Author Topic: enantioselective isomerization of safrole to isosafrole, anyone? -drone 342  (Read 2310 times)

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dormouse

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Author  Topic:   enantioselective isomerization of safrole to isosafrole, anyone? 
drone 342
Member   posted 10-19-98 08:35 PM          
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Now that everybody's in the midst of a major pavlovian response to the possibility of photoamination of safrole, you'll also notice that in the ref's I posted, as elsewhere, the yields of the photoamination are higher using trans-methylated styrenes. This is due to the fact that the cis-is open for attack by the very catalyst that activates it, meta-dicyanobenzne, resulting in something really scary-looking as a byproduct.

Anyway, my point was that what this means is that yields for this reaction would be considerably higher if the starting material was 100% pure trans-isosafrole, rather than cis. With this in mind, I wanted to open the discussion up on the possiblilty/feasibility of enantioselective clandestine isomerization techniques. What'dya think? This one should be pretty easy. I can post a gazillion different reactions like this, but I think I should leave it up to other people's ideas first. So? How would you do it?

-drone #342


drone 342
Member   posted 10-19-98 09:30 PM          
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Errata: that should read "Pavlovian response to the photoamination of isosafrole"
 
Strike
Administrator   posted 10-19-98 10:50 PM          
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Drone - please stop posting every recipe that comes into your head. It is diluting this entire board, makes you look like rabid show off, and does absolutely nothing to get work done.
Strike (and Strike will wager others) have many of the articles you have been posting in this board (including the photoamination). The reason Strike does not post them is because it is reckless and is very unprofessional to just throw things out time after time after time when it is obvious that all one is doing is just regurgitating the latest snipet one found the night before.

Your constant posts show no indication that you have done any work to substantiate the articles you provide. It is obvious. That is why Strike doesn't comment. That is why, Strike thinks, most of the others don't. That is why nearly every post of yours on this board is just you answering yourself.

If you have read the entire bodies of the articles on photoamination, you would have seen that the REAL apparatus involved, and the apparatuses in similar experiments, are not in any way applicable to street chemists. And now, in this thread, you are talking about the preferrable dynamics of using cis versus trans isomers. Who on the street level (who even in the academic level!) can consistantly make the discretionally pure isomer so flippantly as you submit?!

This showy crap is useless to the street chemist. Even Strike can't think of a way to do the stuff you are proposing.

This board was a good idea but Strike purposely avoids it now because you are making a mockery of it. Please think more carefully before you post.

And, NO! Strike is not mad right now. Strike has just been watching this for so long now and Strike has a lot of respect for you. Strike has just never known how to get this out. Strike probably even screwed it up regardless. But what the hell.


r2d3
Member   posted 10-20-98 02:27 AM          
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I know what you mean Strike. What we need is more bubble gum wrappers. Find any more?
 
r2d3
Member   posted 10-20-98 03:07 AM          
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Drone: I hope you don't think I'm putting you down. Frankly, I am amazed at your dedication to chemistry, and can appreciate the time you must put into it. At the same time, I understand where Strike is coming from. Quite a few whining bees asked for this board, and as you can see, not very many are using it. I suppose it's all in a person's expectations. Let me tell you a story about a foaf.
This person started reading the posts at the hive, and decided that this looked like a great hobby. A kg of sass was obtained and various SRV catalytic reactions were tried. The kg was gone and not one crystal of product produced. Well, this foaf went to the basics, and tried the formic/al-hg route and turned out 225g of excellent product, which is given to friends 3-4 at a time. They are hand encapsulated in size #1 capsules and are between 135-150mg. You might think the story might end there, but you have to remember this foaf took this up as a hobby. The fun would be in trying to get higher yields and simpler methods. To this end, all posts are read with interest, with the hope of cutting costs, and making x available for less than the price of a draft beer. To this end the foaf bought a micro-sized lab kit and will play with new methods (still lots of caps left, but the pile is going down).
I guess it comes down to expectations. I have explained this foaf's expectations to you, and feel they are shared by many. Perhaps that's what Strike is trying to say.
 
