Author Topic: DETAILED METHODS for NON-CHEMISTS The Sequel !  (Read 1198 times)

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LaBTop

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DETAILED METHODS for NON-CHEMISTS The Sequel !
« on: February 19, 2001, 12:41:00 PM »
If you don't have or take the time to read the first part of this Quest for Knowledge (

Post 26263 (missing)

(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 NOBODY 8) We all failed the build-in IQ-test! 8)  ;D  :o



PS : You can't post in here, post your help and thoughts in "The Sequel!" thread in the Newbee forum 

Post 26263 (missing)

(LaBTop: "DETAILED METHODS for NON-CHEMISTS Edit: IT'sDONE!", Newbee Forum)
.
LT/

LaBTop

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Re: DETAILED METHODS for NON-CHEMISTS The Sequel !
« Reply #1 on: March 11, 2001, 11:13:00 AM »
IMPROVEMENT for AL/Hg REACTIONS.
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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!  
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Rhodium (Chief Bee) 02-19-01 13:24 No 174349
22.5g freebase or 22.5g hydrochloride salt?
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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.
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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?   
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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.
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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?   
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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.   
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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.
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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 ).
120g p-Benzo
2g PdCl2
50mL H2O
400mL MeOH

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.
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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?
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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?
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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.
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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.
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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.


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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)
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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 in consideration, whereby the reactionmechanism for such Ephedrines is particularly important, no direct results for so far for (-)-pseudoephedrin and (-)-norpseudoephedrin. The Ephedrine preferably is used in a weight/weight ratio of approximately 1:1 to 1:10, preferably 1:2 to 1:5 compared to the acid.

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.

Example 1
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 %.

Example 2
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 %.

Example 3
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.

Example 4
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 .

Example 5
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 %).

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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.
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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?
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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.
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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.   
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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.   
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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. 
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COMMENT:
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/


WISDOMwillWIN

LaBTop

  • Guest
Re: DETAILED METHODS for NON-CHEMISTS The Sequel !
« Reply #2 on: March 19, 2001, 08:24:00 PM »


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 [1] 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 [2]. 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 [3]. 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 [4]. 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. [4]

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 [5] 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%.

[1.] Iso-safrole was prepared by refluxing 250mls distilled safrole in a 1l rb flask heated on an oil bath with 4g KOH under low vac (vacuum compressor)  and mag stirring for 14hrs. Iso-safrole was distilled under high vac directly from rxn flask. (thanx Osmium) A 245ml fraction bp 120-124°C was collected. Yeild 98%. 

[2.] It is neccesary to vent this rxn by means of a hose outdoors, as it produces toxic nitrous gasses which can cause lung failure. BE CAREFUL! Also, if desired, an erlenmeyer flask with a sep funnel in a stopper and a hose from the sidearm, leading outdoors is another acceptable way of proceeding.

[3.] It is neccesary to shake the rxn mixture to break the cake of pseudonitrosite crystals in pieces small enough to exit the flask.

[4.] The etheral layer can be distilled to recover spent ether. The recovered ether can be stabilized by adding a couple mls of EtOH and a few grams of NaOH.

[5.] This pseudonitrosite has a coarse texture completely dissimilar to that of asarone or anethole which are both very fine.

[6.] If cooled rapidly the nitropropene tends to precipitate as an oil.


Synthesis of 2,4,5 Trimethoxyphenyl-2-nitropropene from asarone. 
By Antibody2. Jan 2001.


Asarone is a much more difficult molecule to nitrate than iso-safrole as it is  prone to polymerization in acidic conditions, and ring nitration resulting in a red, alcohol soluable, mess. To  compensate for these shortcomings the procedure requires some minor modifications. The 1st of which is a pipet attached to the spout of the dropping funnel which will extend into the bottom aqueous layer. This prevents yield-reducing contact between your asarone and the dilute acid being added to the rxn. Another modification that can be considered is to use a slight excess of NaNO2 to ensure that there is no free acid in the aqueous layer to come into contact with the asarone at the interface. (one additional equivalent should be sufficient for this purpose). The last modification to consider is the substitution of HCl for H2SO4, although this seems to cause the etheral layer to redden prematurely, it can also result in slightly higher yields. It must also be stated that yields fluctuate substantially, in both the following steps.

Nitrosation of asarone.

