Rhodium, I'm flabbergasted!
Did you really miss all these months and years my write up for the Classic Performic acid method ?
The first one I posted in the first One Pot MDMA/NaBH4 thread in begin 1999! You can find that one back at the end of my following write-up. That was the one where for the first time the use of SodiumBIcarbonate was mentioned by me, in contrast with Ritter, who used Sodiumcarbonate, and a different method of preparing the mixtures.
Then a VERY extensive write-up I posted in my Detailed Methods for NON-Chemists, IT's DONE sticky threads in the Newbee and Methods forums.
They hang there allready nearly a YEAR !
Notice a few things there:1. I start with 16.25 gram Isosafrole, end with 16.00 gram pure MDP2P, I also gave a w/w and mole % !
2. I allready explained that you only needed half of the 15% H2SO4 solution from the original reference, to safe a lot of waste!
3. My write-up is exactly the same as Baalchemists, only much more explained, there are no differences at all, chemically spoken.
So did he follow this write-up, yes or no?
4. I have multiple times explained in many threads here that in my opinion this method is the most easiest, most consistent and secure method to get real pure ketone. Why did you never take notice of them, while you declare now to be very interested in it?
5. Already in 1999 it was posted by Gyrogearloose that my form of the Performic worked better than Ritters, he even got into discussion with Ritter about it, but his use of the english language gave way for some misunderstanding at first, because both participants did not understand that they both talked about a different interpretation of the performic.
They both thought to be talking about one method, but they weren't.
At the end of my write-up you see Ritter declaring again that his write-up works better, but I disagree, the way I explained it gives consistently higher yields. If I remember right, also Methylman and some others have followed my write-up, and all mentioned the high yield on this board.
6. I gave amounts of reactants for small scale and big scale together, so any sane person can conclude from that, that this method is infinetely upscalable, and I know of no other method which is also.
Biggest scale ever done by me was 1500 kilogram Isosafrole. Same yield.
Here's the write-up, for your convenience :
MDP2P : MethyleneDioxyPhenyl-2-Propanone (Classic Performic acid method) :
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Isosafrole --> MDP2P via Modified Classic Performic Acid :
Materials :Same as for ISOSAFROLE, plus :
1--minimum 500 liter stainless steel milk coolingtank, with a big-ass cooling coil in the double walls, preferable in the bottom also.
1--Mixer motor, 220 Volt, non-sparking, induction type, for :
1--Mixer propellor + axle (diam. 1.5 to 2 cm), stainless steel, diam. 40 to 60 cm.
1-- 100 liter plastic container to prepare the PerAcid mix.
and/or :
1--big-ass 80 liter dripping funnel, stainless steel, plastic or glass. Homemade is cheap.
1--1 meter cooled refluxing column, glass or stainless steel, to fix on the only opening of the milktank which is left open to the air.
5--meter heating cable, chemicals resistant, to use in milktank for the hydrolisis step with 15 % H2SO4.
Chemicals :Reaction :27 kg IsoSafrole, purity >/= 96 %.
99.7 kg DiChloroEthane, ClCH2CH2Cl, Industrial quality >/= 98 %.
or :
99.7 kg DiChloroMethane, CH2CL2, Industrial quality >/= 98 %.
8.3 kg SodiumBiCarbonate, NaHCO3, pure.
41.5 kg Formic Acid, HCOOH, 86 %.
25.1 kg HydrogenPeroxide, H2O2 30 %.
22.43 kg Sulfuric Acid, H2SO4 Industrial quality ~99 %.
127.07 kg water, H2O, pure.
42.4 kg Methanol, CH3OH, Industrial quality >/= 98 %.
Extraction :To extract from 218,9 kg hydrolized Glycol/15%H2SO4/CH3OH mix :
60 liter DCM or DCE = 3 x 20 liter, Industrial quality >/= 98 %.
Method :Here are the
original figures from literature in grams, for a
27 KG batch of Iso-safrole to MDP2P :
---
(all figures multiplied with: 27000 grams devided by 16.25 grams = multiply them with 1661.54 ) ---
M1. - Combine 16.25 grams [or 27 kg ] of Isosafrole with 50 ml=60 gram (1 liter DCE or DCM = 1,2 kg), [or 99.7 kg] DCE (DiChloroEthane) or DCM (Dichloromethane)
plus 5 Grams [or 8.3 kg] Sodium bicarbonate (Sodium Hydrogen Carbonate : NaHCO3).