Labrat
Member   posted 10-20-98 10:09 AM          
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This is not about choosing sides, but I agree with what Drone does. That's what this board is all about! Searching thru the literature and finding interesting reactions. Not everybody is interested in getting rich by making as much dope as one can with the cheapest reagents available. There are many people already working on this; Drone and myself contribute on that too. This board was set up to let the real chemists flex their brainmuscles. Too bad not everybody understands what we're talking about, but that's why this is a separate forum. There are enough forums left to find information that everybody can understand.
I'd like to recall the recent post by Drone on making phenylpropanolamine from alanine and benzaldehyde. I got so excited, I didn't sleep much that night, I was thinking about this all the time! And I just couldn't stand it that this thing was in Japanese. I see chemistry as a sport, a challenge. I like simplicity, but I'm not afraid of difficult procedures too.

I'm not the one running the show here, but Drone has my blessing! Go on, my friend. Lr/


 
drone 342
Member   posted 10-20-98 12:59 PM          
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Strike,
Obviously, I couldn't disagree more, and I don't even know where to begin.

First off, I do believe I'm getting work done, though perhaps we're working on separate projects. My "work" here is investigating novel syntheses of phenethylamines, then fleshing-out those that look most attractive, and attempting to develope street-useful methods out of them. That's what I've been doing. Consistantly.

Aside from the material I'm discussing, who else is bringing up new topics in this board? When folks do bring up their pet projects, like Labrat, I assist. I happily await someone else comimg up with novel methods, or wanting to discuss their own chemical interests. Still, almost nobody does.

But let's get back to your response. You said, "Your constant posts show no indication that you have done any work to substantiate the articles you provide. It is obvious. That is why Strike doesn't comment." Fascinating. You then say, "If you have read the entire bodies of the articles on photoamination, you would have seen that the REAL apparatus involved, and the apparatuses in similar experiments, are not in any way applicable to street chemists." Again, highly insightful and informative; I feel like I've gained a great deal in the process of reading it.

However, when actually looking at the methods described in Tetraherdron, 50, 31, on page 9276, I read "The photoaminatin of 1-8 (D) with ammonia and alkylamines (RNH2) were performed by irradiating a deaerated MeCN-H2O or MeCN solution containing D, m- or p-DCB, and RNH2 by a high-pressure mercury lamp through a Pyrex filter under cooling with water." This is the apparatus that you couldn't set up?! Dood, I can get a mercury vapor lamp at the local surplus store, the Pyrex filter refers to the fact the light was beamed through the reaction vessel, and DCB and acetonitrile are cheap, plentiful, and unwatched. seting up a water cooling bath is no serious problem, either. What part gives you a problem? "Deaeration" is easily done, too. Enlighten me; what part is beyond the grasp here of even an average person? What am I missing?

Isomerization *can* be readily done selectively, and its not even that bad of conditions. Maybe YOU can't do it, but I CAN (actually, I do believe you can do it too, though you don't know the methodology yet.) I am willing to post ref's, methods, etc., though you don't seem too interested in learning how. Its ironic you complain about me posting too many refrences and when this is the first thread in this section I've hesitated on doing just that.

What type of preparation do you want before I post? When I'm posting in this forum, the topic is almost exclusively theoretical, since I'm trying to discuss possible new methods, that either have never been done by anyone, or only slightly in the literature. How would you want me to "substanciate" photoamination, other than provide the literature showing how and why it works, when I'm trying to ask people how they might modify the details of it for MDA/MDMA production?

The whole point of posting is so I can get other's input on methods, and to let other people get a chance to think about these reactions. I'd wager that a large number, if not majority, of bees have never heard of photoamination of styrenes, and I'd bet there are quite a few who'd find it fascinating, and a number of them might have insights into improving the practicality of this already attractive method.

The Hive is chock-full of wacky chemical ideas; I give references and a modicum of detail to mine, as well as information on other's ideas as well. Others do this too. What's the problem?

So I invite you, Strike, to show us something new. Heck, its your board and nothing in the World is stoping you from flexing some mental muscle, especially in the spooky "Serious Chemists Only" forum. What novel reactions have you thought up lately? What insightful new approaches have you taken recently that nobody's discussed already? What references? Honestly, I don't mean this in a rude or flippant way; I think you probobly have plenty of things to discuss here (though you haven't.) Go ahead, dilute my postings with something more well-researched and more creative; it could only benefit us all. I gleefully await with baited breath. Your alternative catalysts for the Wacker thread was a good start.

I provide more references, more thoery, and generally more hard chemistry than almost anybody here, though I wish it weren't the case. Go ahead, tell me why photomaination isn't a good idea, and then show me up by tossing something new out there.

