30
No 369415
No one has NH3OH!
I think you mean NH2OH and it's easily available as (NH2OH)2.H2SO4 or NH2OH.HCl at photography chemical supply shops. How were you planning to go to the amine without it?
Btw, I have experience distilling the results of a peracetic on asarone at atmospheric. My advice: do not bother. Yes, you'll get a forerun of acetic acid (even after base washing) and you'll get a very, very thick orange distillate. You won't be able to distill asarone ketone without a vacuum. Do not even try. It will turn to crap (this comes from a person who HAS distilled isosafrole ketone without a vacuum).
I gave up on distilling (my pump was broke) and after the 15% H2SO4 hydrolysis I went straight to forming the oxime and reducing. Try it. It will work... better yet, acquire a good vac pump and distill your ketone before the the amination.
There is only TWO acids I would recommend for rearranging. Either use tosic acid in toluene or 15% aqueous H2SO4 with methanol. Do not try anything else as you don't want to increase the amount of variables in your procedures! Try to keep the variables minimized...
(Newbee)
10-17-02 19:51
No 369627
of course, NH2OH is what swim dreams he doesn't have. if he ever dreams of having 50 bux, he could get 3lb of 99% nh2oh.h2so4. he assumes this is photo grade stuff which other bees have gotten to work, or is reagent grade really necessary? the reagent costs 5x more, and is, presumably, more suspicious especially in similar quantity. somenight swim will be an amalgam master. he has access to 5lb of Hg!!! eat shit and die totalitarians!
presently he dreams of having some formamide and formic which would be used exactly as written by RC in a 28h leukart + 8h conc. hcl hydrolysis. is extraction of the formyl intermediate really necessary (swim bets so)? as a tweak, he intends to wash the post-hydrolysis mixture with dcm before basifying and extracting the amine with dcm.
does anyone know how hard it is to distill tma-2 freebase? bp???
he would hate to dream such a good dream and then burn the freebase. he knows how to gas with hcl but heard this is useless without distilling first. he is kicking around the idea of acidifying with conc. sulfuric in acs IPA and crashing the salt with ice cold acetone. this is only frowned upon for MDMA, not MDA/etc? heard phosphoric was reccommended as well, has anyone tried both for comparison?
anyway, if the salt doesn't crash he will strip everything off (wishing he hadn't added so much acetone) and recrystallize from 70/30 EtOAC/IPA like barium wrote. promise to resist the urge to feed it to humans without 1 type of purification.
how is it that chromic, uemura (maybe others) have gotten piss poor yields of tmp2p from atmospheric distillation but the epoxide thermal rearrangement works? especially after the 1h reflux, you'd have ketone, which mrs. anonymous then distills at atmospheric in 50% yield. Rd, has this source ever fed you a bad line before? or a good one??
swim thinks to skip the reflux, but wants to keep the faith and avoid epoxide contamination. how far off are epoxide and ketone bp's?
anyway, swim has the unbuffered oxone, in a few days he'll be seeing the light or else making more burnt crap. thats what the capillary, aspirator, and sandbath did to the glycol, burnt the hell outta it. smoked alot, temp in the head hit 110C but oil looked so carbonized that he gave up. added .5g NaI, saw more yellow gas, yuck.
hey, anybody know how much higher the epoxide boils than asarone? swim could try to vaccuum distill it first as VL found it greatly increased yields with isosaf.
edit: uemura pulls epoxide at 125-135C at 2-4 mmHg which, using the nomograph on Rd's site, translates to 290C at 760mmHg or 190C under swim's 45mmHg vacuum. weird, as asarone is supposed to be 300C and swim pulls it at 180C under vac. can someone confirm whether the epoxide boils higher than the propenylbenzene???
dang uemura's extra low bp's...
OT: chromic, that GABA->GBL method is almost enough to make swim stop crying over the 16kg GBL he destroyed in 99 after one mind-breaking acid trip. at least the other 4kg was put to good use. swim had developed a severe aversion to the taste by then anyway, even in orange juice, but its still a shame.
thanks to the bees, just for bee-ing yourselves.
(Chief Bee)
10-17-02 22:04
No 369661
See Pihkal (link below) for TMA-2 freebase bp.
(Master Whacker)
10-17-02 23:54
No 369697
presently he dreams of having some formamide and formic which would be used exactly as written by RC in a 28h leukart + 8h conc. hcl hydrolysis.
Take it from someone who knows: Randolph Carter has been around here since day 1 but it appears his writing skills(when you can actually read what he wrote) are far advanced compared to his proficiency in organic synthesis. There is no way he produced the ultra-high yields of TMA-2 via Leukart reaction as claimed in the writeup at Rh’s. Phenylacetones simply do not work as well as other ketones with this rxn. If the rxn. is run as Randolph described, you will be lucky to isolate anything greater than a 30% yield of primary amine. Use the FSE and study up on the Leukart before you waste your precious ketone.
