|DETAILED METHODS for NON-CHEMISTS The Sequel !||Bookmark|
If you don't have or take the time to read the first part of this Quest for Knowledge ( Post 26263 (LaBTop: "DETAILED METHODS for NON-CHEMISTS Edit: IT'sDONE!", Newbee Forum) D.M.f.N-C. Edit:IT's DONE), read the following please, and don't be lazy and think "let the others do it", give me your feedback if it's in your might.
YOU ALL HAVE MORE OR LESS TO BE THANKFULL FOR THE PRICELESS SECRETS WE GAVE TO YOU AT THE HIVE, IT'S PAYBACK TIME NOW !
GIVE ME AS MUCH FEEDBACK AS YOU CAN ! I NEED IT TO WRITE THE SECOND PART!
All this so badly needed info lays scattered and hidden around here in the search engine, we need to dig the most relevant info up and place it in these series of threads, so any newcomer or oldy can quickly find the latest info.
Rhodiums site is a beautifull place, but is not always really uptodate. So he will dig around here for easy access to the compacted knowledge we all provide, and has an easy job then to upload what he likes to his site.
For those interested, the first thread has been editted extensively, hundreds of small and big edits/additions and also some major corrections were made.
Why f.e., has NOBODYWe all failed the build-in IQ-test!
PS : You can't post in here, post your help and thoughts in "The Sequel!" thread in the Newbee forum Post 26263 (LaBTop: "DETAILED METHODS for NON-CHEMISTS Edit: IT'sDONE!", Newbee Forum) . LT/
|Re: DETAILED METHODS for NON-CHEMISTS The Sequel !||Bookmark|
IMPROVEMENT for AL/Hg REACTIONS.
RollWitMe (Newbee) 02-19-01 09:41 No 174315
High Temp Amalgamation
Not sure if anyone else has done this but SWIM this morning did. Added 0.4g of HgCl2 to 750mL MeOH.
Stirred and heated until boiling. Let cool to ~55C. Added 27.5g Al. Basically instant amalgamation. How does SWIM know it's amalgamation and not MeOH boiling off of the aluminum. Well the aluminum is floating on top and the solution is starting to turn grey. Immediately started dripping Ketone/Nitro/MeOH 25g/20mL/50mL at a rate of 3-4 dps. Typical yield of 17-19g on previous runs for SWIM, this one resulted in 22.5g. Might have been better ketone, or maybe adding the solution to an already pissed off boiling amalgamation helps boosts yields. Work up was done in the typical way, 35% NaOH, extracted w/ Toluene, washed 4X w/ dH2O 1X w/ Sat'd NaCl. Rotovapped down to 100mL. Dried w/ 30g MgSO4. Gassed, filtered, washed & dried. Hoo-ray. I like to cook!
Rhodium (Chief Bee) 02-19-01 13:24 No 174349
22.5g freebase or 22.5g hydrochloride salt?
RollWitMe (Hive Bee) 02-19-01 13:44 No 174355
That's 22.5 of the salt. SWIM must admit that he wasn't prepared for immediate amalgamation and had to run inside to go get the ketone out of the freezer and run back losing valuable time. Next time SWIM will know better and have everything ready to go before hand when starting it hot.
Seillean (Newbee) 02-21-01 11:57 No 174709
RollWitMe - How many times did you have to gas to get the almost an ounce of xxxx.hcl out of the 100ml toluene? I have heard that somebody has seen the same amount gassed in about 500ml of toluene and that shit was thick, like a milkshake, twice! Was the stuff fluffy or like flour when it was dried?
RollWitMe (Hive Bee) 02-21-01 21:10 No 174788
1 gassing, took about 10 minutes of bubbling. the color is really white, but the texture is like flour, kinda compresses packs easy. taste is definitely right. measured dose definitely works. ran the same high temp amalgamation again today w/ same results. im pretty pleased. I did notice one thing. when doing it this way, all the aluminum does not react. Even using 500mg of hgcl2 for 27.5g Al. I only let it spin for 1.5 hours on top of that. Stinks like MeAmine when I add the NaOH so on and so forth, workup is easy. gas inbetween 125-175 mL toluene. until it looks like a soda can of white gelatin material. this seems to save time and boost yields for me, waiting to hear back from others if they try it.
sYnThOmAtIc (Hive Bee) 02-21-01 21:48 No 174793
Sure I know someone who could verify this but firtst he needs o know a lil more. For one he has never done that al/hg with an addition rate that fast. What were you using for a flask size wise and what kind of cooling setup condenser wise?
