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Author Topic: Could use some help, from the ozzies among us  (Read 486 times)

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Offline Lestat

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Could use some help, from the ozzies among us
« on: April 11, 2016, 01:31:42 AM »
Alright, this is a bit of an unusual request. But I cannot obtain the thing I seek myself,

What I'm after, are samples of an australian fern species called in the common parlance, nardoo, or to give it its proper binomial, Marsilea drummondii.
Why? for a biotech project. I'm currently working on new and ideally facile routes to replace the classic two-step rxn to synthesize chlormethiazole, the brominated homolog of chlormethiazole, and perhaps other modifications as I have time to explore the qSAR of the compound. Its an antiquated GABAa receptor positive allosteric modulator and inhibitor of the hepatic enzyme alcohol dehydrogenase. Easy enough for ME to synth, but the classic route, which goes thusly, as below, requires thionyl chloride, which is hard to
get for most chem/bio hobbyists, although they could get small amounts from certain types of long-life batteries for specialist applications. The russkis do that to chlorinate codeine for subsequent red phosphorus/iodine or RP/HI reduction. That gives the russian addicts a truly noxious mixture of godawful byproducts (due to the iodine/phossy reduction, its a very harsh rxn, involving prolonged reflux of a substrate in a mixture of red phosphorus and either concentrated hydriodic acid or iodine, same as the classic methamphetamine from ephedrine or pseudo synth so popular in the US amongst those who don't favour birch-benckeser reduction using lithium metal dissolved in cryogenic liquified anhydrous ammonia, a far more dangerous but infinitely cleaner and faster route, to methphet, beats the pants off the I2/RP LWR (long, wet reaction or long, wet reduction) any day.

The russkis, they call the shite desomorphine/godknowswhatelse slurry they are making 'krokodil' for the way it turns the addicts skin into scaly, diseased crocodile-looking shite, and the way the corrosive byproducts literally EAT the poor bastards, like, corroding them right down to the bare bones of limbs they shoot (good fucking god!) this stuff.


My project on the other hand, is to replace the SOCl2 used in the chlormethiazole synth, first its a bisulfite or metabisulfite cleavage of the B vitamin thiamine, B1 IIRC, its available in pots of 100mg tabs as a supplement cheaply, or vitamin pill.This splits it into a substituted pyrimidine fragment, and a thiazolylethanol, which precipitates out, of the aqueous solution of bisulfite/metabisulfite, leaving the pyrimidine bit in solution. The  thiazolylethanol is removed via mechanical filtration, or decantation, washed of remaining meta/bisulfite, dissolved in an acceptable solvent for the use of thionyl chloride, and then thionyl chloride in a further portion of said solvent is added, the mixture heated to reflux, held at reflux for a while and then the reaction should be quenched with water, or alcohol, methanol will react with residual SOCl2 to give methyl chloride, a volatile gas, water quench ends up with sulfur dioxide and hydrogen chloride, which are the boiled out of the solvent, the solvent stripped and either the resultant chlormethiazole base treated with a solution of ethanedisulfonic acid to form the edisylate salt (chlormethiazole is NOTORIOUS for being nigh impossible to form solid salts of, or just clean the base of SOx and HCl gas by boiling.


OR, for those who cannot get thionyl chloride, I came up with another way to perform the second step, using triphenylphosphine and ideally, carbon tetrachloride to form a triphenylphosphonium chloride, the active halogenating species here, which is then used to halogenate the thiazolylethanol from the initial cleavage step.

Carbon tet these days has been named anathema in commercial applications and much research even, but chloroform should work and chloroform can EASILY be produced at home in a matter of a couple of hours work, by means of the haloform reaction, which uses a strong base of the alkali metal hydroxide kind, such as NaOH, caustic soda, or KOH, caustic potash , which then is reacted with hypochlorite bleach and (NO PLASTICWARE! the dichlorocarbene intermediate from the deprotonated chloform will liquify plastic and turn it to slop, spilling a highly corrosive, oxidizing solution everywhichwhere. It'll eat people just as happily. GLASS, folks. Then this dichlorocarbene in-situ prep (its highly reactive, so much so it exists only transiently as an intermediate, consumed as its formed), is reacted with acetone. The result, is the haloform reaction (actually substrate just has to be a methyl ketone or the secondary alcohol isopropanol), if a methyl ketone or isopropanol is reacted thusly, chloroform is the result. CHCl3 can be a bit dear online, so I usually make my own.