0.5M NaNO2 (34.5g) is dissolved in 50mls dH2O with mag stirring in a 500ml erlenmeyer flask with a sidearm. The flask is placed in an ice bath and 0.1M asarone [1] (21g) dissolved in 150mls Et2O is added. The flask is stoppered and a sep funnel charged with 0.25M H2SO4 (25g) in 80mls dH20 is placed through the stopper with an oil pipet attached to the spout which extends to the bottom of the flask. (substitute 0,5M HCl (18g) in the form of 50mls 31%HCl in 35mls dH2O if desired). A hose is attached to the sidearm extending outdoors. When mixture has had a chance to cool, a slow drip of acid (1 drop/10sec) was commenced.  Very slow (45rpm) mag stirring is commenced ( you can also mag stir only at 20 minute intervals if desired). The acid addition will be complete in 3 hours at which point a 0.5 inch layer of canary yellow crystals will be visible at the interface. Mag stirring is discontinued and rxn allowed to sit an additional 3 hours, during which time the entire etheral layer will be filled with pseudonitrosite crystals. The etheral layer has by this time become  extremely red, although no polymerization was evidenced. [2]

The entire rxn mixture was vacuum filtered, the filter cake being washed 2X with dH2O and 2X with EtOH. The filter cake is left in buchner to air dry, yielding 56mmol (16g) pale  yellow pseudonitrosite (of asarone) crystals (molar yeild 56%).

Hydrolysis of pseudonitrosite.

56mmol of the above pseudonitrosite is slowly added to 150mls of  vigourously stirred 8%KOH in EtOH solution. Care must be taken that temperature does not exceed 30C at any time. Keeping temp well below that is preferable. When all pseudonitrosite had gone into solution (be patient), the cloudy solution was vacuum filtered and the filtrate poured over 100g ice and before ice had melted a cooled solution of 48g 31% HCl in 50mls dH2O is added dropwise over a few minutes with mag stirring. Yellow crystalls of nitropropene will precipitate almost immediately. The mixture was vacuum filtered, the filter cake being washed with water and air dried on filter paper yielding 31mmol (8g) 2,4,5 trimethoxyphenyl-2-nitropropene [3] (molar yeild 55%), as bright orange needles.

Overall Molar Yield 31%.

As of the writing of this proceedure the hydrolysis technique used for isosafrole had not yet been developed. Feel free to use it for asarone  as well. I believe that this will increase hydrolysis yields. However, if the iso-safrole hydrolysis technique is used, it is unlikely the crystals will precipitate as quickly as with the technique described for asarone.

[1.] Asarone fractionally distilled from EO of indian calamus under high vac (2 torr), the fraction with bp of 130-140C being collected.

[2)] Red colourisation of the etheral layer is a BAD sign during the nitrosation of asarone. Usually yield will diminish if pseudonitrosite is allowed to sit in red solvent for any length of time. It is best to filter rxn as soon as a red colourisation becomes pronounced. This does not apply to the same extent when using HCl, in which case the red colourisation will appear early in the rxn, but should be filtered if any evidence of polymerization is witnessed.

[3)] The nitropropene of asarone does not precipitate as an oil if the hydrolysis technique  dsecribed immediately above is used.


Working with anethole.

When nitrating anethole, the same procedure and molar proportions as used for iso-safrole will suffice, yield fluctuates between 60-80% when forming the pseudonitrosites. However as of yet, no method of hydrolysis has resulted in anything short of devastating yeilds.  It has been suggested that using sodium carbonate may be preferable for digesting the pseudonitrosite of anethole.


Solvent Notes.

The best solvent available for the formation of pseudonitrosites are ethers, thus far the best yields have been reported using diethyl ether, although the use of isopropyl ether has also been reported to have been sucessful by Uemura. Substituting petroleum ether resulted in much increased polymerization and ring nitration with asarone, and much messier work-ups using anethole. Reports regarding substitution with either THF, toluene or hexane all indicate that these are unsatisfactory solvents for that rxn. Recent experiments by Agent Smith however seem to indicate that Trifluoroethane (available OTC as computer cleaner) may be satisfactory for the nitration of iso-safrole. Yields using this solvent are ca. 60% of that using diethyl ether. The last thing to note is that when using starting fluid as a solvent yields were increased by distilling prior to rxn.

Reduction Notes.

These nitropropene's can be directly reduced to their amino derivatives using Urushibara Nickel Catalyst. Or reduced to a nitroalkane with NaBH4 in IPA/THF, then further reduced to an aminoalkane with Al/Hg in 10% MeOH. Or  processed to its oxime with SnCl2 and further reduced to the amphetamine (MDA) with Na or Al/Hg in THF. If a chemist would prefer a  methamphetamine this nitropropene can be processed to the ketone with HoAc (acetic acid) and Fe (iron turnings),  and from there to the methamphetamine (MDMA) with MeNO2/Al/Hg. It can be stored with refrigeration, but should be used sooner rather than later if a chemist has any big dreams for it.

Antibody, March 2001.




Nano Scale, Curbshot Style Edited!
By pubecs420.


I hope this helps a little.

Materials list:
*EXTRACTION*


1. 8 ounces denatured alcohol.
2. 24 cartons pseudoephedrine pills 60mg/pill.
3. 12 ounce glass jar+lid.
4. 2 coffee filters+funnel.
5. corning or pyrex plate.
6. heat source (no open flame).