Antibody2 02-22-01 07:15 No 174866
Synthomatic - a 2l flask is ideal for that size amalgamation. It seems like alot of flask but with the fast addition rate you NEED the head room. I've seen it done with a 300ml west condenser w/ addition funnel atop the condenser.
RollWitMe (Hive Bee) 02-22-01 14:10 No 174934
Sure, once you get a nice rolling boil, add the aluminum, turn off the outside heat. Wait about 1 minute and then start dripping your ketone into it. 2L 3 neck flask w/ a 7 stage reflux condensor. Actually when running this reaction pace, my condensor has never clogged, gurgled, choked whatever. When starting the amalgamation at lower temps, you're dripping ketone nitro into the solution and its not all reacting, so when it does get hot you have this build up of ketone that reacts and gets the reaction out of hand sometimes.
This doesnt happen when you drip it in when the temp is already boiling. Nice 3 drips per second the entire time. Good yields, Less time. (30 minute addition, 1.5-2h stir time.) Workup the usual way.
BENZOQUINONE to KETONE
RollWitMe (Newbee) 02-19-01 00:11 No 174253
SWIM dreamed up some Ketone this evening. I know everyone has seen this before but SWIM just wanted to add a few things not listed on the normal write-ups for people new to this ( like myself ).
All allowed to stir together for 2 hours in a 2L 3-Neck Flask w/ low heat to ensure everything is in solution.
An egg-shaped stir bar works best for RB Flasks. ( Of course I dropped one in and it fell right through the bottom of my Flask the first time I ever did this. Oops. )
In a 250mL addition funnel was placed 150g Alkene w/ 50mL MeOH.
This was mounted and started dripping while a 9 stage reflux condensor was placed in another neck.
Addition was made over a period of 45 minutes while a decent reflux was attained.
Stirring proceeded for 6 hours with heat on, allowed to spin for 2 additional hours while cooling.
While cooling 1500 mL of 5% NaOH was made up and allowed to stir.
Also 1.7 L of 1N HCl was made.
It says to filter the entire mess, I say skip it, who cares. Wastes time and product if you ask me.
Dump your solution into the HCl. Using a 4L beaker works best, throw in a stir bar and let it spin in the HCl for a few minutes and then dump 500mL DCM and crank the stirring again for 5 minutes ensuring really good mixing. Turn off the stir bar and let settle for 15 minutes. Decant as much of the top layer as you can and then dump the rest into a sep funnel to seperate the rest.
Wash your DCM layer 2x w/ Sat'd Sodium BiCarb.
I think we all know about the crap ( looks like frog eggs/gunk/green apple splatter etc) that forms in the middle. Well it contains a lot of product so make sure you keep it w/ the DCM washes.
Wash your DCM layer 1x w/ Sat'd NaCl.
Same thing, don't throw away too much, if it has a strong methylene chloride smell it most likely has some goods still in it. Save your washes to extract once in the end.
Wash your DCM layer 3x w/ 5% NaOH
We all know the first wash is really dark black, also the middle gunk layer is becoming smaller w/ each NaOH wash. After your 3rd wash, combine all washes in the 4L and extract 1x w/ 100mL DCM. Turn the stirring on full tilt for 5 minutes. Your final DCM wash will be a lot lighter then all the washes and easy to decant/seperate. After the last wash throw 50g anhydrous MgSO4 and filter. Distill off the DCM w/out Vacuum and save for a later day. SWIM has 2 vac pumps, one that boils Alkene at room temperature and is more powerful then SWIM can find a use for until he gets a bleed valve for it. The other ones boils alkene at 92C and knows to watch for ketone @ ~ 130C. Well only 2 drops of unreacted alkene came over at ~95C and then a neon green ( very pretty, SWIM first tone runs were darker yellow w/ only slight green undertones compared to this which was practically glowing flourescent green ) fluid came over @~138-145C and amounted to ~100mL's which is roughly 110 grams. The previous darker tone aminated @ ~ 60 % molar yield so SWIM expects this to be a little better.