Let's go to another quote, and maybe this will explain wher the impass first eveolved from. You then said "This showy crap is useless to the street chemist. Even Strike can't think of a way to do the stuff you are proposing."

The truth of the matter is that this stuff ISN'T for the street chemist...yet. This is all academic stuff, but after discussion, I hope that at least a few of my methods will indeed trickle down to the average schmoe. That's the way this kind of stuff works.

Chemistry is my profession, my life. Its the focus of 18 hours a day for me. For me, phenethylamine chemistry is absolutely fascinating, and the greatest thrill I find in it comes from novel syntheses. I love the challenge of finding yet another way of making the stuff. This is what I'm trying to share here. I don't see the problem.

Finally, I wanted to quote Labrat, who said it so eloquently "There are many people already working on this; Drone and myself contribute on that too. This board was set up to let the real chemists flex their brainmuscles. Too bad not everybody understands what we're talking about, but that's why this is a separate forum. There are enough forums left to find information that everybody can understand." And he's absolutely right. This isn't about getting rich, but sharing information. This forum is for the stuff that just won't get the readership it otherwise would in the other forums, thus the name.

I have to admit, I AM hurt by all of this, and I think rightly so. Now that this little bit of bandwidth has been sufficiently wasted, let's get back to actually talking about chemstry.

-drone #342


Rhodium
Administrator   posted 10-20-98 07:23 PM          
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I'm sorry to say this, Drone, but I'm more on Strike's side this time... I, too have piles of "possible methods" all over my apartment, but I refrain to post about them until I've hired a greek peasant to try them out on at least one substrate before posting about them, to avoid wasting anyone else's time with any no-good method. The chemical literature of today is so full of shit that it is of no use to quote that a certain reaction has been done by this and that researcher. Especially if the substrate that researcher used was completely different.
It wouldn't take you more than a few days to try this photoamination out in practice before posting, and after that, you would know if it was bunk or not, and if it works, your FAQ on the subject would make you a hero. And your enolate synthesis of P2P - it is a big mystery to me that you haven't tried it out even once - you MUST have PhBr, acetone, DMSO and KOt-Bu lying around in your lab - throw them into a beaker, illuminate it with a cannagrow lamp and see if it works? As it stands, it is unknown if all the kilobytes posted on the subject is useful or not.

With your intellectual and chemical capacities, why haven't you tried a single one of all your ideas? It's unfair to excite people with all those ideas, and let everybody else do the dirty work...

Protocol:

10 Find new method
20 Try method
30 If the method works, goto 50
40 Else goto 10
50 Write up a synthesis guide
60 Post it

I'm tired of the same old 10 60 10 60 10 60...


drone 342
Member   posted 10-20-98 08:57 PM          
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Getting back to the subject at hand, if you look at Bull. Chem Soc Jpn, 71, 1655-1660 (1998), you'll see it looks like this use of strictly trans- isnomers is really overkill, and that the mere use of m-DCB rather than p-DCB makes a huge difference. Perhaps enantioselective isomerization isn't necessary.
Rhodium,

I have all the necessary chemicals at my immediate disposal for virtually every reaction ever discussed on this board by anyone. But the truth is, I have only so many hours in a day, I hate labwork, and considering the huge number of ideas I have, I only am willing and able to test a few. Some of them I post (many others things I do in my lab are research-related, and the way I see it they'll get posted in a real journal soon enough.) The way I look at it, keeping new ideas all to myself is a crime; everybody should get a chance to develope these things, and maybe someone out there might have a better take on it than me.

There is a saying we use in my research group: six months in the lab will save you an afternoon in the library. I much prefer one day spent executing a single over-analyzed lab prep but many days of library research over a day or two of library research, followed by several days of mixed results.

But I remember, during that last bout of chastising I had to endure, you said I ought to post more experimental methods, giving the example of your methaqualone experiment -- where you gave all the necessary details, but claimed that 100% of the experimental procedure was lifted directly out of the books. If memory serves, your point was that I needed to provide experimental method details, though not necessarily from my own experience. Now you want me to go through each reaction write up an experimental method, and post the results, too? What up with 'dat, homey? Sorry, but unless I get a research grant, it ain't gonna happen, except sporadicly.

Incidentally, I do use a modicum of discretion when posting; I have more ideas, but these ones catch my attention.