Part 1.
 *Crush your pills and put in 12oz glass jar , pour the denatured alcohol also into the jar and fit with lid. Shake jar hard a few miniuts, put in freezer and wait 10. min. Shake again and keep in freezer another 20 min.
Carefully pour the top layer into funnel pouring on top of coffee filters exiting funnel onto glass dish. Evaporate alcohol to get your pfed . Should be around 1.5gm:
 
Materials list:
*REACTION*
:
 
1. test tube (cigar tube works good).
2. 3 inch balloon ( standard kids size water balloon).
3. black electric tape.
4. soup can filled with damp sand.
5. candle (buy the kind that sit in glass bowl).
6. pfed / iodine / red phosphorus.

 Note 1.: using 2 soup cans one on top of the other makes perfect source of heat to the moist sand. Construction very simple; the lower can has holes drilled through it for cooling and air supply for flame. Now with candle lit in 1st can place 2nd can right on top. Sand will warm instantly and your ready to go . You will be using 1 to 1 1/2 gm's E, 3gm's I,  2gm's RP.
 Note 2.: the ratio is based on your more then likely usage matchbox red phosphorous and iodine from tincture. DO NOT ADJUST RATIO. Reason being never once while nano pondering had failure or half reacted product, and never yielded under 60 %, so follow instructions and don't make any adjustments. From start to finish takes me 2 hours, give your self probably 2 1/2 . You will end up with at least 0.7 gm of get your dick hard meth.
 
* Put test tube in freezer about 5 min before adding chemicals, once all 3 are added ( I2 1st , pfEd 2nd , RP 3rd ), you will have 3 distinctive layers in test tube.  With an eye dropper add 4 drops peroxide, fit the balloon on tube (only needs to be on 1/2 inch let the slack hang over), now tape the balloon to the glass tube, shake the 3 reactants to mix well (dont let any get into the balloon), the reaction will start, push tube into the sand 2 1/2 to 3 inch. Set your timer for 1 hour and exercise your observational skills. For now go with 1 hour no more, no less, blow your candle out and let cool in sand for 15 min. Take your now room temp. test tube and cut balloon off, add 20ml dH2O. With thumb over the hole shake up and filter out the red P (its good to have a few test tubes clean and handy) by pouring liquid into another test tube using small funnel and 1 coffee filter (saturate filter with dH2O prior to using), now you'r left with clear/yellowish liquid.

*CRYSTALLIZING*:

1. RED DEVIL LYE.
2. CHARCOAL(for barbecue) LIGHTER FLUID.
3. MURIATIC ACID (diluted HCl, 33-38%).
4. DH20(distilled water).
 
 *Add 8gm's of lye (NaOH or KOH) crystals into test tube (not the one with yellow fluid in it use a new one). Add 20 ml of dH20 to lye and mix well, it will get hot,  put into sand to let cool. Now pour 50ml  barbecue lighter fluid into tube with the yellow fluid, now grab the other tube with the lye/dH2O and start pouring into tube with yellow fluid/lighter fluid (dont pour it all in at once ! Add little splashes till all gone. covering the hole give it ONE !!! Shake, release small amount of pressure that built up and set tube in the sand wait 15 min.
Your lye mix will be locked on bottom of the tube. This is fine,  pour
off  lighter fluid into a clean test tube and add 20ml dH20 and  4 drops
of muriatic acid and shake hard.  Using an eye dropper (may have to
extend length using fish tank air tubing to reach bottom of tube),
retrieve bottom layer, pour onto your glass dish and evaporate . Thats
all folks what remains after dH20 has evaporated is pure, get your dick
hard, meth, so have happy hollidays.

Converting iodine tincture.

Tincture of iodine is iodine salts in alcohol, it is found in supermarkets in small one ounce bottles. Each bottle can generate a little over a gram of I2, the price has shot up from 0.60 cents to $1.80 / bottle. Tincture comes in 2% or 7%. Wall mart carrys 2% for $0.87.
It is also available at feed and track stores in pints and gallons.
 
Formula one.

1 pint 7% tincture iodine.
3 pints of hydrogen peroxide, H2O2.
2 ounces of HCl 33%.
1/2 cup of dH20.
 
Shake it up, in a one gallon jug,
Wait 20 minutes.
Filter through a pantyhose.
Wring out fluids.
Put iodine crystals in a glass jar,
Re-wash four times with distilled water, cover, shake, pour off the water into a filter.
On the final water wash, wash the iodine into a fresh filter,
Wring it out hard,
Open up filter roll into a dry filter.
Wring out hard.
Put crystals in a dark place to dry.
Use a Drying agent like Calcium Chloride and store with the I2 in a sealed chamber.
Grocery stores, for mildew prevention near the moth balls.
I2 is light sensitive and will degrade.
When completely dry, store in light-resistant container.

Formula 2:
 
1) 1000 ml 2% Iodine tincture = 2.5%I+2.5%KI in EtOH (ethanol) and H2O.
2) 250 ml Muriatic acid = 34.4%HCl.
3) 475 ml Hydrogen peroxide = 3% solution of H2O2.
4) 1750ml Distilled H2O.