Anyone have any other findings they'd like to share that I missed. I do think that not filtering and using less washed helps w/ yield a lot. Let me know if anyone else dreamed up something different. Peace.
noj (Hive Bee) 02-23-01 11:45 No 175082
I've noticed the problem with filtering too. The first nap I took using a reflux on the wacker I placed in freezer overnight, and alot of the hydroquinone became immobilized on the bottom of the flask. Maybe that would help out.
Also, the color of the ketone. I see posts mentioning that a lighter yellow color is better than the deeper flourescent color. Having only had a couple successful dreams, both a dark yellow flourescence and a pale lemonade color, I noticed the roll was slightly milder with the color being pale. Whereas when it was deeper, 140mg left me on the floor for about 30 minutes reveling in the intricate textures of the carpet, unable to stand up.
Anyone know what influences the color of the ketone?
RollWitMe (Hive Bee) 02-23-01 13:22 No 175096
Yeah could anyone fill in about the ketone color variations? What is the exact color of 100% pure MD-P2P?
I've also had a palish yellow w/ green tones, a dark yellow w/ green tones and a fluorescent green w/ no yellow tones in sight. All aminated fine, texture of product varied but that's just from gassing and recrystallization. Any input?
terbium (Hive Addict) 02-23-01 13:28 No 175098
Pure MDP2P should be a pale yellow.
LT/ : no, it is blank like water, when you discharched the first and last few ml of your distillate. If you keep it under a N2 atmosphere in a tightly closed bottle, it will stay that way. Leaving it open to the air for too long will give it that pale yellow color.
RollWitMe (Hive Bee) 02-23-01 13:42 No 175099
Pure yellow with no green at all? Weird, cause i swear this stuff is like neon green. I even distilled it twice which I was real hessistant to do because of decomposition worry. Well it works so I guess I can't complain.
LT/ : Vacuumfilter the green oil through very fine active coal a few times, that should leave you with pale yellow ketone. If not, try after that simply to wash your green ketone with warm distillated water and separate the water and dry the clean ketone with NaSO4 or silicagel or MgSO4.
Test a small portion of your green ketone for platinum rests by acidifying with HCl and adding a few drops of stannous chloride solution : a yellow or brown colour develops according to the quantity of platinum present. The yellow colour is soluble in ether, thus rendering the test more sensitive. The dilute HCl will render the green colour allready to a much paler colour, so you can see the difference in colours easily.
P2P KETONE FROM EPHEDRINE(-TABLETS or BULK)
(Translated by LT/)
Bwiti (Hive Bee) 02-16-01 19:27 No 173860
What's up folks?! Last night I was poking around a patent database when I ran into an interesting P2P synth. Here's why I think this patent would be useful to evil chemists: Someone can scrounge up a shit-load of pseudoephedrine from cold pills, or ephedrine from ephedra powder, but the hard part is obtaining RP. Who wants to scrape RP off of match-books? Fuck that! I did my best to translate the patent, but it still needs work. Anyone here good with german? (LT/: I did)
Procedure for the Production of Phenylacetone (P2P).
Patent # : DE3200232
(addition for patent application P 30 26 698.9-42)
The invention concerns a new arrangement of a procedure for the production of phenylacetone.
The subject of the principal patent (patent application P 30 26 698,9-42) is marked as a procedure for the production of Phenylacetone from Ephedrine by sulfuric acid (H2SO4), by the fact that one executes the conversion to P2P with 50-70 % acid at 150 to 155*C and in the presence of 0,02-0.5 % zinkchloride as a catalyst and that one continuously distillates the formed Phenylacetone out by means of steam distillation, directly from the beginning of the reaction.
It was now found that one can execute the conversion also in the presence of 0,05 to 0.3 % of other metalchlorides in place of 0,02 to 0.5 % zinkchlorid.
As other metalchlorides are suitable Iron(III)chloride and in particular aluminumchloride, borontrifluoride and Titan(III)chloride, which are used as Lewis acids in organic chemistry.
The concentration of the sulfuric acid is selected in such a way, that it
amounts to a content in the reaction mixture of 50-70 weight %.
The reaction runs particularly well with a weight/weight(w/w) sulfuric acid content from approximately 60 %.