So now I'm curious. You say you have a ton of untested ideas floating around your apartment. What are they? You've been holding out on us! I'm dying to know; tell me what experimental stuff you've kept from the masses? I'm perfectly comfortable with merely the theoretical details behind it all; no need for lab notes. I'm dying of curiosity.

-drone #342


drone 342
Member   posted 10-20-98 08:57 PM          
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Getting back to the subject at hand, if you look at Bull. Chem Soc Jpn, 71, 1655-1660 (1998), you'll see it looks like this use of strictly trans- isnomers is really overkill, and that the mere use of m-DCB rather than p-DCB makes a huge difference. Perhaps enantioselective isomerization isn't necessary.
Rhodium,

I have all the necessary chemicals at my immediate disposal for virtually every reaction ever discussed on this board by anyone. But the truth is, I have only so many hours in a day, I hate labwork, and considering the huge number of ideas I have, I only am willing and able to test a few. Some of them I post (many others things I do in my lab are research-related, and the way I see it they'll get posted in a real journal soon enough.) The way I look at it, keeping new ideas all to myself is a crime; everybody should get a chance to develope these things, and maybe someone out there might have a better take on it than me.

There is a saying we use in my research group: six months in the lab will save you an afternoon in the library. I much prefer one day spent executing a single over-analyzed lab prep but many days of library research over a day or two of library research, followed by several days of mixed results.

But I remember, during that last bout of chastising I had to endure, you said I ought to post more experimental methods, giving the example of your methaqualone experiment -- where you gave all the necessary details, but claimed that 100% of the experimental procedure was lifted directly out of the books. If memory serves, your point was that I needed to provide experimental method details, though not necessarily from my own experience. Now you want me to go through each reaction write up an experimental method, and post the results, too? What up with 'dat, homey? Sorry, but unless I get a research grant, it ain't gonna happen, except sporadicly.

Incidentally, I do use a modicum of discretion when posting; I have more ideas, but these ones catch my attention.

So now I'm curious. You say you have a ton of untested ideas floating around your apartment. What are they? You've been holding out on us! I'm dying to know; tell me what experimental stuff you've kept from the masses? I'm perfectly comfortable with merely the theoretical details behind it all; no need for lab notes. I'm dying of curiosity.

-drone #342


Rhodium
Administrator   posted 10-20-98 10:23 PM          
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My problem is that I have not the money to immediately test all ideas I get, without resorting to crime to finance my hobby. Therefore the publication of my results happen slower than I'd want to. I haven't got access to any research lab.
That the written procedures in the methaqualone FAQ are quoted more or less verbatim from journal articles does not mean they weren't tested for feasibility. It was done in that fashion just to save time, and this is one of the reasons the version number of my FAQ's mostly begin at a lower number than 1.0 - they will not become 1.0 until I am satisfied enough with them to really call them a final version. In time, the FAQ's will be written with my own words only.

Okay, among the interesting preps I have no idea if they work or not, I can mention a few here below, and you should know that I feel really bad presenting the methods as is here, without having any experimental proof ready, and that the methods aren't yet optimized for use with our interesting substrates.

* US Pat 5053550
Prep of 4-chlorobutanal using common bleach, which according to another journal article is easily reacted with 1) aqueous dimethylamine 2) methanol/H2SO4 3) phenylhydrazine to give DMT in very high yields.

* US Pat 5146001
Prep of a P2P by rxn of a benzyl chloride, Zn and acetyl chloride with 0.01 mol% of a Pd(II) catalyst

* JOC 56, 7022-7026 (1991) + Tet 40(9), 1469 (1984)
Prep of epoxides and diols in high yields by refluxing alkenes in aqueous potassium peroxysulfate, which is rearranged to ketones with LiI or H2SO4.

* US Pat 4952718
Prep of phenylacetonitriles from cyanohydrins with PCl5.

* US Pat 4442286
Reductive amination by refluxing with H3PO3.

* JOC 27, 2037 (1962)
High-yield vanillin and eugenol demethylation by refluxing in DCM with Pyridine or triethylamine.

* US Pat 5057624
Prep of 2C-B and other phenethylamines with an overall yield of 70% from the corresponding benzaldehyde using dirt-cheap reagents, the worst being NaBH4.

