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Hive BB  Methods
Discourse  Peracetic
anecdotes
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| Author | Topic: Peracetic anecdotes |
| Tao
Corning NewBee |
 posted 12-28-1999 04:34 PM 
This is written to give hope to the peracetic movement, for those who are tired of breathing copper sulfate and vac distilling concentrated formic. Furthermore, I have dreamed of nothing but disappointingly low yields via performic. Like DpHarma said, they lacked ‘pizzazz’. Peracetic dreams have not been better, but have been easier by virtue of reagent preparation, and I feel that just a couple more dreams will have it nailed down. I first read the idea from Purplxd (reiterated by Gyro) and tried it in two separate dreams. My lab technique is pitiful, and I will relay some fuckups so that if you’re better than me you can expect to yield accordingly higher. In my dream 28.6g 35.7%H2O2 were added over the course of 5 minutes to a stirring mixture of 60g Glacial Acetic Acid and 1.2g H2SO4 in a 500ml Arby’s flask. (round bottom for our non-American associates) This was allowed to stir for 24 hours, after which was added slowly 32.4g Isosafrole suspended in 50ml DCM. This addition was self regulated by means of the following glassware arrangement: into the flask go two condensors stacked on top one another to make one super-condensor. On top of this goes the addition funnel. This addition funnel is not stoppered. In this dream, it was actually a west condensor and a jacketed column which both came in a standard 19/22 organic kit. As the addition funnel is opened and the reaction begins, the heat begins to boil the DCM, which condenses and cools the reaction. (A little of the DCM is added to the flask before addition, as an insurance policy against initial overheating.) The reaction soon overcomes the ability of the DCM to cool it, and when this occurs, the vapor pressure of the DCM blows a little stream of bubbles up into the addition funnel, preventing further addition until the reaction has sufficiently cooled for the pressure to drop. Anyway, the addition was not supervised, but the reaction allowed to stir as vigorously as possible for 24 hours from the commencement of addition. From halfway through addition until the end of stirring, the mix looked like cherry coffee. Those two words should suffice for you when you see it. At the end of this time a shitload of chlorinated solvent (TCE & DCM) was used to extract the goodies, even though it was very likely separated - I was too brain dead for it to occur to me that I should check. The solvents were removed under vacuum and the residue dissolved in the 60ml Methanol and hydrolyzed in 360ml 15% H2SO4 for two hours at 75 degrees. Upon vac distillation a beautiful flourescent yellow oil with just a little green condensed out. Final yield 19.2g crude MDP2P. The lab technique employed here couldn’t have been any sloppier without intentionally trying to fail. The distillation temp range indicated a lack of purity, but no horrible pre run of iso. But the truth would never be known because some asshole put too big of a nitromethane kicker in during amination and blew most of the solution onto the basement ceiling. The amination phase of the dream was continued anyway with a little more methanol and about three and one half grams of Hcl salt recovered. Given my usual dreaming prowess, one may safely believe there were at least 5.25g of ketone left after the eruption. I believe there was at least 15g at the start, but who knows? This dream is a recurring one, and came to me just the same as the previous but with larger amounts, to wit: 120g Acetic, 64.8g Iso, 150 ml DCM, 2.4g H2SO4 and 85.8g 35.7%H2O2. (Not necessarily in that order.) Another difference in this dream was the lack of patience, and peracetic formation was only afforded 12 hours, while stirring remained 24 hours. Of course it was in a 1L Girlenmeyer (Earl & Meyer, pick your tripe...) flask. Final yield of “ketone”: 53.2g BUT, before any little peckers flip up in premature joy, listen to the rest of this dismal story. There was an obvious forerun of iso, and the final mix smelled of it, so I knew I would dream bisulfite before I wasted my hard earned methylamine on some fucking root beer oil. (Bisulfite after any distillation is SOOO easy...) Bisulfite crystals still slightly damp with everclear were over 9 grams and recovery yielded 6.05g of quality R2D23PO. A subsequent aminative dream with said ketone yielded 3.8g of artificial joy that will spread Christmas cheer well into the new overbilled millenium. (BTW, all my amines are Y2K compliant.) That amination was subconsciously modeled after dpHarma’s post in the “Success with Nitromethane” thread and was 6g Al, 7.1g MeAmHCl, 4.5g NaOH, apprx 200ml MeOH, apprx 3ml Nitromethane, and apprx 20cc H2O. Dream #2 went bad primarily because of incomplete peracetic formation, I believe. Someone (?) hypothesized, and I believe this wholeheartedly, that the peracetic is less brutal to the methylenedioxy ring than performic. I believe that because this is true, it affords a longer period of time in which the proper amount of oxidation has taken place- and I need the biggest window of opportunity I can find. Personally, I do not at all mind prepping my peracid the night before, or the day before. I also believe the other side of this to be the lack of oxidizing power the peracetic has and my