For the continuous discharge of the Phenylacetone from the reaction mixture, water vapour is initiated into the mixture, which removes the developing Phenylacetone immediately from the mixture.
The received distillate is extracted with toluene and the latter is removed by distillation. Thus one obtains Phenylacetone, whith a purety of
over 99,5 %.
For a source of Ephedrine comes Ephedrine, Pseudoephedrine, Norephedrine and Norpseudoephedrine as well as Bis-(1phenyl-2-methylaminopropyl1)-ether
The yields, which can be obtained with the new procedure, are within the 80 % range. The procedure runs at a relatively high rate/min.
A further advantage of the procedure consists of the fact that it can be executed continuously . Thus one can let a hot aqueous solution of the Ephedrine of choice flow into the hot acid, whereby the Phenylacetone/Water azeotrope continuously gets distillated out. Here it is only necessary, to remove the developing ammonium salt, e.g. methylammoniumhydrogensulfat occasionally.
The use of the mentioned metal halides in place of ZnCl2 offers advantages regarding environmental protection, because these are more harmless and do not disturb the biological reduction of the waste water.
1025 g 75 % sulfuric acid are mixed with 2 g AlCl3. In there one dissolves 426 g (= 2.58 mol) Ephedrine or Pseudo-ephedrine derivate from 50-100*C. Subsequently, the mixture is heated up to 145-150*C. At 125*C steam in moderate current is introduced in the fluid for better mixing. At 145*C one increases the steam introduction and distills in a period of 2 1/2 to 3 hours the Phenylacetone/Water azeotrope over. From the distillate one isolates by toluene extraction the raw Phenylacetone, which is free from Propiophenon. After distillation with a short Vigreux reflux column attached also, one receives Phenylacetone, yield 270 g (78%)with a purity upto 99.8 %.
One gets similar yields from Nor-ephedrine or Nor-pseudo-ephedrine for
Phenylacetone in a yield of approx. 80 %.
In 1000 g 79 % sulfuric acid, an amount of 100 g (-)-Pseudoephedrin-derivate gets dissolved, whereby the H2SO4-concentration is adjusted to 65 to 66 weight%. This solution is poured into one of the necks of a three-neck roundbottomflask, mixed with 4 g AlCl3 and heated up to 125-130*C.
By injecting steam, one increases the temperature to 145-150*C and keeps it going in a steady rate from now on with a flow-rate of approximately 1 to 5 g/min.
The 70-90*C warm solution of the (-)-pseudoephedrin(derivate) mixed with
79 % sulfuric acid solution(weight ratio 1:1) is added by means of a steam-heated dropping funnel. The Phenylacetone turns thereby into an
azeotrope and is similar to example 1 regenerated.
In both cases, after 4 hrs, the reaction is interrupted for 5 minutes and during that 5 minutes there is so much sulfuric acid removed that the original volume is re-created. Then the reaction is continued. The removed sulfuric acid can be re-used after one removes the methylammoniumhydrogensulfat developed during the conversion. The yield of Phenylacetone amounts to 76 %.
1350 g 79 % sulfuric acid is added through a reactionflask neck and mixed with 590 g 95 % (+)-Ephedrine.
10 ml 18 % TiCl3 is added subsequently, the solution mixed and the mixture heated to 125*C, and then heated to 145-155*C with steam, the distillate collected, from which by toluene extraction 358 g Phenylacetone were isolated. From this, 335 g = 73.6 % yield of Phenylacetone, with a purity of 99.5 % was collected by fractionated distillation over a Vigreux column.
In 1350 g 79 % sulfuric acid is dissolved under agitating 561 g d-l-Ephedrin (99-100 %), mixed with 15 g BF3 / glacial acetic acid solution (10 %) and heated to 125*C.
One injects steam and increases the temperature thereby to 145-155*C whereby developed Phenylacetone is collected. After approx. 6 L steam distillate is collected, the conversion is terminated. One isolates 386.4 g Phenylacetone from the distillate by toluene extraction and distillation. From this, 367 g (80.6 %) pure Phenylacetone is collected .