* JCS Perkin 1, 265 (1995)
Reductive amination with Mg/MeOH in 65-80% yield, 50% with ammonium acetate.


 
drone 342
Member   posted 10-21-98 01:32 PM          
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...You've been holding out on us! A lot of those look quite original, practical and worth a lot of investigation. The advatage of sharing is that other people can help in the process of developement -- thus getting the method out faster. You, labrat, and I, as well as many other chemical researchers around here already have our hands full with more projects than we even could finish; by at least tossing out a brief overview for others to see, we can let other people "share the wealth." True, one risks losing the glory that one might obtain from giving out a complete, peer-tested FAQ of practical chemistry before everyone else, but maybe some developement time can be saved by letting others have a crack at your ideas, or maybe people can divert you from a dead-end alley before wasting precious time and materials.
Leastways, that's my humble opinion. I do see what you mean, but I really think that sometimes tossing out educated ideas is helpful. Admittedly, not as helpful as tossing out an FAQ, but I think that it can be a step leading to that. That's what I'm trying to do.

But let's get back to the chemistry! Going back to that soon-to-be-classic Bull. Chem Soc Jpn, 71, 1655-1660 (1998), there are examples of very successful uses of MeNH2 and EtNH2 as the aminating agents, respectively. This means that this method may indeed still have its place in the pantheon of kick-ass MDMA synth's.

-drone #342


Rhodium
Administrator   posted 10-22-98 09:51 AM          
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Well, always when a new idea gets posted, there is usually just a lot of talking, but noone seems to take the method to the lab. Look at the LiBH4/TMSCl reduction for example - that was a method I mentioned here on the Hive long before it was tested, and it took several months before a single bee tried it out. I think that is a little discouraging.
And what did you think was the driving force behind my chemistry page if it weren't for the ego flexing it provides me with?


 
drone 342
Member   posted 10-22-98 12:59 PM          
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Rh,
Definately, I can see the ego-flexing, and I'm all for it. You deserve a little praise and worship for the work you've obviously put into it all. If I haven't thanked you lately for your efforts in our cause: thanks, man.

I do agree about how sad it was to see the reduction go untested for so long, but that's what you get when everything's done on a volunteer basis. Still, this lagging isn't always the case; the turnaround time for someone using my hydrogen generator "in the bush" (aside from myself) was less than a week!

I guess unless a method looks reeelly groovy and reeely easy, people want the damn thing spoon-fed to them; maybe that's the lesson to take away. Still, even when a chemical idea starts out as "only" talk, progress (however laxidaisical) is being made.

So maybe this is how to summaraize this all: If you want an idea out there, you can just toss out to the group.

If you want a meaningful discussion and quicker developement, add references.

If you want the process to go a little faster, offer full-text journal articles.

If you really want it being practiced on the street ASAP, add a peer-tested synthetic procedure.

The more I learn about this method, the more I will describe it -- I have to admit I'm still very much in the investigative process of it all. As more is learned I'll keep everybody updated.

-drone #342


Strike
Administrator   posted 10-26-98 11:11 PM          
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Drone - You know Strike does not come down on anybody. Ever. And Strike does not want to seem that Strike is trying to stifle your initiative. Because Strike is not. Strike wants you to keep up what you are doing.
As before, it is a fine line that Strike walks when trying to explain to you what Strike means without looking like Strike is being unfair and unwarranted. There are subtlties about your postings that probably few can detect.

Yes, Strike agrees that we need to keep looking as hard as you have for new stuff and post it. But the way you are going about it it is very frustrating to watch. You seem to find an article or two, post them regardless of applicability, then ask what people think. Almost seeming to ask for people to explain them to you.

Well, Strike would like to know what YOU think about them. How do YOU see this method being translated to street use. How YOU propose getting or using the wierd ingredients. This site is, in a way, an academic discussion for denovo, novel reaction mechanisms. But it is, finally, the quest for the easiast methods that get the most people high and screws the government at the same time.

A STORY- When Strike was given Strike's first assignment in Strike's graduate biochemstry lab, Strike's new supervisor and mentor asked Strike to research and devise a strategy to solve a polymerase(don't ask) protocol. This was gonna be Strike's first segue into a thesis project.