Can be made by bubbling CO2 gas in a strong soda solution (Na2CO3.10H2O ), the sparsely soluable NaHCO3 will precipitate.
M2. - Let it
vigorously stirr for 2 or 3 hours, depending on the strength of your mixer [a total of 135 kg ].
This gives it time to form a pH-buffering complex which facilitates the next reaction enormously.M3. - Seperately s.l.o.w.l.y combine (under external cooling) 25 gram [41.5 kg] 86% Formic acid and 15.1 grams [25.1 kg] 30%
fresh Hydrogen Peroxide (to create Performic acid) and cool to 0 C.
Note :
It is critical to cool when preparing this mixture or else it will, after sitting for 3 or 4 hrs without cooling, start boiling and nasty fumes will fill your lab and you will have to evacuate the place.
M4. - Then drip this cold Performic-acid [66.6 kg] VERY VERY slowly , into the 135 kg ISO-DCE-Sodiumbicarbonate mix, keeping temp under 40 C with external ice-bath or other means of cooling until all is in , CO2 bubbles out of the reaction mix while dripping in (and watch the temp for the following 1-2 hours, after completing dripping in, closely, so it still can not exceed 40 C).
M5. - Stir
!VIGOROUSLY!, preferably with an overhead stirrer, for a total of 6(six) hours.
M6. - Stop stirring and move the whole batch in portions to a big seperatory funnel, and let it sit for one hour in there.
M7. - It will be orange-juice color DCE/pre-MDP2P(Glycol) mix at the bottom and clearish performic acid mix (H2O2/HCOOH) on top, the orange layer with the pre-MDP2P (Glycol) and DCE is heavy, so it goes fairly fast to the bottom of the funnel.
M8. -
Important Note: --------------------------------------Many members have reported a switch of layers when they used DCM. Iso/DCM layer on top OR at bottom !
There is a perfectly logical explanation for this phenomenon : The one's who's cooling equipment functioned o.k. and thus kept the temperature between 36-40 Celsius will see the Glycol/DCM at the bottom after separation period,
because they still have all their DCM left in the mix. The one's who were not so lucky and let the temperature get out of hand will see the orange layer at the top, due to an extensive loss of DCM which evaporated into thin air. The densities of the normal Glycol/DCM mix and the PerAcid mix lay close together, so if you evaporate too much DCM this balance is switched and suddenly the PerAcid mix is the heaviest layer, and falls to the bottom. You will notice then a light yellowish PerAcid mix at the bottom and a orange-juice coloured Glycol/DCM mix on top. This is no reason for real worry, unless you boiled most of the DCM away (not good for your health if you were in the same room (carcinogenic) AND not good for the reaction which did not have enough cooling capacity anymore in the last stage, depending on how high you overshoot the temp. Boiling temp of DCE = 83 C, DCM = 40 C , that's the reason WHY you must keep the temp under 40 C when you use DCM! And you must also do this when you use DCE !
Instructions are allways given with a reason, which is in literature expected to be common knowledge, but not here at a forum crowded with C(r)ooks (hehe) and a few real chemists.
Thought I owed the Cooks the explanation for this reason.
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M9. - Seperate into a new empty container and evaporate (low-vacuumdistillation, but KEEP the TEMP under 60 C!! so use more vacuum , so go lower then 700 mbar if the temp rises too high) the DCE off and stock that recovered DCE for future use.
M10. - You should add now 180 grams [but in reality, in contradiction to the official reference, only HALF the amount necessairy!, so 90 grams = 149,5 kg] of 15% Sulfuric acid (H2SO4) [so : add 22.43 kg 99% H2SO4 to 127.07 kg water], boil it until it starts refluxing back with slight addition of 60ml=51 gram Methanol [only HALF! needed, so 25.5 gram = 42.4 kg Methanol (1L methanol=0.85 kg)] through the cooling/reflux condenser added on the distillation kettle for 2 hrs.
No longer then 2 hours !!! Or you will begin to loose product-yield. You now converted the Glycol to raw MDP2P, mixed with some pollutants.
M11. - Let it cool and extract 3 times with enough DCM (or DCE), (minimum 10 reactionvolume-percent per extraction).