In a 1 gallon container (plastic or glass),
mix 1 liter of 2% tincture of iodine,
with 250 ml of Muriatic acid,
stir and allow to sit for 15 min.
Add 475ml of a 3% hydrogen peroxide,
stir and let sit an additional 15 min.
Add 1750 ml distilled H2O,
shake and let sit for 15 min more.
An orange water layer appears on top of a dark gray layer of I2.
Pour off most of the the orange water.
Add fresh distilled H2O shake and let sit.
Pour off most of the the orange water.
Wash a total of three times with distilled water (more can't  hurt).
On the last wash pour the I2 into a stack of 5 coffee filters.
Wring it dry.
roll the iodine ball into 5 dry coffee filters.
Wring it dry.
Roll it into 5 more dry filters,
wring it dry.
Put the I2 in a small clean glass jar, break up the iodine ball,
place the jar of I2 on a piece of cardboard, cover the I2 with a larger jar, put in freezer for several hours.
Remove jar of I2, seal it tight, with cellophane then screw on the cap,
store it in a dark cool environment.

Potential problems:
 
Not rinsing the I2 enough with water to remove the chlorine and salts from the tincture.
Not drying the I2 out enough and adding it too wet to your reaction. If in doubt at all re-wash the iodine with distilled water in a filter and wring out, The iodine is only very slightly soluble in water, you lose very little washing with water. If it is not clean and dry you can lose a lot more in a failed reaction.

Red Phosphorus:

Materials:

- 5 Gallon Bucket.
- Drill (1/2" chuck).
- Mud/Paint/Concrete Mixer.
- Coffie Filters.
- Strainer (big enough to fit over pot and bucket opening).
- 2 gallon Cooking Pot.
- Tin Snips or Siszers.
- 200 Matchbook Boxes.
- 2 Gallons Acetone.
- Sulfuric Acid.
- Hydrochloric Acid.
- Water.
- Iodine.

EXTRACTING RED PHOSPHORUS FROM MATCHBOOKS:
<1> Ripp off matchbook covers. Line up as many matchbook covers as you can cut through with tin snips or good, sharp siszers.  Cut out and save all the striking pad strips.
<2> Drill 3/4" hole in the lid of the 5 gallon bucket. Put the mud mixer through 3/4" hole in lid and into the drill.
<3> Dump the 200 matchbook boxes worth of striking strips (10,000 striking strips) into the 5 gallon bucket. Pour 1.5 gallons of acetone into the bucket. Cover bucket by inserting mud mixer then snapping on the
lid.
<4> Mix Contents for about 5 minutes. Check to see if strips are mostly white. If not then continue mixing.
<5> Take off lid and pull out mixer. Put the strainer on the cooking pot and pour all the actone in. Pull out all strips from strainer and bucket and place on clean table or in a bowl. The strips will be covered in red
phosphorus, rinse them by placing the strainer on bucket and throwing a     handful of strips in it. Then slowly pour some of the acetone in the cooking pot, through the strainer untill strips are clean. Empty strainer
into garbage. Continue untill all strips are rinsed.
<6> Pour all the acetone/RP into the cooking pot. Let the RP settle for about 15 minutes. SLOWLY pour off the acetone into your local lake. Keep pouring as long as the acetone is pretty clear. The last bit of acetone will be redish colored. Filter this through a coffie filter in the
strainer. Scrape the mushy RP back into the pot or dry the filters, roll
and ball them up well, then unfold. All the RP will fall right out in a
dust.

Cleaning Matchbook Red Phosphorus:

SULFURIC/HYDROCHLORIC WASH:
(This can be done as 2 different washes) With mushy RP in cooking pot,
pour enough 1:1 water/sulfuric to cover the glob. (It's optional now to
add heat or not. If so then add no more then enough for a light boil) Mix 
contents for 5 to 10 minuates. Add an equal amout of hydrochloric acid
and continue mixing for 5 to 10 minuates. If heat was applied take off now. Add an equal amount of cold water. Filter through a coffie filter in
the strainer.
Scrape the chunky RP off the filters back into the cooking pot. (This
will eat up alot of small paper fibers, hair, cotten, lint or whatever.)

ACETONE WASH:
Add enough acetone to cover the globs and chunks of RP.
(Again you can add heat if you like. Bring it to a controlled boil).
Mix for 5 to 10 minutes. Let cool or add a little cold water. Filter RP
same way and return it to pot. (This will remove any glues or other acetone solvent junk.)

WATER WASH:
Add enough distilled water to cover the RP globs. Bring this to a boil or
5 to 10 minutes. Filter out the RP and leave in filters to dry out.
When dry roll and ball up filters then brush out dust. Collect dust in a
baggie and store.  (This is a general cleaning to remove any chemical
residue.)