RC: Please don’t take this personally, I’m only in this game for the chemistry.
(Chief Bee)
10-18-02 01:13
No 369723
Ritter: The document has been updated with your comments. Could you please PM me whenever you find any errors or omissions on my page so that I get the chance to correct it?
(Newbee)
10-18-02 12:08
No 369903
are the 30% yields from leuckart with formic or GAA? HCl or KOH rearrangement?
so RC's procedure is just one substituted from another molecule...
swim always wondered where the freebase b.p. was in that document.
swim hopes the bees all saw the steel/GAA nitropropene reduction Rd posted! might as well put it in the sweet flag document too.
btw, shulgin only lists mp of 132-133 for tma-2 acetamide, 188.5-189.5 for hcl salt. advantage of having the nitropropene, lah, and ether swim supposes- no distillation did the good doctor do. not for tma, tma-6, etc either.
swim is going put this dream on hold a bit and dream a nice md-type dream chasing that sweet 70% leuckart psyloxy reported. distil->vac isomerize->distil->performic->h
(Chief Bee)
10-18-02 17:21
No 369945
The bp is broad, between 90-110°C at 0.5 mmHg.
(Hive Bee)
10-18-02 19:14
No 369970
Check out Post 302161 (Antoncho: "Leuckart with 92%+ overall yield", Methods Discourse) and... a Dean-Stark trap? Post 342520 (MaDMAx: "**Simple glass --> fancy glass!**", Chemicals & Equipment).
(Newbee)
10-19-02 01:03
No 370056
thanks moo, seen those threads but swim doesn't think anyone is suggesting decomposing formamide to ammonium formate. and psyloxy's 70% leuckart reads so nice, amine in 8-10h swim thinks.
read somewhere, the dean-stark is only really needed for straight p2p, not so much for heavier ring substituted analogs. how is it that removing the amount of water in the trap increases the reaction temperature? further, isn't the idea of the trap to remove water & nh3 while remaining almost completely full so that the formyl derivative can constantly overflow over the top of the trap and back into the reaction? swim doesn't see how the trap does anything different than a distillation setup if it never overflows...
(Hive Bee)
10-19-02 03:57
No 370101
Now that you asked, I realized I'm not completely familiar with the reaction mechanism. In Post 303940 (Rhodium: "Wrong again Neuromodulator", Methods Discourse) Rhodium sez the ammonium ion and the ketone react to form an imine, then formic acid adds across the double bond to form the amide.
The Dean-Stark trap is filled beforehand so that the water released by imine formation returns to the reaction mixture, as does the formyl derivative. In that case removing water from the trap raises the reaction temperature. The only thing I can't understand is: How is it possible to add a carboxylic acid to the double bond of an imine to form an amide?
(Chief Bee)
10-19-02 05:18
No 370108
Formic acid is not your typical carboxylic acid. Have you read the Leuckart Reaction review on my page?
(Hive Bee)
10-19-02 14:30
No 370199
I should've formulated my question differently. How can Zealot get quantitative yields of the formylamide using less than two equivalents of ammonium formate? One formic acid for the reduction, one for the formyl group, no matter which one of the reaction mechanisms take place. (R2C=O + 2 HCOONH4 ---> R2CH-NH2 + CO2 + 2H2O + NH3).
(Chief Bee)
10-19-02 19:33
No 370241
Addition of formic acid across the double bond of an imine to form an amide IS a reduction. In theory, if that pathway is followed, you only need one equivalent of ammonium formate.
(Hive Bee / Eraser)
11-27-02 18:17
No 383922
I have been quietly watching the ongoing leukart and asarone-> TMA discussions for some time and I have exception with ritter's allegation that the leukart is inherently low yielding....
actually when applied to unhintered p2p's ie straight p2p and n-methylformamide it damn near approaches 100% on io...
note i stated "approaches" not = 100% on io....
it is more of an art than a technique tho....
the skill and attention to ALL details of the worker bee is more important than any other single variable....
most of the important aspects i touched on in the write-up...
follow the reccomendations CLOSELY but not on earth...
your yield will decrease logarithmically with the increase in yer sloppiness as well as distance from the equator of europa...
check the literature and also numerous post at Rhod's site ....
also check with anyone ya might know who has did the ole p2p / n-methyl redux and ask if it wasn't "high yielding".....
as to other high yielding leukart raves on the hivage that have more than 30% yields....
see these linkages....
