asarone epoxide/glycol rearrangement questions

[moo]

Now that you asked, I realized I'm not completely familiar with the reaction mechanism. In

Post 303940 (missing)

(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?

[Rhodium]

Formic acid is not your typical carboxylic acid. Have you read the Leuckart Reaction review on my page?

[moo]

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).

[Rhodium]

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.

[randolph_carter]

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 (missing)

(Antoncho: "Leuckart with 92%+ overall yield", Methods Discourse)

Post 61613

(psyloxy: "Re: Leukard scaleable ?", Methods Discourse)

Post 27089 (missing)

(Chopper_: "Re: Ducks need help with Leukart", Methods Discourse)

Post 240004 (missing)

(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......"

[madprosr]

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.

[Rhodium]

you should add the 75% steel/AcOH tmp2np reduction you posted here awhile back

Where is that document?

[GC_MS]

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!

[randolph_carter]

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......"

[Vitus_Verdegast]

...I just wanted to point out that Randolph_Carter states in his TMA-2 write-up at

https://www.thevespiary.org/rhodium/Rhodium/chemistry/tma2.html

:

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 (missing)

(uemura: "Re: More Asarone info", Chemistry Discourse)

http://www.naturalhealthnotebook.com/Herbs/Latin_Herbs/Genus-A/Acorus_calamus.htm

A Simple Process for Asarone free Acorus calamus oil.

http://www.tifac.org.in/offer/tsw/ihbt5.htm