DCM

Kovalenko S A, Ernsting N P and Ruthmann J 1996 Femtosecond hole-burning spectroscopy of the dye DCM in solution the transition from the locally excited to a charge-transfer state Chem. Phys. Lett. 258 445-54... 

Science dealerships aren t the only places to get the stuff one needs. At those mega hardware stores one can find pure acetone, methanol, ethanol, toluene, methyl ethyl ketone, DCM(as a constituent of some stripping agents), sodium hydroxide in the form of lye, and some acids such as sulfuric and hydrochloric. These precious tools can be bought there cheaply and in great quantity. 

NOTE a really good procedure for busting up the emulsion caused by introducing the water is to slowly acidify the water layer with HCl. As the water layer acidifies one will see the emulsion vanish. As this occurs the water layer will lighten as particulates and stuff start to exit the water layer and go into the DCM layer. Works every time. 

If you netralize the formic acid mix with 25% NaOH the layers separate out nicely. It takes 75 / of 25% NaOH to neutralize the soln for 150grm 88% formic, so you ll need a big sepatory funnel. After you hit ph 4.5 add it rery carefully cause it ll run away to 9+ real quick. You can then back extract the water with DCM, or I guess preferably ether. If you use too much DCM when extracting it sinks to the bottom and some product floats on the top, so you end up with three layers... But then my lab tech SUXSI (not that I d partake in iilegal activities. p"... 

The soiution is aliowed to cool and the crystals of the P2P-bisulfite addition compound are then separated by vacuum filtration, washed with a little clean dH20 then washed with a couple hundred mLs of ether, DCM or benzene. The filter cake of MD-P2P-bisulfate is processed by scraping the crystals into a flask and then 300mL of either 20% sodium carbonate solution or 10% HCi soiution are added (HCI works best). The soiution is stirred for another 30 minutes during which time the MD-P2P-bisulfite complex will be busted up and the P2P will return to its happy oil form. The P2P is then taken up with ether, dried and removed of the solvent to give pure MD-P2P. Whaddya think of that ... 

The solution is ready for extraction. In her first dream she used DCM and broke it into 4 extractions of about 1500 mLs each (she had a 2-liter separatory funnel). Since DCM goes to the bottom, a separatory funnel is a must. Buy or make one. The extractions should go without any problems, as there isn t any emulsions to contend with. She used 100 mLs of DCM for each extraction. 

Set-up for vac-distillation. She wraps the flask and still head with aluminum foil to act as an insulator. Speeds up the distillation process. Begin to heat the DCM extraction slowly under maximum... 

To separate the oil added an equal volume of fresh cool water (note waited until solution cooled before adding the water). The oil started to drop out perfectly, used DCM to extract all traces of the oil. This woik up is by far the cleanest, easiest and simplest to date... (This dreamer was tried all method of ketone synthesis)... Once the oil was extracted, the extracts were pooled washed with sodium bicarbonate lx, saturated solution of NaCI 1x, and two washes with fresh dHzO... Some time was required for the work up as there was a little emulsion from the use of the base wash and then with the first water wash. The JOC ref suggested using an alumina column to remove the catalyst (could be a better way to go). 

When completed, the solution is merely dumped into 1L of dH20 and extracted 3 x lOOmL Et20 or DCM or benzene. BUT when that solution hits the solvent, the biggest, ugliest emulsion Strike has ever hypothesized occurs. It is wicked The chemists can try all the usual tricks to get rid of that bitch, but when it comes down to it, there is only one way that works. The chemist is going to have to extract with hundreds upon hundreds of mLs of solvent. The idea here is to saturate both the aqueous and emulsion layer with so much solvent that a separate solvent layer can form. Once saturated, the entire mix can then be properly extracted. 

METHOD 7 Another piperonylic acid method for your perusal [22, 23]. 70g piperonylic acid or 65g phenylacetic acid in 250mL DCM is stirred in a flask and 64g SOCb is added dropwise. The solution is heated to reflux until no more HCI gas is released from the solution. The chemist should have a tube leading from the top of the reflux condenser to a glass of water to catch all that HCI... 