OTHER WASHES:
Any of the following solvents have been safely used to wash RP...:
Methanol, Ethanol, Denatured alcohal, Isopropynol, Toluene, Xylene.
These would be done the same as written above.

SCREENING:
Put RP in stainless steel screen or coffie filter with metal screen and
run acetone through it.  (Removes anything that non-soluable to acetone
and too big for screen.)

WASHING ORDER: The order does not matter as long as the RP is finished
off with an acetone wash then a distilled water wash.

PREFIRING RED Phosphorus:
React RP/I2: Weight out your RP and put it into a bottle. Add half as
much I2 to it and shake it up. Add (dropwise) H2O2 when not reacting.
Continue shaking and adding drops of H2O2 untill it's done reacting.

FILTER OUT RP: After prefiring add water and shake. If it won't loosen up
then put the bottle in boiling water for 5 minuates. Filter the water/RP/I mix. Wash the RP with acetone then water. Dry it out, baggie
and save for a rainy day.

NOTE: - Make sure drill has a 1/2" chuck.
     +-----+
     |     |
     |     |<---------- Drill
     |     |
     +-----+
        |
        |
        |
________|___<---------- Lid
|       <       |
|       |       |
|       |       | <---------- Bucket
|   ____|____   |
|   |   |   |   |
|   |   |   | <---------- Mixer
|   |___|___|   |
|               |
|               |
+---------------+



This was compiled from many sources and through trial and error was refined to what you see.  It was written to be printed up and used as a
reference for anyone like swim that hasn't been able to get lab grade RP.
Swim's current run was scaled down using a 2 gallon bucket with 114 boxes!  It took over 3/4 gallon of acetone to extract the RP.  Clean up
will be H2SO4/HCL, ACETONE, H2O, PREFIRE, ACETONE, H2O, DONE!

Swim is expecting to yield about 250mg per box.  Their hoping to end up
with an even ounce. :)


Fester Fiend



LaBTop

  • Guest
Re: DETAILED METHODS for NON-CHEMISTS The Sequel !
« Reply #3 on: September 05, 2001, 12:34:00 PM »
This is my latests write-up for the buffered Performic reaction, to produce MDP2P ketone starting from Sassafras oil:

To help everybody out in this somewhat chaotic 2 year long discussion on one of the most interesting subjects for most of the readers, I offer you the following effusion :


A correct timeline of the-Hive's development of the following high yielding procedure is as follows:

Ritter first posted on the young Hive, end of '98 a short, buffered Performic acid oxidation, and he used Na2CO3, Sodiumcarbonate as the buffer, and DCM as the solvent, then Beagle posted a similar procedure, and LaBTop posted a short one using NaHCO3, sodiumbicarbonate (a.k.a. baking soda or sodiumhydrogencarbonate) and DCE, where he mentioned that DCM could be used in practice with similar yield. Then Gyrogearloose reproduced that one in practice also, on medium scale, 500 g MDP2P, then LaBTop wrote in april 2000 a very extensive writeup from past practice in the sticky threads, where he advised to use a new find from Osmium to produce the precursing Isosafrole with Aliquat phase transfer catalyst in 5 minutes after the heating reached the boiling point of safrole.
Then Baalchemist got enthousiastic and reproduced in practice LaBTops extensive practical MDP2P write-up, and made a few small alterations during the following year.
Ritter as the last one posted again, from practice, saying there is no real difference between the use of sodiumbicarbonate and sodiumcarbonate as the buffer salt, and proved it with hard facts, so feel free to use either of these salts.
Now Rhodium included this procedure in short form in his latest write-up at his page.

LaBTop build all the latest info into his latest extensive write-up, with some important new additions for large scale production of MDP2P, which is mainly different compared to small or medium scale in producing performic acid portions only 1 hour before needed during the proces of adding it to the isosafrole/DCM, thus providing a constant supply of FRESH performic acid, no use of cooling when dripping the performic, and preheating the intermediate  and the 15% H2SO4  before adding them together, which seems rather unimportant, but will increase yield substantially, if also a good professional vacuum source is used, yield percentages between 80 and 90% can be reached! Thanks go to Baalchemist for the last two.
And now LaBTop provides you with the latest extensive write-up, because he knows that 90% of the members will manage to majestically misunderstand these ultrashort writeups, because of the nature of this board, 90% non chemists and 10% chemists.

* * * * * * * * * * * * * * * * * * * * * * * * *

For small, medium and large scale MDP2P ketone entrepeneurs, I would strongly advise to pay full attention to the following write-up.

See first

Post 23325

(LaBTop: "Detailed Methods for Non-chemists Edit: IT'sDONE!", Methods Discourse)
, and

Post 184407

(Ritter: "Re: Medium scale performic", Methods Discourse)
to get a grip on the Hive's historic development leading to the following newest procedures to produce MDP2P ketone.

