'A twist to tradition' (Modified formic)

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Author	Topic: 'A twist to tradition' (Modified formic)
dr.strangelove Member	posted 09-03-99 11:35 AM Hi, y'all... Long ago, in a land not so far off, there was a guy who had a lot of olefinic oil. This guy wanted to put it thru a rxn called the performic acid epoxidation. But this guy had no access to lab-grade formic, and he had no access to labgrade H2O2 either. But he had GAA from the photo shop.... One time, in another incarnation, this person had a conversation with a big ol' fat bee... This bee whispered of an idea that almost all of the formic can be replaced, with no harm done, by GAA...hmm.... So, this guy went to work. " Hmmm...I need a source of H2O2 that is strong enough to do the job..." He had heard rumors of a 'wood bleach kit' that supposedly contained 30% H2O2... After verifying these rumors, the guy calls the helpful 1-800 numbe ron the package... "What's the strength of your solution, in this here kit?" Helpful Lady: " 25-30%" Guy: "Cool" So now guy has the peroxide, he has the GAA he only needs formic. Guy goes to page d'rhodium, (wink) gets formic acid via oxalic-glycerol recipe. Makes a nice yield of 77% formic. Now: Guy takes PIHKAL 109....Follows it to the letter with his reagents, adjusting the amount of H2O2 upward by 5% vol... ....and replacing 90% of the formic acid with homemade 77% formic acid. When dripping the iso in, the rxn temp was stabilized @31-33 degrees. Rxn was cloudy-opaque when the stuff was all in... It slowly took on an orange-pink tint as stirring proceeded, and then became darker, to about a rose color after 36 H of stirring. When stirring was stopped early on, the mix separated into two phases. When it was stopped at Hour 20, the same results, 2 phases. When it was over, the stuff sep'd easy. Hydrolyzed as usual. The water in this rxn seems to have kept the formed glycol-epoxide from being as soluble in the GAA - formic mix...it was orange at the end of 36h... I believe this route is cleaner and easier than std. formic. I always hated the way the formic dissolved all your product, and then ya have to extract it all w/ DCM and all that shit.... With imagination and effort this EASY reaction can work for YOU.
dr.strangelove Member	posted 09-03-99 11:39 AM sorry...error check... " replacing the formic w/ GAA" NOT HOMEMADE FORMIC the homemade formic is used w/ the GAA to get a 90% GAA : 10% aqueous formic mixture, and this is all. Whoops.
Rhodium Administrator	posted 09-03-99 12:14 PM I still don't get it. In the final acid mix: How many percent GAA? How many percent Formic Acid? How many percent Water? And most important, what was the yield of MDP2P?
Osmium Member	posted 09-03-99 02:29 PM Big ol' fat bee, HOW NICE! I know which bee you are talking about, and she definitely doesn't like to be called that way. You're in deep shit now, up to your lower lip
Rhodium Administrator	posted 09-03-99 05:12 PM Osmium, do you by chance know the young lady J R Shaap, alias The Apprentice...
purplxd Member	posted 09-03-99 11:27 PM dr strangelove, thank you for bringing up a dream SWIM once had. this dreamer did indeed replace the formic with GAA, plus a bit of conc.H2SO4(2% by wt. of GAA). in addition, the solvent used was DCM instead of acetone(you didn't specify yours). the necessary color changes took place over time and of course the rxn was 2-phase. but without access to necessary equipment the final product could not be checked(no bisulphite available either). however a test was run for "a ketone in the presence of organic acids"(sorry but don't have SWIM's notes to give reference on this simple test but it was in an early issue of Analytical Chemistry). the result was positive. don't remember why SWIM used the H2SO4. got any ideas? BTW, the use of DCM(and NA2CO3) was proposed by Kojima back in 1959. SWIM has the paper in Japanese. could any bee translate it? much thanks
Semtex Enigma Member	posted 09-04-99 12:45 AM If one can use a mixture like 90% GAA and 10% formic, this would lower the cost of the formic considerably. Rhodium, didn't you mention a method(email) that used/uses GAA instead of formic? Was that theoretical or real world? If I remember correctly SWIM tried it once, but something broke, so it couldn't be finished. Thoughts??? Anyone???
Semtex Enigma Member	posted 09-04-99 12:48 AM purplxd: I think the answer to your query is the H2SO4 is used as a catalyst since the GAA is a weaker acid, it takes longer to form the peracid(I think SWIM was told to let it sit overnight before use)...