To 400 kg 60 % sulfuric acid added in a distillation apparatus, 500 kg of 80 % sulfuric acid are being gear-pumped. Added to this mixture is 400 kg (-)-pseudoephedrine (60 %) under mixing, and 1.5 L aluminum chloride solution (30 %) introduced. One heats the reaction mixture to 125-130*C and introduces then steam, while increasing the temperature to 145-150*C ,
whereby a mixture of steam/Phenylacetone distills over. After approx. 2000 1 steamdistillate is collected, one terminates distillation. From the distillate the lower heavy oil phase, consisting of Phenylacetone, is separated and the aqueous phase is extracted with approx. 400 1 toluene. The separated Phenylacetone and the toluene extracts are combined and concentrated by distillation. The remaining arrears are afterwards fractionated distilled. One receives pure Phenylacetone to 155 kg (80 %).
terbium (Hive Addict) 02-17-01 07:42 No 173956
Re: P2P via German Patent.
That is a great find now that red Phosphor(rP) is so hard to get. P2P from OTC reagents! The methamphetamine would be racemic but it sure beats scraping matchbooks to get rP.
foxy2 (Hive Addict) 02-21-01 12:35 No 174715
How would one produce anhydrous Lewis Acids?
Can hydrated FeCl3 be dehydrated in any reasonable way?
Would anhydrous HCl gas and dry iron fileings be the way to go?
uemura (Hive Bee) 02-21-01 12:53 No 174719
Would anhydrous HCl gas and dry iron fileings be the way to go?
Think so, at least Gattermann-Wieland uses this to get anhydroneous AlCl3 from Al and HCl.
PolytheneSam (Hive Bee) 02-21-01 16:34 No 174755
You can get anhydrous FeCl3 from some electronics companies. Its mixed with water and used to etch printed circuit boards. I have a mail order catalog around somewhere that has it in.
terbium (Hive Addict) 02-22-01 15:49 No 174948
But according to the patent you would not seem to need anhydrous materials. Steam is injected into the pot as the reaction is proceding in order to steam distill off the P2P as it is formed. The patent even talks about doing this as a continuous process where ephedrine is also continously added.
It seems to me that hydrated aluminum chloride should work just fine. Also, zinc chloride in most any form should work.
jim (Chem_Guy) (Newbee) 02-23-01 09:16 No 175060
I found a similar article quite a while ago, but it didn't mention any yields. I am glad to find out that the yields are respectable.
My suggestion is: Don't steam distill, it will complicate things. Take the sulfuric acid and ZnCl2, put into flask. Heat and add the crude ephedrine pills. The ephedrine turns into P2P, the fillers are chewed up. Extract with nonpolar like toluene after reaction has run its course and cooled down. Use P2P in any fashion you like to get racemic amphetamines.
For those of you who have access to bulk amounts of pure ephedrine, like in asia, from MaHuang, this is the preferred way of making P2P in continuous big scale operation there.
Steam distillation is then preferred.
After that, you convert the P2P with the OnePot Meth ICE method to racemic d,l-methamphetamine, and with the help of d-tartaric acid, convert that to d-methamphetamine, and l-methamphetamine.
Or use hydrogenation techniques. LT/
|Re: DETAILED METHODS for NON-CHEMISTS The Sequel !||Bookmark|
High yielding iso-safrole to 3,4 methylenedioxyphenyl-2-nitropropene procedure.
By Antibody March 2001.
Having had a few successful dreams while synthing TMA2 from asarone and PMA from anethole via the pseudonitrosite route, Antibody was delighted to find that iso-safrole suffers from none of the yield limiting factors suffered by either asarone, which easily polymerizes during nitration or anethole whose pseudonitrosite is difficult to hydrolyse in satisfactory yields. In two consecutive reactions with iso-safrole near quantitative yields of the pseudonitrosite were obtained. Its pseudonitrosite is also more stable during hydrolysis. The hydrolysis method outlined below is gentler than that in common usage and was inspired by a Weiland ref that Uemura came up with and a re-read of TSII.
1. Nitrosation of iso-safrole.
A 2l rb flask is charged with 2.5M NaNO2 (173g ) in 250mls dH2O. The flask is placed in an icebath and the NaNO2 is dissolved with mag stirring. 0.5M freshly distilled  iso-safrole(89g***) was dissolved in 900mls diethyl ether (distilled from Zerostart starting fluid). This is added to the flask. A pressure equalized dropping funnel charged with 1.25M H2SO4 in 500mls dH2O is placed in the rb flask. A hose is attached to the top of the funnel leading outdoors . After the content had been allowed time to cool, the H2SO4 solution was dripped in over 6 hours time, with slow mag stirring, ice being replaced as necessary. Flask was then allowed to sit for an additional 9 hours while ice was allowed to melt. During this step, a 6-7cm layer of white spongy precipitate will form at the interface of the two layers.