So Strike goes off to the library and finds tons of stuff relating to the problem. This seemed like it was gonna be the easiest problem in the world. And in only a two day's time, Strike wrote a long LIST of all the hypothesis Strike had found proof (or even partial proof) for. Strike thought Dr. Sousa (his real name BTW) would be very impressed with all the ideas Strike had. But when Strike handed it to him in his office he almost immediately leaned back in his chair and scowled. He threw the entire list in the trash right in front of me saying that 'he didn't want this conjecture' but rather a single working method and sent me away.

Strike was so pissed at that motherfucker. But he was right. Strike was assuming that if Strike provided enough info on the subject, Strike could get the doctor to figure out how to make a cohessive protocol out of what Strike found. But this turned out to be the first time ever that Strike had to think up some idea that no one had ever done. This was graduate school. Strike could not just come up with some references and write a paper about it.

Strike was actually expected to apply knowledge and come up with a solution on Strike's own. Well, Strike changed course and decided on one method. Then Strike researched the one method to see if there were any anomolies, then conjured up a plausible lab protocol. Strike then presented it to the doctor. He bitched a little but started to nod his head as read more of Strike's proposal. Strike got his approval and was very proud.

This changed Strike's whole idea about the professionalism Strike needed to be a competant scientist (not exhibited in most of Strike's work). And Drone, Strike is not necessarily saying that there has to be a code of professionalism for this board. Everyone can be as goofy as they want! But a ‘Serious Scientist' would not flood my board with conjecture. The operative word being ‘flood'. If all you are is a ‘theory junkie' then go to the Novel Discourse for this. You are one of our elite chemists and are expected to come up with a little substantiation if you are to propose a new theory in this board AND be taken seriously OR provoke serious discussion.


drone 342
Member   posted 10-27-98 02:58 PM          
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I'm just curious -- what thread, aside from the one that wind up devoted to defending my other threads, haven't I asked worthwhile questions or given plenty of information and shown some understanding of chemistry?
Even in this one, I posted this because its a separate topic related to photoamination. At first, I though using the trans isomer of isosafrole would be necessary, since I thought the methyl group acted as a sort os strearic hindrance from a side reaction involving DCB. With the examples of dihydronapthalenes (essentially rigidly-bound equivalents of cis methylstyrenes), I see that its not 100% necessary.

Incidentally, I also wound up dispelling beliefs that photomaination required etremely exotic and expensive equiptment.

propenyl benzenes -> amphetamines in one step : I've given tons of useful information on this reaction, and have gone into the mechanism. The question I had? Since photoionization of DCB is generally understood to be an integral part of the mechanism, and the photoionization potential is 10.14 eV, which corresponds to a lightwave with an unusually short length of 123 nm, but the literature cites reactivity using light around 300 nm, then how does one resolve this dilema, keeping in mind that quantum mechanics would normally predict otherwise?This is hardly a flippant or "hi-mom-I'm-high" question. The other thing I'm requesting that someone else help me find is hard data on the spectral output of high-output lamps -- again, not terribly unreasonable of a request.

Regardless, I showed in quite explicit detail again and again, that this method could be exceedingly applicable to street use, since all thats needed is isosafrole, methtylamine, a couple cheap and innocuous catalysts, acetonitrile, and a marijuana grow light.

There's the MDMA mass-production thread -- something that definately needs discussion. This one is new, so there really hasn't been enough there to make it 100% respectable, but this obviously has plenty of application.

The propiophenone thread was chocked full of information from myself, and especially others. This was one where I honestly only had a little information to start with, but the result was a discussion where plenty of others contributed, and a senblence of a respectable information exchange occured, complete with ref's to plenty of new methods and ideas, and lots of creative material.

With the "Grignard reagents and methylenedioxy rings" discussion, I opened up discussion of a route that had been previously dismissed, and through the discussion, I went on to disprove that the methylendioxy ring couldn't stand up to a strong nucleophile like a grignard reagent, provided the right conditions were given -- this was the original reason people threw out this idea. Labrat and I went on to discuss other potential road hazards in this method, and inexpensive soltuions to the problems.

The "oxazoline-based rigid bodied analogs of X" discussion resulted at least a small amount of exchange of information between labrat and rhodium, and good for them. Labrat had just so happened to been researching just that, and had full texts to offer the rest of the class.