Now the chemist need only extract the MDA oil from the water with some DCM. Yes, this time the MDA will go into the DCM. The chemist merely pours about 400mLs of DCM into the container and stirs it really well for a few minutes while she watches TV. As much of the water as possible is poured off or separated... 

The cleanup of this oil is exactly like that which was done in Method 1. The oil is dissolved in about SOOmL of 3N HCl and the solution extracted with TOOmL of DCM. The chemist remembers that in this particular case the MDMA or meth is going to stay in the HCl/water but that unreacted, valuable MD-P2P or P2P is going to be in that DCM so it, of course, is saved. The HCl/MDMA solution is then basified with concentrated NaOH so that at around pH 9 the happy little beads of final, freebase product will appear in the solution. As usual, the oil is extracted with DCM, dried through Na2S04 and the DCM removed by distillation. The final product here is usually a little darker in color than the product achieved in Method 1, but it is still remarkably clean and may be crystallized as is with the crystallization process removing most of the color impurities. Of course the chemist may wish to vacuum distill to afford clear product. The average yield with this method is 60-70%. 

You know how just a couple of paragraphs ago where the chemist first filtered the crude crystals from the chilled reaction mixture, then washed them with water or acetic acid Well, all that liquid filtrate has a lot of valuable, unreacted piperonal or benzaldehyde in it. To rescue the stuff the chemist dilutes the mixture with 500ml dHaO and extracts it with DCM. The DCM is washed with 100ml 5% NaOH solution then vacuum distilled to give a dark oil which is unreacted aldehyde. Hey That s a lot of good material that can be put through the process again. 

Once the reaction mix has cooled after reflux, 500mL of room temperature dHsO can be added and the whole solution extracted with DCM. The DCM layer is separated and the solvent removed by distillation to give the li-nitropropene as an oil of all things. This oil can then be recrystallized in hot methanol just like the crystalline form was [38]. 

The reaction itself works by the action of Na or K from NaOH or KOH which form what is called a catechoxide dianion with the two OHs of the catechol species. This makes the two ripe for an attack by a methylene halide which can be either DCM (methylene chloride, or dichloromethane), DBM (methylene bromide, or di-bromomethane) or DIM (methylene iodide, or diiodomethane). DCM is cheap and works pretty well, but DBM and DIM work better yet are more expensive. 

DCM - Dichloromethane 100ml pour into the reaction flask with the DMSO. 

In a plastic container the chemist dissolves her golden yellow freebase oil into some DCM, ether or ethanol. The chemist then starts a steady dripping of the sulfuric acid into the HCl/salt and white, puffy HCI gas will start to exit the glass rod or pipette which is at the end of the hose. That tip is then plunged into the sol-vent/freebase solution to bubble the gas through the solvent. 

There is a very important point to stress about the above procedure. Strike listed ether, DCM and ethanol as crystallization solvents. But the one chemists should use is DCM. That s right...DCM Strike is telling all of you right now that DCM is an absolutely superior solvent for crystallization. In fact it is so good that one need not purify the freebases acquired from the ends of half of the recipes in this book. 

Most of the final product producing recipes in this book will provide for the chemist to take up the final free base product in DCM. Usually the freebase oil in the DCM is dark. Used to be that Someone-Who-ls-Not-Strike (SWINS) would have to distill the freebase to get clear yellow oil before crystallizing because when SWINS used ether or ethanol as a crystallization solvent, the colored crap would contaminate the final product. But not with DCM. Even with the grungiest (well...not too grungy) freebase, the crystals that come out are pure snow. The DCM so strongly solvates the contaminants that none remain in the mass of crystalled final product. The filter cake is sooooo clean even in the darkest solvent ... 

The other amazing thing about DCM is that the crystals produced in it are weird. Crystals produced by ether are little and powder-puffy. Nothing wrong with that per se. But the crystals produced in DCM are large, crystalline and sparkly. And although there shouldn t be a difference, SWINS swears the effects are more powerful. 

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