After that I advise instead of the messy and time consuming Aliquat procedure mentioned there, to follow the most simple, next procedure, to convert your safrole, vacuum distilled from minimal 85% Asian or Brazilian sassafras oil, to vacuum distilled Isosafrole, and then the LT buffered Performic acid oxidation procedure to produce MDP2P from it :

Here's first the conversion from Safrole to Isosafrole done by LaBTop, Osmiums simple route was followed, yields are ~95% without vacuum, ~99% with vacuum :

No vacuum:
Weight 130 kg distilled safrole and add 2% = 2.6 kg KOH grinded flakes or pellets >98%.
KOH flakes are in some countries 85%, the 15% rest is water, check it on the label.
Then heat up. At 100 C the eventual 15% water will start evaporating, or, when 98% KOH was used, only a small amount of water will come off.
This removal of water is critical to the reaction, water present when refluxing will totally stop all isomerization.
Add more heat until all water is evaporated. Then at last connect a reflux condenser vertical on your vessel and continue heating until the safrole starts boiling, without vacuum, reflux will be constant at circa 232 C until boiling stops, that means it has nearly all converted to higher boiling Iso.
Do NOT crank up the heat then, but disconnect heating and let cool to roomtemperature. Reaction takes roughly 3 hours for non vacuum. You now have ~95% Isosafrole which you use for the MDP2P conversion step. You could distillate it now, to get >99% Isosafrole, but that seems to be no option for the ones who choose for this approach, they probably have no vacuum source, and ~5% safrole will not really interfere with the MDP2P step.

Under vacuum :
Same as above, only boil off eventual water first with a normal condenser attached, so you can check for any water present, when eventual water stops condensing in the condenser, change horizontal condenser to a vertical reflux condenser, and keep heating (far under 200 C, boiling temperature depends on vacuum source.)
Vac reflux should be done overnight because of lower temp, reactions at lower temps take longer.
Start a vacuum reaction f.e. at 21:00 hr and next morning its done, all boiling has stopped and safrole is nearly quantitatively converted to isosafrole.
Then just distillate the now isosafrole out of reaction flask, dont distill it completely dry though, because you can add a next batch safrole to that little bit leftover {isosafrole/safrole + all the used KOH} again for a next run.
Just add at the next run 50 gram of new KOH to refresh a little.
Trying to wash reaction in a sep funnel for purifying is terrible: results in a terrible emulsion that's nearly impossible to break up and ends up in alot of LONG labor and endproduct loss.
Distilling is a must for best result. Don't worry about leftover safrole with O's Isosafrole vacuum route, usually all converts.
However, if a small amount leftover safrole is present, f.e. because you have no vacuum, it wont screw up the performic route.

Notes:
No CaO at all, 98-99% KOH only. Make sure the KOH are roughly grind-up solids, (not a liquid mix with water), where you sieved all powdered KOH out for an easier workup at the end, use a nylon insect-screen.
Add 1-2% of safrole weight KOH flakes and away you go. Make sure that there is no H2O present anymore when you start the actual reflux!. At atmospheric it runs quicker because of higher temp, ~3 hours.
Bring it to a reflux and hold it till refluxing stops. Then you know it has converted to the isosafrole which has a higher boiling point. Vac reflux is much longer, but if you're into yield maximalization, then thats the way you want to go. ~98-99% yield.

* * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * *

Here's first Baalchemist's write-up for LaBTops modified performic as he posted it lately, then the second part is scaled to what LT/ would do. This can be scaled up or down according to your wishes, may they always come true :

Baalchemist:

There is no need to pre-stir for more than 5-10 mins. In a nutshell; With stirring in 2L flask add in this order> 250g Iso, 76.9g Baking soda, 770ml DCM, let stir 5-10 mins. Begin dripping in performic solution (232.2g 35% H2O2, 384.5g 86% Formic acid) over a period of a couple hours. It should reflux slightly during addition,but not a hard reflux.Solution will turn from yellow to orange,keep stirring 24 hours,no less. Allow to sit and remove DCM layer,and extract top layer with a small amt. DCM. Evap DCM extracts, add orange syrup to 2768g 15% H2SO4 (preheated to 80c). Stir for 2 hours, no more. Let cool, 2 layers will form. Remove bottom layer, and extract top layer with some DCM, add this to bottom layer. Evap off DCM and proceed to vac distill ketone. Yield 190g+ Ketone ~76% w/w.    

============================



LaBTop's ultimate procedure :

( If you prefer a small scale procedure, just change ALL kg in grams, and liters in milliliters !! )


PERFORMIC ISOSAFROLE GLYCOLIZATION STEP:

In a 1600 liter vessel ( f.e. a second hand stainless steel milktank ), add, in this order (while heavy stirring anti-clockwise, (a must-have is a stirringmotor which can turn clock- and anti-clock wise (1), otherwise too much oxigen and other gasses from the air will be mixed in; you will notice no vortex, but a 1 cm high and quite wide bubble on top instead) :

first:  125    kg Isosafrole, distilled.
then:    38.45 kg Baking Soda, NaHCO3, SodiumHydrogenCarbonate 98%.
then:   385    liter DCM, CH2Cl2, DichloroMethane a.k.a. MethyleneChloride, 98%.
Totals to 681.28 kg (weight of 1 liter DCM is NOT 1 kg!).