Yields are not fantastic really for bulk synthesis of chloroform, but it can work out cheap enough given how available bleach is and caustic, as well as acetone.

And if anyone wants to take that rxn further, a useful sedative/hypnotic called chlorbutol or chlorobutanol, a derivative of chloral hydrate, 1,1,1-trichloromethyl-2-propan-2-ol, by base-catalyzed condensation reaction of acetone with some of your  chloroform yield, the chlorbutol being volatile minty-scented whitish clear needlelike crystals which are purified by sublimation, heating the stuff to volatilize it and condensing the vapor on a cold surface, leaving the rxn byproducts/waste behind.

It can be used to test for IPA and methyl ketones too , if its used to produce iodoform instead. bromoform can be synthed thusly also.

How, you ask, does a fern fit into this scheme? nardoo fern contains an enzyme called a thiaminase, it destroys thiamine in the body if consumed, has killed a group of ozzy explorers who didn't know to leach it with water to remove the poison first, it caused the thiamine deficiency disease beri beri, and killed them despite having enough food, it simply wouldn't give them any energy from consuming the food, due to no vitamin B1 to aid in energy usage.

So if it can poison by hydrolysing thiamine, why not use it to perform that same hydrolysis OUTSIDE the body, when hydrolytic breakdown of thiamine is the desired outcome, to use the fern as a source of sustainable agent for the first step.

There are Pteridophytes here that produce those same thiaminases, such as bracken fern (a toxin called ptaquiloside, mutagen and carcinogen need removing from bracken
if I tried to use it, that afaik isn't present in nardoo, also, nardoo contains 100 times as much thiaminase as does bracken.

Could our ozzy folk maybe keep their eyes out if they happen to see any of this fern? and be willing to send me some, of course I'll cover all shipping expenses, can't just get some myself, as it doesn't grow here.




Beyond the pale. Way, way beyond the pale.

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Offline renaeden

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Re: Could use some help, from the ozzies among us
« Reply #1 on: April 11, 2016, 07:32:48 AM »
It wouldn't get through customs.
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Offline MLA

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Re: Could use some help, from the ozzies among us
« Reply #2 on: April 11, 2016, 09:16:58 AM »
I think you are seriously overestimating the degree to which the membership here takes you seriously.

Offline Jack

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Re: Could use some help, from the ozzies among us
« Reply #3 on: April 11, 2016, 04:40:31 PM »
I cannot obtain the thing I seek myself,
Have you actually tried? When google searching: buy online Marsilea drummondii, am seeing the plant and seeds online inexpensive and ships all over the world.

Offline Yuri Bezmenov

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Re: Could use some help, from the ozzies among us
« Reply #4 on: April 11, 2016, 08:38:41 PM »
Quote
I think you are seriously overestimating the degree to which the membership here takes you seriously.

My irony meter just pegged.

Offline Genesis

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Re: Could use some help, from the ozzies among us
« Reply #5 on: April 11, 2016, 09:32:14 PM »
Quote
I think you are seriously overestimating the degree to which the membership here takes you seriously.

My irony meter just pegged.

 :congrats:

Offline Gopher Gary

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Re: Could use some help, from the ozzies among us
« Reply #6 on: April 11, 2016, 09:55:59 PM »
For the love of goddamn God, don't ever take me seriously.  :GA:
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Offline Lestat

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Re: Could use some help, from the ozzies among us
« Reply #7 on: April 12, 2016, 08:33:33 AM »
Anybody touting fern seeds, needs to contact me urgently via my official email, lestat_rett@stinkingrichcrownprinceofnigeria.fuckingsucker.com
Pteridophytes don't PRODUCE seeds, they propagate via spores, produced in lines of sporangia aranged along the leaflets of the large leaf structures (in those that grow feathery,
divided leaves rather than the likes of adder's tongue, with one-part, straightish shaped leaves without splitting into leaflets, those produce sporangia along the leaves down the middle)

The spores are so tiny, a sample could EASILY get through customs, all that would be needed would be to sprinkle some into folded paper sent as a letter, or better still, the sporangia sliced from the leaves, or leaving them on a narrow strip of leaf to keep all in one place. To actually see them individually with the naked eye is impossible, they can only be seen.