Post 302161 (Antoncho: "Leuckart with 92%+ overall yield", Methods Discourse)
Post 61613 (psyloxy: "Re: Leukard scaleable ?", Methods Discourse)
Post 27089 (Chopper_: "Re: Ducks need help with Leukart", Methods Discourse)
Post 240004 (PolytheneSam: "Re: Benzedrine method", Stimulants)
lizards KNOW that high yields are in fact DREAM-ABLE not just possible!!!!
RITTER - your experiences may have indicated low yields and i will not disagree that some ketones do not have high yields, just that some ketones i have dreamed of DO have high yields if dreamt immaculately...
maybee not the norm but definitely dreamable....
my apologies if it sounds like i'm arguing but we all are out for the same thing HONEY!!!!
and creative debate is always GOOD!!!
i would look forward to seeing refs to the low yields being discussed etc...
jus my lil 64,362 cents worth in the am....
"remember little ones, love is real,not fade away, so pass some ammo on today......"
(Newbee)
11-27-02 19:23
No 383940
RC, after seeing how 15% HCl hydrolysis turned swim's mdp2p formyl derivative into total crap as soon as the acid was added, swim cannot reasonably believe that you hydrolized tmp2p FD with concentrated HCl in 78% yield. KOH hydrolysis of mdp2p FD looked much better (until swim over-acidified it and the same shit happened). Sure other bees got 50% yield with 15% HCl but it is apparently a nasty, picky reaction.
Ritter, so your 30% yield resulted from using formamide/formic and conc. HCl hydrolysis as described by RC? you never tried alcoholic KOH hydrolysis?
Rhodium, loving the new stuff on your site, you should add the 75% steel/AcOH tmp2np reduction you posted here awhile back to one of the TMA documents.
Of course it's already established how much acidic al/hg reduction of the oxime kicks ass, but nh2oh while still available (for now) is not OTC in swim's area. It's good to have options.
Hopefully my next post will be back on the topic of this thread.
(Chief Bee)
11-27-02 19:24
No 383941
you should add the 75% steel/AcOH tmp2np reduction you posted here awhile back
Where is that document?
(Hive Bee)
11-27-02 21:17
No 383974
Randolph, you forget that the aromatic ring of asarone is highly activated. I'm almost sure that a substantial part of your formed crystals are in fact condensation products. Substituted P2Ps normally give lower yields than the ordinary P2P, since the ratio impurities/active compenent is higher. I think that Leuckart in this case gives you a bunch of pyrimidines instead of active component.
Ave Hive, synthetisandi te salutant!
(Hive Bee / Eraser)
12-02-02 19:51
No 385560
Survey sez....
GC_MS you may bee entirely on the buzzer there....!!!
ever since my Perkin Elmer GC went south i have been bumble beeing in the dark somewhat...
as to WHAT the byproducts could bee pyridimines is a good guess but without proper instrumentation this bee cannot verify and currently no experiments are planned for several months maybee all year...(all times quoted are approximate jovian coordinated universal time units) so i am not sure if we will have the time top spend on researching this now...
as you acurately surmised yields were purely based on "raw" weights of proto-honey and not on an actual yield of GC verified TMA-2 only...
so like .....
GC_MS can you loan me a GC or MS unit to verify...
wishful thinking i know.....
"remember little ones, love is real,not fade away, so pass some ammo on today......"
(Hive Addict)
01-09-04 05:28
No 481347
...I just wanted to point out that Randolph_Carter states in his TMA-2 write-up at ../rhodium /tma2.ht
Sweet flag grows throughout most of north amerika east of the rockies in the wild state in wet areas where wild rice and reeds would feel at home. I found immense stands in Tennessee and northern Mississippi.Therefore my granola-head sensibilities were not offended by the copious gathering, for extraction and transplanting of this aquatic plant to the wilds of extreme north Georgia. It's most prevalent constituents are asarone, eugenol and esters of acetic and heptic acids.
Then he goes on by stating that he extracts with a steam juicer/extractor 10 kgs of above-mentioned roots and yields 320 gr oil containing 210 gr asarone.
This is not possible, as North-American and Canadian varieties of Acorus calamus (the var. americanus) have diploid chromosomes and are practically void of asarone. Their essential oil chiefly contains esters and terpenes.
Post 372820 (GC_MS: "stench", Chemicals & Equipment)
Post 42281 (uemura: "Re: More Asarone info", Chemistry Discourse)
http://www.naturalhealthnotebook.com/Her
A Simple Process for Asarone free Acorus calamus oil.
http://www.tifac.org.in/offer/tsw/ihbt5.
The Other War (http://www.markfiore.com/animation/drug