The dropping funnel is removed, and the reaction mixture is stoppered, and shaken vigourously, with care being taken not to break flask with mag stir bar . The entire content is gravity filtered using coffee filters and a 2l gasoline funnel. The etheral layer and the aqueous layers are saved for later . The filter cake is then scraped into a 2l beaker containing 1l dH2O and stirred with a spoon for a couple of minutes. What will happen is that all the NaSO4 will settle at the bottom, while all the pseudonitrosite will float in suspension. The water is decanted with the suspended pseudonitrosite from the NaSO4 which can be saved for other uses if desired.
The water layer with pseudonitrosites is vacuum filtered and washed with additional dH2O. The filter cake can then be washed 2X with EtOH (ethanol)or more expediently the filtercake is then dropped into a beaker containing 200mls EtOH and stirred thouroughly, and then vacuum filtered.
Yield 0.49M pseudonitrosite (from iso-safrole 98%***) (127g) as white crunchy granular nuggets. 
Hydrolysis of pseudonitrosite.
A 2l beaker sitting in an ice bath is charged with a mixture of 0.5M KOH (28g***) dissolved in 700mls EtOH. When mixture has reached 10°C the pseudonitrosite is added portionwise over 10-15 minutes with care being taken not to allow temperature to exceed 20°c. The solution is mag stirred vigourously until all pseudonitrosite has gone into solution. While this is stirring prepare 500mls of 2M aqueous HCl (approx 105mls 31% HCl and 395mls dH2O) and refrigerate. When all the nitrosite is in solution it was vac filtered and the filtrate returned to the ice bath and one tray of ice-cubes is added and the whole cooled to 5°C. Then as 500mls cold dH20 is added slowly the solution goes from an umbra to an ochre color,the chilled dilute HCl solution is added as a tiny stream to the stirring solution over 5-10 minutes. During the addition the solution becomes cloudy and most of the ice melts. The entire mixture is poured into a 4l wine jug containing 2l dH2O. And the entire mixture is refrigerated for a couple hours. During which time the entire jug will transform into a bright yellow crystal matrix, and probably a brilliant yellow bottom oil layer, which is also the nitropropene in oil form. The crystals and solution are decanted from the oil layer and vac filtered, the filtercake is dissolved in 300-400mls boiling IPA (isopropylalcohol) to which the yellow oil layer is also added. Agitate until all is in solution, then allow to cool slowly  to room temperature when it may be refrigerated for an additional hour to complete recrystalization. Then vac filter, wash filter cake with dH2O, and place in a stoppered filter flask charged with dry silica gel and attach to low vac (fridge compressor) overnight to desicate.
Yield 0.36M 3,4 methylenedioxyphenyl-2-nitropropene 73% (80g***) as bright yellow needles with the texture of compressed glass wool insulation.
Overall molar yeild 72%***.
The assumed molecular weight of safrole (178g/mol) is actually the molecular weight of MDP2P!!!
Safrole is 162g/mol!
89g safole are (89/162)=0.549 moles, not 0.50 moles! Yield of 127g=0.533mol pseudonitrosite means (0.533/0.549)=97%. Somebody better recheck those numbers again.
Hydrous Boro One Pot ! AT LAST!
(Rated as: Exeptional priceless info)
See : Post 328680 (Barium: "A really wet reductive alkylation", Novel Discourse).
READ it CAREFULLY and INTENSELY, especially the PTC post!
This method should replace all Boro One Pot methods I have posted, for small to medium scale reductions. I mean: up to 1 to 2 kg endproducts.
Bigger scale production can also be done like this new, novel procedure, but ONLY in case you have access to methylamine gas in cylinders, (your yield will then be nearly quantitative) you still be using the old LaBTop One Pot Boro procedure.
Yours is the choice.
I'm very glad and proud that at last someone out of our own ranks, Barium, found the solution for an hydrous reduction with NaBH4 and 40% Methylamine.HCl salt solution in water.
Very clever, and found all by himself ! LT/