Rhodium Administrator	posted 09-04-99 09:29 AM Semtex: It was real world, but it was performed by french chemists in the 1800's
purplxd Member	posted 09-04-99 06:12 PM semtex: thanks. then if one should wait for the peracid to form with GAA, does this mean the in situ method is not recommended? In general, for the in situ method does it matter if one drips the acid(formic or GAA+catalyst) or the H2O2 onto everything else?
r2d3 Member	posted 09-04-99 10:24 PM There seems to be alot of interest, and for that matter confusion about this reaction. Strike, who I believe followed Shulgin's method in #109, drips the iso and solvent(acetone) into the peracid. Ritter's post of 09-21-98, which cites a CA from 1975 drips the peracid into a solution of iso, solvent(DCE) and a buffer (sodium carbonate), and reports better yields. Since nobody has commented on this, one would tend to believe it doesn't make any difference. Now comes the speculation that GAA, could replace most of the formic acid. This would indeed be a breakthrough if only for cost and availability reasons alone. Even if the GAA/formic peracid needs a catalyst(H2SO4) and longer to form(12-16HRS)it would be a usefull alternative. I would be interested in hearing comments relating to the addition order of reagents, and how they relate to yields. Also DR. post your yield so we can put it into perspective.
hellman Member	posted 09-05-99 07:33 PM Dr Strangegloves, I do like your post, and believe that as usual you tell no lies. This facinates me greatly!!!. So We would use 90% GAA and 10% of 77% formic,. This would be great for the formic challenged, who have to resort to using the oxalic and glycerol, which seems to produce only small amounts in my exp. Everyones dying to know?.... 1) how long do you let the h202 and formic/GAA mix for before addition into the iso/corbonate/dcm? 2) Are the results pleasing?. hellman
Semtex Enigma Member	posted 09-05-99 09:17 PM Rhodium, your fucking mail isn't working yet AGAIN. Anyways, if you remember that little ditty about sustitution of formic for GAA in molar ratio's, I gots a question for ya. If one were to combine the GAA and the H2S04 and the H202 and let sit, would there be a problem if it was left for say, 3-6days before it was used? In a stoppered flask at room temp if I remember correctly from the fax I got. Thanks for any and all help in this matter...
Osmium Member	posted 09-06-99 11:58 AM The performic acid isn't stable, and can't be stored for longer periods of time. It starts decomposing as soon as it is formed. Peracetic acids might be different, but I don't think that they are rock stable either (although they are sold, so at least they should keep good for several months at least). The idea behind substituting acetic acid for some of the formic is the following: most of the formic used in Dr. Shulgins classic #109 synth acts only as a solvent, and doesn't form the peracid. So it should be possible to substitute at least 50% or so with acetic acid. Leave at least one mole of formic in there for every mole of H2O2, a little excess might be better. Rhod: ??? The Apprentice? Never heard of.
Semtex Enigma Member	posted 09-06-99 01:50 PM Yeah, the method that I am reffering to used acetic instead of formic 100%(READ NO formic at ALL). How would one know if the peracetic was still good or if it has decomposed somewhat??? Thanks again for any and all help...
Rhodium Administrator	posted 09-06-99 06:44 PM There is a good monograph in Organic Reactions (I have forgotten which volume, look in the index in volume 50), which goes into detail on how to prepare performic and peracetic acid, and how to use any of them to oxidize double bonds. It should answer any question in this thread. Also check the peracid review in Chem Rev. vol 45, page 1 (1949). Semtex: Are you really using <rhodium@anon.nymserver.com> ? I haven't had a single mail complaint since you had problems several months ago.
Semtex Enigma Member	posted 09-06-99 07:03 PM Opps, no sorry I was using a different one, hmmm, currently(and possibly for a week or so) I won't have access to ANY ref's, let alone the one(s) you just mentioned. Would you be willing to give me your opinion on wether or not peracetic should still be good a few days to a week later? Thanks again, and sorry about the mail thing, the PGP key I have for you has your other email addy on it...
Rhodium Administrator	posted 09-07-99 06:11 AM Look at my page, I have a new PGP key and a more reliable address nowadays. I haven't worked with peracetic acid myself, but from what I've read, I doubt it would be active for more than, say, 36 hours. Why do you want to keep it for so long? Mix acetic acid, H2O2 and a few drops of H2SO4 and let react for some 12 hours and then add your alkene of choice, and then let it stir together for another 12 hours and then do the usual workup.
Semtex Enigma Member	posted 09-07-99 10:06 PM In the peracetic notes thing on your page, someone mentions that the peracetic has to be run for like 36h instead of the 12-16h normally for the peracid method(s)... I'll get that new key and drop you a line...
dr.strangelove Member	posted 09-08-99 01:04 PM I know that when you get the formic down to a minimal level the system is two-phase, obviously due to water present in the 77% azeo formic. The best thing I can say about it is that the finakl product was not infinitely soluble in the peracid matrix. It was separated without extraction solvent and the yield is around 60-65%. Rhodium: A minimum of formic was used. Just enough to protonate the mix was what I wanted, and it ended up being ~5-10% in my experiments.
hellman Member	posted 09-09-99 01:13 AM Dr stangegloves. Your a hellman!. thankyou Who needs to take mdma when you can sit down to a nice episode of party of five, followed by dawsons creek, and a little Dr stangeglove to top it off. hellman. Even though you are busy, everyone is screamin out for a formal write up, with this 5-10% fromic 77% and the 90-95% absolute formic. I doubt that write-up are your style, and who cares. Sweeeeeeeeeeet.
