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dormouse
(Member) 04-19-00 04:58 No 122763 |
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enantioselective isomerization of safrole to isosafrole, anyone? -drone 342 | Bookmark | |||||
Author Topic: enantioselective isomerization of safrole to isosafrole, anyone? drone 342 Member posted 10-19-98 08:35 PM ---------------------------------------- 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 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. I'm not the one running the show here, but Drone has my blessing! Go on, my friend. Lr/ 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 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 I'm tired of the same old 10 60 10 60 10 60... 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 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 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 * US Pat 5146001 * JOC 56, 7022-7026 (1991) + Tet 40(9), 1469 (1984) * US Pat 4952718 * US Pat 4442286 * JOC 27, 2037 (1962) * US Pat 5057624 * JCS Perkin 1, 265 (1995) 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 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 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. 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. 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 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 Enough said. Let's get back to some yummy chemistry. -drone #342 |
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