future plans include more H2O2, maybe a slightly elevated temperature (35C?), less solvent and/or strictly acetone (single phase mixture). On that second dream, I stirred as fast as I could, but didn’t see the smooth solution I did with the smaller batch in the round flask. Finally I should mention that in my dreams the acetic acid was homemade with (God bless) dpHarma’s recipe post: neutralizing 5 gallons of grocery store vinegar with about two cans of lye and baking to dryness in the oven over several days. (smells like baking bread, mmm.....) I found that boiling leaves your stove top covered with the acetate. The dried acetate is mixed with H2SO4 and distilled, but I believe more than a trace amount of sulfate remains in the distillate. I redistilled and got out the sulfate smell, but it appears that there was a water(?) azeotrope which came over at about 107 degrees. That was about 400ml and then it kicked up to the 118 degrees I was expecting for about the last 120ml, which I collected separately as pure. This may have influenced my dreams. I really loathe the copper sulfate treatments, so if someone knows of a friendly, suitable drying agent for acetic like MgSO4 or something, please post here. I just treat the 107C boiling acid like it’s pure and say fuck it. Oh, and the hydrometers in the pet store for measuring salinity are nice for acetic because they’re smaller and look more accurate in the range from 1-1.049rd. (I just bought it today.) The H2O2 was pool store shock which was labelled at about 27%. But my handy dandy wine making hydrometer (God bless dpHarma) told me that some settling of contents must have occurred during shipping and handling. So I put it into a distillation setup and started boiling the water out of it. When I stopped, the hydrometer told me it was 35.7% Use the highest concentration you feel like you won’t explode while making. No guts, no glory. BTW, if you go to a local glass shop or preferrably a plastics supply house (yellow pages!), you can get some 1/2 inch thick acrylic scrap for cheap and then rig it up to hang in front of your beaker - instant peace of mind. DpHarma, if you’re out there and listening, you’re name appears more than once already in this post and I would like to thank you publicly for your contribution to the Hive. You have been the one I listen to unequivocally, as I respect the fact that you don’t pedantically spew out conjecture but only relay your EXPERIENCE. Your tips on formic acid concentration were invaluable. Your pet ether extraction of cann. was a beauty. When I read someone who disagrees with something you posted, it’s a sure bet they’ve never tried it. I would like to switch to dreams with aqueous MeAm, but would like to know the specific gravity (density) of 40% solution. I would be eternally grateful if some bee in a less anal country would measure their commercial solution and tell me a target density. I would also love the same data for bubbling into chilled methanol, which I would then dream about as the solvent in a standard Al/Hg. I love the concept, but I just need a route for quantitative analysis. In my dreams I usually add little nitromethane ‘kickers’ after a while. But be careful of that dreaded boil-over. So much work can wind up on your ceiling, and then you start beating yourself up... When I cleaned up the products from degradation of hexamine with annhydrous ipa and then chloroform, it yielded a nice crop of ammonium chloride and yellow shit. Does the nitromethane reduction run clean? Has anyone bubbled for the hydrochloride salt and then cleaned it with chloro to prove its purity? I would go with the in situ reduction dream, but I don’t want to wind up with some shotgun amination product. And let’s face it...I don’t want to repeat the purely academic research of others. Maybe I’m missing the big picture and just using MeOH saturated with MeAM as best I can manage (without stinking up the entire neighborhood) will work at the 800ml/mole level. (God bless Osmium) Sorry to carry on so, but I have so much to say to the hive and since every post aggravates my paranoia (I’m delusional) I’m just trying to get it all in at once. For every soul that comes out of the woodwork to post, you can be sure there’s ten who are reaping the benefits in quiet thankfulness. Ok, two quotes and I’m done. Prohibition will work great injury to the cause of temperance. It is a species of intemperance within itself, for it goes beyond the bounds of reason in that it attempts to control a man's appetite by legislation, and makes a crime out of things that are not crimes. A Prohibition law strikes a blow at the very principles upon which our government was founded. Abraham Lincoln (1809-65) Government is not reason, it is not eloquence, it is force; like fire,
a troublesome servant and a fearful master. Never for a moment should it
be left to irresponsible |
| Osmium PimpBee |
posted 12-28-1999 06:45 PM
Hehe, not bad newbee! 40% aq. MeNH2 SG=0.90g/ml |
| Blanka unregistered |
posted 12-28-1999 08:36 PM
Bravo |
| Stonium Hive Bee |
posted 12-29-1999 03:35 PM
Nice one. A pretty big dpharma fan myself. Sooooo... let's hear it for him, then...Woo-hoo-hoo!!! Little known fact: Ol' dp won the Hive award last year for "Bravest Personal Experimenter." Didn'tcha now, dp? Uh-huh, he did. I'll take this to mean there must bee a method to our madness. Just
knew there had to bee a reason for giving out those yearly Hive awards...