"JACS,106,24,(1984) 7573-7578; ammonium persulfate CuII complex as an oxidizer" Was what I thought a nice novel way of making ketones from styrenes using cheap reagents. There was a bit of confusion (still to be resolved) where I simply couldn't understand the mechanism bheind the isomerization of 2-phenyl propanal into phenylacetone. I'm not too proud to admit when something is strange to me, but if you feel this really is a superficial question, then you shouldn't have trouble answering it.

"More oxazoline goodness" was one that I didn't feel entirely good about starting, but did so anyways for Piglet, who for whatever reason hasn't been allowed to post to this group yet. He had a question, which I though worthy of a "serious chemist" answer, so I posted it for him. He should have posted it here, but due to inadvertantly not getting the password, I did it for him.

"what happened to my enolate review?!" was in response to the fact that a lot of data that I'd collected for The Hive on a reaction I found quite fascinating and useful disappeard. Fortunately for me, Rhodium archived it, it was posted. In addition to a review of articles relevant to the method, I posted the experimental methods listed in the literature, and talked about alternative reagents for making the thing go (using home-made alkoxides rather than KOtBu, etc.)

"possible improvement on bromosafrole->MDMA" was a discussion that, in order to be resolved, required a massive amount of in-depth study of the problem. After a huge discussion between myself and Labrat, it was resolved that using a strong nucleophile (like a metal amide) would not be advantageous in the Sn2 reaction of going from a halosafrole to MDMA. This was by no means superficial, and it was totally necessary in order to resolve this issue. This had immense practical potential, since it may have meant a reaction time of a few seconds, rather than hours.


I got to go right now, but I think I've shown prety well that the stuff I'm posting simply isn't as shallow as you think. A lot gets discussed in my posts, and much of it quite useful.

When I ask for other people's input, its not out of weakness. I understand plenty. What I'm hoping to do is get other people's input. I certainly have plenty of my own ideas, but in the course of a dialectic, new ideas and new approaches -- ones that neither person originally saw, come up. I try to open it up so that other people can be a part of it.

-drone #342


drone 342
Member   posted 10-27-98 05:16 PM          
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Rather than take an entirely antagonistic approach here, I wanted to say that I would like some more genuinely constructive criticism. What sort of information should I add to make my current threads more suitable that I haven't already? I'm looking for some guideance here; show me why my ideas won't work, or why they do, or what more you want with each of them, or whatever.
A lot fo the stuff I'm discussing really IS pure theory. But before I can even plan to come up with a lab proposal, I want to know what I'm doing beforehand. I like to think the hypotheses I come up with are of interest to at least some other chemists (I get plenty of private e-mails that say so), and perhaps the thoughts I have will ispire others to come up with better solutions. Perhaps in the process of developing an understanding of the reactions, a workable synthetic method can be developed, and one or two of these ideas will be applied.

All these ideas have some common threads: usually they use less-watched chemicals, or the synthesis (in theory) should be simpler to follow than those commonly in practice. You and I are on the same team, here, and this is how I'm fighting for the cause.

-drone #342


Strike
Administrator   posted 10-27-98 11:12 PM          
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Drone - you know no one is asking for complete recipes or protocols. Yeesh! Don't play the obvious retorts so soon. And Strike does not have any constructive criticism. Believe it or not you are a better chemist than Strike. Strike has no authority to tell you any of the stuff Strike has already. Strike just wishes you would consider a quality over quantity approach. We have enough trouble making simpler, existing methods work without diluting our attention so massively. Imagine if as little as five other Drones came in and produced the same amount and type of material. It would be an a.d.c. of 'theory' with everyone asking questions and no one giving the real life answers that everyone needs.
Strike don't want to fight with you about this anymore. Strike can't adequately express what Strike means. No one else seems to understands EXACTLY what Strike means. Strike justs wants to kiss Drone on the lips and make up. Besides, it looks bad to the rest of the site who probably looks into here for the answers and all we (Strike mainly) are doing is bitching.


drone 342
Member   posted 10-28-98 06:48 PM          
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Alright, I see your point. I'll try to cboost the signal-to-noise ratio (though I still think I got plenty more signal and plenty less noise than a lot of folks.)
Let's just pause for a second and imagine a 100% "dronian" version of a.d.c.... Hm...Damn, I'm sorry, but I still can't see too much wrong with it. For as much theoretical stuff I come up with, I still do answer a lot of other people's questions, and give plenty of practical advise. I just happen to have a lot of questions of my own.

Enough said. Let's get back to some yummy chemistry.

-drone #342