The leaves of pteridophytes are all thin, and fairly flat, and would very, very easily go into a letter envelope, within a piece of folded card, or a paper letter. Packages have to go through customs, but there shouldn't be a customs declaration even, in the case of a letter. Certainly here one does not, and nor in any other country I've had mail from, that wasn't in the form of boxes, packets, tubs, baggies, petri dishes/culture tubes etc.)

All the likes of those that come, I've seen there is a customs form attached, meaning obviously that my suppliers, and those I buy items online from that come from overseas, like the time I bought my lab microscope (hehehe, the seller was an indian [indian-indian, not red indian that is], and all he wanted from his business, was to work hard, please his customers in doing so, make honest money and earn his crust. So he was more than delighted to knock a few digits off the price tag as stated on paper for me. Meant paying a grand total of no pounds and sweet bugger all pence in import duty and taxes instead of having to fork out quite a hefty slice of the contents of my wallet. The guy was just running a hardworking, honest business, and as such, wanting to please his customers.

And of course, pleased indeed this particular customer was. Pleased as punch, considering quite what a high quality model like that costs, even coming out of india.
And I really like that he even threw in a box  each of slides and glass cover slips,a spare condenser and other optics, including a quite powerful magnification oil-immersion type lens, and some immersion oil, and sent me too a microfiber cleaning cloth, and a few sundries like a spare bulb for the light under the stage.

All in all, leaving lil ol' lestat a very happy customer indeed,  because he didn't have any obligation to knock the stated price down to below the threshold of having money stolen from me to bloat govenment coffers , although that alone, didn't cost HIM anything to do. But he really didn't have to send me a gift of some quite pricy, new, and fairly decent optics for the new 'scope (new at the time, its served my lab and I well now for a good few years.

ESPECIALLY comes into its own for either any microbiology work I do, and more so still in assisting me in the identification of the wild mushrooms I so love to go picking and eating when the descriptions in some of my field guides do not provide sufficient information for me to identify a given species, thats a que for my portable field reagent-kit to get brought out, and also for things to be separately packed than the rest of my day's discoveries for further ID at home, using my bigger, heavier, bulkier, from a carrying perspective (in the woods that is) advanced, and far more comprehensive textbooks, take spore prints from the fungi,  then load a bit of spore powder onto a slide, pop a cover on and go get really, really up close and personal with the buggers.

Does a really nice job too, although sometimes some kinds of samples being viewed do need to be treated with stains, or Melzer's reagent (a mixture of chloral hydrate, elemental iodine, potassium iodide, made up with distilled water. Its used for testing fungal spores to aid identification of the species being examined. The response being either amyloid (blue-black coloration develops when a sample of the spores is treated with a drop or two of Melzer's, and if needs be, given a little time to develop, although it usually responds quite quickly. At least, reasonably enough so that if it does delay, its not so long as to preclude the development of the reaction whilst still out roaming wherever one happens to be out roaming, and
have the test develop its end result before one must leave and go home again.

The other reactions, are inamyloid-no true reaction, although it can change color slightly, but its not a proper reaction, but rather, a light tan or  yellowish, this is due to solely mechanical
reasons, namely absorption of the Melzer's, and the I2 content coloring the spores directly, without it having to have truly reacted, as opposed to simply being stained.

Or dextrinoid, a reddish-rustyish brown.  In the case of an amyloid reaction, I just learned something earlier today that until then, I didn't know. That there are two separate sub-reactions for amyloid reacting spores, aside from the simple, widely known amyloid blue-black without other factors influencing the reactions development or the way it is expressed.