Later, |
| Semtex
Enigma Hive Bee |
posted 12-30-1999 09:48 PM
Nice work, one note though, SWIM tried to adapt Gyro and Labtop's performic variation to the peracetic, all seemed to go well until after the distillation. When it was put into the freezer overnight it gel'd or froze soild, even though it looked right, smelled right and came over in the right temp range. Since there was some peracetic ketone in the freezer at the same time you could really tell the diffence, so amination wasn't even tried. IMHO stick to the single phase for the peracetic, unless you wish to be the one to work out the bugs in the two phase, either way, good work, and lot's of luck... 
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| ChemHack Hive Bee |
posted 12-31-1999 01:50 PM
Check out the thread named "OTC replacement for performic" in the forum on Novel Discourse. Semtex Enigma wrote out a synth that I dreamed about 1/20 scale. It was a white Xmas. |
| dpHarma Hive Bee |
posted 01-02-2000 01:47 PM
Tao Your words of detailed instruction define you as person of deep insight and perception. May the blessing you intend return double to you. I thank you each for your gracious comments. I have enjoyed these times. The community of searchers and doers and wanna bee somebees is a truly transcendant organism. If my tiny offerings have benefited anyone in their personal quest than
I am grateful. someday, when the name dpHarma has disappeared from cyberspace, and his spirit no longer wanders the souq' of the lycaeum and his 16bit digitized voice ceases to stream from endless tired servers, remember a foolish and courageous sot who dwelt among you. one who dared to dream and lost himself and found self in Him. You are learners
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| Penis
Seinfeld Hive Bee |
posted 01-02-2000 03:31 PM
That was beautiful. |
| dpHarma Hive Bee |
posted 02-03-2000 04:41 PM
Tao Corning: you wrote: The H2O2 was pool store shock which was labelled at about 27%. But my handy dandy wine making hydrometer (God bless dpHarma) told me that some settling of contents must have occurred during shipping and handling. So I put it into a distillation setup and started boiling the water out of it. When I stopped, the hydrometer told me it was 35.7%
thank you for your info. dpHarma |
| Tao
Corning NewBee |
posted 02-07-2000 05:16 PM
DpHarma: Actually, you got the blessing on that one because I remembered
(apparently in error) that you gave a sort of general formula for
calculating the concentration of formic acid. It was based on the ratio of
densities Needless to say, you've got me doubting the accuracy of this method.
Makes me feel bad that I cursed the peracid methods. (Actually that Semtex
dream Chemhack mentioned is a beauty) A seltzer bottle, a pair of flaired copper pipes, a little sweat soldering and $150 worth of short tank w/ regulator from the welding shop. SHAZAAM! My eyes are cracking open, slowly, my life is full of the healthiest relationships I have ever found possible and I have a deep sense of teleological meaning to events that unfold before me. (I was never able to be a spiritual person before, not really) I am sorry that I was a dead end, informationally. I saw your post immediately after mine asking others to undertake some fact finding in this area. This puzzled me. Could you please tell me how much formic acid you started with in your
stovetop leukart dream? I am interested in the 4gm reduction and thought
the 5gm of 65% was for the test tube (small) run. Forgive my ignorance. I
have burned the search engine up on randolph carter to no avail. My
girlfriend thanks you in advance, as non-methylated dreams make my love
lean more towards eros than agape. (Sometimes she gets tired of
cuddling...<grin> ) |
| Tao
Corning NewBee |
posted 02-07-2000 05:20 PM
I didn't know the colon was reserved for that little expression-face. Yes I did temperature correction when using the hydrometer per the instructions included therewith. I think it was calibrated for 60^F. |
| Tao
Corning NewBee |
posted 02-09-2000 10:22 AM
Never mind me. I found it under the TMA-2 story. Um nada smaht mayan jenny... |
| Bright
Star Hive Bee |
posted 02-09-2000 10:45 AM
dP- Magnificent. I bask in the light of you. |
| dpHarma Hive Bee |
posted 02-16-2000 11:27 AM
Tao I've revised my estimation of the quoted S.G/ % method. although it SHOULD work, there appears to be a 'slew' factor at higher concentrations. This may be a surface tension issue and may be related to the specific liquid under exam. efforts to 'graph' s.g/% using available numbers are underway. If anyone has ANY known number pairs for various % of formic acid and/or H2O2, please contribute them. I'll track down the posts I used to set the ratios in the stove top exp., and advise. several exps. later, suggest SOME yeild results no matter what ratios
are used. yah! no methyl makes dick a busy boy. sometimes sore too.
you flatter me, undeservedly too I might add. thanks friend dpHarma |
mixture, minus 1)
divided by (pure substance, minus 1) I have no books from where I am
writing this, but I think pure H2O2 is 1.47rd. My hydrometer (must have)
read 1.168. (.168/.47=.357)
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