M12. - Combine the DCM or DCE extractions and then boil the solvent (DCM or DCE) off (in fact no vacuum needed, but if you are in a hurry:)with one or more aspirators combined or diafragm vacuumpump to get brown oil that is peppery and cardamon smell.
M13. - You get around 16 grams [26.6 kg] -dirty- MDP2P.
M14. - To get the real clean MDP2P, you will have to vacuum-distillate this dirty MDP2P-base again to get a reasonable yield of about 73-75 % (grammole-percent)= 17.8 kg clean MDP2P which should be light yellow, or if you distill exact and have no leaks to let tiny amounts of air in, and you don't let the temp go over 170 C, at ~20 mbar vacuum, it would be clear with no color.
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Note:
In weight/weight procents you get 16 / (16.25 / 100%) = 98.46 w/w % , but yield is scientifically allways given in Mole-percents, so:
(16 gram x 178.188=molecularweight MDP2P / (16.25 gram x 162.188=molweight Iso / 100%) = 2851.008 grammole / (2635.555 grammole / 100%) = 108.17 mole %.
But the effective mole % after distillation (=ultimate clean-up, no washings then necessary!) is 75%.
20 mbar x 0.01450138 = 0.29 psi, which is good enough for all distillations we work with !
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Here are the four threads on the old board I found back again which are relevant for the classic performic:
1.
Post 107771 (missing)
(smokemouth: "LaBTOP/Gyro performic results - Sumerian", Methods Discourse) LaBTOP-Gyro performic results - Sumerian .
2.
Post 107780 (missing)
(smokemouth: "LaBTop/Gyro's Modified Performic Questions - Synthia", Methods Discourse) LaBTop-Gyro's Modified Performic Questions - Synthia.
3.
Post 107770 (missing)
(smokemouth: "New Performic Scale Up Question? - artech", Methods Discourse) New Performic Scale Up Question - artech.
4.
Post 107739 (missing)
(smokemouth: "The correct way to mdp2p via performic - gyrogearloose", Methods Discourse) The correct way to mdp2p via performic - gyrogearloose .
And this is the original Classic Performic post in the thread :
http://hive.lycaeum.org/ubb_board/Forum3/HTML/000613-3.html
NaBH4 question : solution: One Pot ! :
Classical Per-acid oxidation of Isosafrole to get Piperonylacetone (MDP2P):
(Iso.) [R]-CH=CH-CH3 ----> [R]-CH2-C(=O)-CH3 (Pip.Ac.)
R=Methylenedioxyphenyl
The PerAcid solution is made from 25 g. HCOOH (formic acid)(86% ,starting from 99% HCOOH) and 15.1 g. 30% H2O2 (hydrogen peroxide).
This sol. is added to a mixed sol. of 16.25 g. Isosafrole(>/=90%) and 1,5 g. NaHCO3 (!!) in 50 ml CH2Cl-CH2Cl at 35-40 C.
The temp. is during 6 Hrs. mixing regularaly checked and kept within 35-40 C.
The solvent is evaporated (vacuum, keep TEMP! UNDER! 60 C.!).
Residue is boiled with 180 g. 15% H2SO4 for 2 Hrs.
Extraction with 3 x 100 ml.CHCl3, wash with water,dry over MgSO4 and evaporation of the solvent gives a brown oil (purity >/=90%).
Supplemental purifying by Kughelruhr destillation (~70 C, 0,2 Torr) gives 70-75% yield of MDP2P (>/= 95% pure!)
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And this is the latest info from Ritter, who by the way posted this method first, then Beagle_boy , then me, then Gyrogearloose, so this method needed 3 times posting to get the attention needed, so lets call it from now on the Classic Performic, to avoid any misunderstandings:
Ritter
(Stranger)
06-20-00 14:26
Re: LabTop modified performic method?
The reaction runs best as described in my writeup! Adding carbonate to formic/peroxide first would surely lead to a nasty volcano and would not help any. Carbon Dioxide is emitted as performic is slowly added to alkene/carbonate solution. As far as advances are concerned a few things have been realized. Extremely vigourous stirring, such as that produced by a mechanical stirring rig, seems to increase yields. If a considerable amount of isoalkene is recovered during vacuum distillation an easy solution is to add more performic acid mix to rxn. This is usually an indicator that the peroxide used has degraded somewhat below 30%.
With this MDP2P you proceed to make :
WISDOMwillWIN