The purpose of the baking soda is to buffer the pH of the reaction in such a way that it doesn't become too acidic, in which case the intermediate monoformyl glycol may undergo oxidative cleavage (and thus lessen the yield). Running the reaction at a higher pH than usual makes more of the epoxide (and thus risk of tar forming) and less of the actual glycol and will decrease yield quite notible. (both will of course form the ketone with 15% H2SO4).
 
Attach a reflux condenser & addition-funnel/container with a dripping valve to the 1600 L vessel. All other openings must be frantically closed with proper tape, or teflon seals, or the reflux will not work accordingly. Leaks will make bad smells.
Allow this to stir fast anti-clockwise while you prepare the first 25 liter portion of the total amount of performic mixture :

192.5 kg 86% Formic acid (preferably made by diluting 99% Formic acid)
118 kg 35% H2O2 (hydrogen peroxide), as FRESH as possible, don't use month's old stock.
This makes a total of 310.5 liter performic mixture.
 
To prevent such a big amount of performic mixture to get exothermic and too hot, while waiting all these many, many hours necessairy for dripping all of it in the Iso/BakingSoda/DCM mix :

Before adding parts of it to the 25 liter dripping container+drip-valve, only 25 (or even 10) liter portions are prepared each time with strong mixing while adding the two ingredients together, and kept in a freezer at around zero degrees Celsius, until needed. Don't cool too deep, it will slow the reaction rate when added to the dripping container and dripped in the vessel.
It means that you make during ~half a day, under strong stirring, twelve 25 liter portions and one 10.5 liter portion performic mix, one portion each time, when the dripping container is 4/5 empty.
Or even better thirty 10 liter portions and one 10.5 liter portion.
That way your performic mix is of a constant FRESH nature, which increases end-yield.

The performic acid portions should be prepared in advance (one hour, at room temp: the last 1/5 of the dripping container takes around 15 minutes to empty) to make sure the formic acid has reacted with the hydrogen peroxide (but don't let it stand overnight, or decomposition will occur).

Using DCM as the solvent is advantageous, as the reaction temperature can never exceed 40°C (bp of DCM), and by keeping the reaction temperature that low minimizes side reactions.


When the 25 liter dripping container is 4/5 empty, refill it from a 25 or 10 liter portion from the freezer.
(If your Formic acid isnt 86%, then down to 77% will work, compensate with more H2O2, based on % of formic acid available.)
The Formic acid is only acting as a solvent in this reaction, it does not react.
Remember, the less performic in the dripping container, the slower the dripping goes, so adjust accordingly, watch the reflux rate AND the temperature, when one of these go too fast or high, close the drip-valve a little, until both reflux and temp are stable again.
The technically gifted can make a pressure-equalized dripping container.
 
Slowly, add the performic-mix drop/or smallstream-wise over a 6 to 12 hour period under constant fast mixer speeds.
If you add it too fast, the reaction will boil over, and contaminate everything.

Use a glass or SS pipe with wide internal diameter, attached to the drip-valve, properly sealed where it enters the top of the 1600 liter vessel, extended just under the fluidlevel, to drip the performic-mix directly into the mass of the fluid, and so prevent too much oxigen or other gasses to interfere with the reaction.
It will start to reflux a little, adjust addition rate so it doesnt reflux too hard.
Once all performic is added, it will have turned from a yellow to an orangejuice color.
 
Keep strongly stirring for 24 hrs total, no more, no less. (included dripping time). If you stir longer, sidereactions will kick in, lowering the end yield.

Note:
Remember, do NOT cool the whole reaction mix at all, let the reaction temperature be controlled by the dripping rate!
A good double check is the reflux rate, at no times, uncondensed vapours should leave the top of the reflux column! A bad smell indicates this.
End note.

 
Turn off the stirrer after these 24 hours, allow the two layers to settle.
Separate off the bottom layer (DCM), and extract the remaining top residue-layer 2 times with a small amount of DCM, and add these to the already separated main DCM body.
 
Take this combined portion to a 22 liter Rotavap or conventional distillation machine, distill off the DCM in 15 liter portions, and collect all the resulting orange syrup portions in a heating vessel and heat it up carefully, meaning don't overheat it, to 80 Celsius. All eventual residual DCM, (if any), will evap off (about 5-minutes).
You will be left with 183 kg monoformyl glycol, nearly quantitative, 100% yield.

Remove the residual fluids from the above procedure for eventual recovery of solvents and clean the 1600 liter vessel with hot, slightly soapy water and then cold water.

SULFURIC ACID HYDROLISIS STEP:

After the vessel cleaning, pre-heat (2) the 1600 liter vessel filled with 1384 kg 15% H2SO4 to 80 degrees Celsius.