Ranter unregistered	posted 09-09-99 05:11 PM Personally, I'm not sure if I would recommend taking chemical advice from "junior members." Especially when they say weird shit that they shouldn't really know unless it was somehow "in their line of work." In fact, I don't think I would take any advice from them at all unless they seemed very sweet and naive and dumb. I'm not saying anything about dr.strangelove per se, just good advice.
hellman Member	posted 09-09-99 10:30 PM Yes, Good Advice,. On the other hand, to post here you must understand the consequences and take adequate security measures to maintain your anonyminity. Once you've done that it really doesn't matter a whole lot on what anybody says, If he is a cop, He's done me proud and the hive,. no -one ever knows for sure. Information is king here, the medium for which it gets here, should always be treated as if it is suspect. hellman Reborn,remade, re-encrypted
dr.strangelove Member	posted 09-10-99 11:15 AM Well, Ranter, I was known as quite a ranter too when my name was...." nutmeg lad"... or " sassafras chap"... or some other equally unimaginative handle. Now, I didn't really see any point whatsoever with your 'advice'.... other than to do the very thing that you did... which was to cast a doubt in the mind of the curious and inquisitive. Agent provacateur? BTW.. this IS in my line of work, It aint some 'weird shit' either. Why doncha offer constructive criticism instead of the usual web of mysterious, unsubstantiated doubts? Even if I gave a write-up that was exhaustively researched and meticulously thought out, there would STILL be a million questions, because not everybody is on the same level here. What I am TRYING to do is give people ALTERNATIVES because the well-known routes are pinch points. Got it?
dr.strangelove Member	posted 09-10-99 11:19 AM PS-- I'd like to know the little trick you moderators and administrators do to place 'Member' status by a name that has only been posted 2 or 3 times. Yeah..... I probably will never be a 'member' if those are the prerequisites, because I post relevant to quality now, not quantity. So, one of you guys e-mail me and tell, OK?
Semtex Enigma Member	posted 09-10-99 08:22 PM What is this world coming to??? Even a PAGAN is a junior member??? If that is the case, HOW THE HELL DID I GET MEMBER STATUS??? Good Dr, if you would be so kind, could you contact our dear little Super Nova and get my addy from said bee, perhaps use this addy to contact me with a way to contact thee??? Thanks...
dr aroma unregistered	posted 09-11-99 02:27 PM dr. strangeglove, That's fine with me. What you do is your business, AS LONG AS I am left out of it. I have never had anything against you personally, however, I don't want to be sent to jail again, really, either OK? Not that that was your fault even... However, as we all know, my I've had to adjust my life considerably since those my days of "youthful indiscretions" to quote Rep. George W. Bush.
Cherrie Baby Member	posted 09-11-99 04:19 PM dr.strangelove Or shall I call you Jr? You're right - I did a search and found only 14 posts by you. Why are you so economical with your companionship? We're all just dying to talk to you here.
Aromaticity unregistered	posted 09-12-99 02:39 PM "Judge me all you want, just keep the verdict to yourself."--Winston cigarette ad
FMAN Member	posted 09-15-99 09:05 PM link to the alliquate 336 thing>>>>>>>>>............
Modesty Member	posted 09-17-1999 06:18 AM When did you aquire a Dr's degree Spiceboy? Just my 5 cents... :-)
dr.strangelove Member	posted 09-17-1999 09:00 AM When I figured out about 6 different ways that work. Y O U ? Just my 3 cents....
dr.strangelove Member	posted 09-17-1999 09:00 AM
Modesty Member	posted 09-19-1999 03:34 PM You have a certain way with words, and a knack for leaving a teeny bit for the reader to find out. Been around for a while you see... But this is off topic so ... snip ....
hellman Member	posted 09-22-1999 08:12 PM Has anybody wondered why Dr Weirdmits hasn't congratulated my methods and sucess on the HBR dingy,.?? Did he merely speculate it's true working and does he now command an opinion that I truly didn't get this baby to fly?. Well sadly I did, but even sadlier, This GAA modified peracid reaction, as mentioned by Gyro, now only answers to me. NO, I mean I've only got eyes for it. hellman
Semtex Enigma Member	posted 09-24-1999 07:54 PM Hellman, do you mean the 90%peracetic and 10%performic, or the 100%peracetic???

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