These being euamyloid and hemi-amyloid reactions, euamyloid rxn taking the form of an amyloid reaction when there has been no pretreatment of the sample with caustic potash or NaOH [neutralization is then required prior to application of Melzer's when caustic soda/potash solution has been applied, as it seems that Melzer's isn't compatible with strong base, which I didn't know until earlier today, having never known of the eu- or hemi-amyloid subtypes of reaction, although I've never actually had any issues in its use to make me need to actually LOOK for anything else different from that in my more comprehensive mycology guides, or my books that aren't field guides/encyclopediae, but specialized works on specific subjects, such as the copy of 'The Genus Claviceps, by Vladimir kren and Ladislav cvak, which is an advanced and very specialist tome dealing with, surprisingly enough, the fungal genus 'Claviceps', that being the genus in which reside those taxa generally termed the 'ergot fungi' or simply, ergots, a family of parasites, which live their lifecycle by infecting and parasitizing the seed heads, and the reproductive tissues in particular of various cereal grain grasses, most famously rye, but also infect various noncereals, such as various kinds of wild grasses, which is where my own ergot samples came from. Once they infect, the ovaries then become taken over by the  fungus  takes over, and instead of a seed ripening, what comes out of the grass florets is in fact a spur-shaped (ergot is apparently derived from the french word meaning 'spur')  structure known as a 'sclerotium', the sclerotia being one of the two reproductive pathways the ergot fungi may propagate by, acting as a resting structure that falls to the ground from the grasses, overwintering, and then sprouting small structures which produce the sexual ascospores,
the other type being when the sclerotia are still forming, or formed and remaining in the grass florets, then sticky 'honeydew' is exuded, which is positively laden with macro- and microconidia, the conidiospores, unlike ascospores, or the basidiospores of a basidiomycete fungus [the ergots are ascomycetes, or spore-shooters, which eject spores, ]the basidiomycetes on the other hand, are spore-droppers, the spores simply dropping from the gills or other sporulating structures, and going with the wind, rather than having a means of
active propulsion away from the fungus fruitbodies to assist dispersal as in the ascomycetozoa], are nonsexual spores that result in haploid progeny. The honeydew both serves to attract flies, hoverflies, wasps, etc. etc. which alight, feed upon the sugary secretion and in doing so, pick up loads of conidiospores stuck in honeydew to their bodies, flying off to pastures and cereals anew to spread the infection.

The hemiamyloid reaction consists of turning reddish in Lugol's (another iodine-based reagent, an aqueous or hydroalcoholic solution of KI and I2) without the application of any caustic potash or NaOH pre-treatment step, and when the hemiamyloid spores react not at all with Melzer's reagent without base treatment, but with base then it turns blue in either Melzer's OR lugol's .


Oh, and not that your comment seemed to be anything but vacuous and opinionated, without providing the slightest reasoning behind it. But you best back  up, put up, or shut up. justify yourself, or fuck off and die.

You don't know me, you don't know a  motherfucking femtogram  of detail about who I am, or what I either do, know,  or much anything else for that matter. The only thing I don't really get, is, given that I actually haven't been around on I2 for quite a long time, until I returned relatively recently, because my computer broke down in several different bits of hardware, and I had no net access until I had enough money to buy myself a new laptop. So you have no idea who I am. Either justify your mouth, or keep it closed. You'll end up choking on a fly if you leave a foetid, ordure-bespattered, stunted offspring of tartarus such as that rancid perdition-gash just below your nose. Or if there is anything right and just with the world, a wasp.
Beyond the pale. Way, way beyond the pale.

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Offline Genesis

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Re: Could use some help, from the ozzies among us
« Reply #8 on: April 12, 2016, 06:27:25 PM »
For the love of goddamn God, don't ever take me seriously.  :GA:

 :'( Okay

Offline Gopher Gary

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Re: Could use some help, from the ozzies among us
« Reply #9 on: April 12, 2016, 06:31:03 PM »
For the love of goddamn God, don't ever take me seriously.  :GA:

 :'( Okay

Except for you, Genesis. You should always take me seriously.  :eyelash:
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Offline Charlotte Quin

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Re: Could use some help, from the ozzies among us
« Reply #10 on: April 17, 2016, 01:01:43 AM »
They don't grow where I am. One of the few places in Australia where they don't.