NOTE:
Dilute 209.7 kg 99% H2SO4 with 1174.3 kg=liter distilled water for this amount of 15 % H2SO4.
Calculation of this amount:
15% / 99% = 0.1515% x 1384 kg total = 209.7 kg 99% H2SO4.
1384 kg 15% H2SO4 - 209.7 kg (99% H2SO4 + 1% water etc) = 1174.3 kg(=also liter) water.
209.7 kg (99% H2SO4 + 1% water etc) x 0.99= 207,6 kg 100% pure H2SO4/13.84= 15.00 % , always double check calculations. NO liters used in calculation here!
End NOTE

Then add all of the 80 Celsius preheated, distilled orange syrupy monoformyl glycol to the 80 Celsius hot 15 % H2SO4 portion in the 1600 liter vessel.
 
Connect a reflux-condenser on top of the 1600 liter vessel, and be sure there are no other open pipes or joints.
Keep the mixture between 75-80 Celsius for 2 hours, NO longer, or again sidereactions will kick in.

DISTILLATION STEP:
 
Switch off the heat, and allow to cool back to room temperature.
Flooding the reaction mix with some extra H2O prior to extraction helps improve yield because it facilitates separation and fastens cooling down.
It will seperate into 2 layers, the bottomlayer is raw MDP2P ketone, which you tap off through the bottom ballvalve.

Extract remaining top watery layer with small amounts of DCM (2x, a few liters), tap them off, then add all these DCM portions to already tapped off raw ketone bottom layer. When your last tapped DCM has the same color as when you poured it in, there is no more raw ketone to extract.

Then wash and separate this raw ketone 2x with sufficient 5% Sodiumbicarbonate/H2O mixture (a few to 10 liters at a time), to neutralize all residual acid. Check pH first with pH paper, then start adding bicarb until pH stays constant, or even goes up, when adding a bit 5% NaHCO3 again. Then all acid is neutralized.

Now place 15 liter portions in a 22 liter Rotavap or newest distillation machine, and vacuum distill the MDP2P ketone  which comes over between 155 and 165 Celsius and lower with the newest vacuumpump, it will begin to come over at circa 20 mBar vacuum and end at circa 1 mbar. A golden, honey coloured ketone will be obtained.
Clean the leftover tarry residue in your destillation flasks with acetone, a bit warm acetone will work faster.

Yield 76 % w/w, with a Rotavap, about 95 kg clean and pure MDP2P, ready for prefered method of amination.
Yield 85-90% with special distillation techniques, about 106.5 to 112.5 kg pure MDP2P.

Clean the leftover tarry residue in your destillation flasks with acetone, a bit warm acetone will work faster.

AND I DO NOT TELL THE OPPONENTS HERE WHAT THAT TECHNIQUE IS, and will be strongly pissed off when someone else does it openly here, we made their oppressive life already too easy.
We have PM's for that. And don't start PM'ing me to ask, only the few I trust to be able to do this can do that, the rest gets no answer. Yes, I'm a prick!
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NOTES:
1: Easy to construct with a stirrer shaft with a pulley on top, and the shaft leading through two ballbearings, one on top of the vessel, with an extra seal under it to seal the vessel airtight, and one at the bottom of the vessel, to keep the shaft+stirrer rigid. The motor has a pulley attached also, and the belt can then be attached to both pulleys normally, to stir clockwise, or in the form of a folded 8 to stir anti-clockwise. Motor must be tilted a little, to prevent the belt from scratching, when used in an 8 form.
You will be surprised what a 2-way stirrer motor costs, this is definitely cheaper to make yourself.
A 350 or 500 RPM motor+pulley and a SS-shaft+pulley with an outboardmotor SS-propellor attached is sufficient for all purposes. Instead of this expensive propellor you can design any other SS-mixerblade made by a machinist shop which will do the same job just as good, but will be much cheaper.

2: Heating such a 1600 liter vessel can be done in various ways, but the best is some sort of coiled-up hard-chromed copper pipe ( do NOT forget to hard-chrome the copper coils at a chroming-shop before ever using them in this kind of reactions, pure copper will solute in 15% sulferic acid and turn your solution to a nasty darkgreen color).
Place the coil, or coils, if your man-hole is too small for one big coil, at the bottom of the vessel and connect the ends outside the vessel to a convenient gear-pump and  heating vessel, silicone-oil filled, and electrically heated, with a connection to a thermostate, triggered by a thermometer at the bottom of the 1600 liter vessel. Make the passages through the vessel top airtight with silicone glue!
This way you are sure to not form hotspots.

Another easy method is to attach electrical heated car motor-oilpan heating pads to the outside of the bottom and eventually the sides of the 1600 liter vessel.
This method can be combined with the above one, to speed up heating, do not forget to stirr maximal when using heatpads.

30 August 2001 by LaBTop.

WISDOMwillWIN

WISDOMwillWIN