Is there a method to convert 1,4 Andro to Boldenone base?

BigVrunga

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Is there a known method to convert 1,4-dione to boldenone base? Ive read of something using MnO2

I found this article, originally posted by crazy pete:

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
#75 (1953)
page 5930
sondheimer et al.

1g 4AD + 100mL chloroform + 10g MnO2 = test base 100% after 2 hours shaking at room temp

yield is 93% when crystalized with methanol and filtered on paper

MATERIALS: (check www.sciencelab.com i don't know if they are the cheapest, but they have everything)
beakers
hotplate with built in stirrer
stirring bars
distilled water
methanol
chloroform (can be cheaper grade)
thermometer (-10 to 150 degrees celcius, its like $4)
4AD powder
activated MnO2 (if this cannot be found, make your own from potassium permanganate and manganese sulfate. also need ether if you do this step)
filter paper
funnel (holds filter paper)
earlmeyer flask with vacuum tube out side for vacuum filtering
scale

now that is alot of MnO2 and it can be done with less. too simple you say, well your right its not that easy. the MnO2 available commercially is not always active. but the authors gave a method of preparing MnO2 that is easy and the product is very active and can be put in a stoppered jar with no loss of activity (those guys would make great homebrewers)

HOW TO MAKE MnO2:

take concentrated aqueous potassium permanganate and add to a stirred aqueous manganese sulfate solution kept at 90 degrees celcius (need a hot plate that has stirrer built in) until a slight excess was present (pink coloration of the supernatant liquid). stir at 90 degrees celcius for 15 minutes. filter, wash well with hot water, then methanol and ether. dry at 120 to 130 degrees celcius to a constant weight. it can be kept for several months in a well stoppered bottle with no loss of activity.

how to get concentrated aqueous potassium permanganate: take distilled water and and add potassium permanganate until not more goes into solution (this is where a magnetic stirrer comes in handy). if you added too much, just add more water until all is in solution. duh!

how to get aqueous manganese sulfate: same idea as above.

METHOD:

i am looking for a source of activated manganes dioxide so that the above does not need to be performed. once we get the manganes dioxide, all we have to do is mix the 4AD, MnO2 and chloroform in the ratios above, basically add the 4AD to chloroform on the magnetic stirrer and then add the MnO2 and leave it for 3 hours at room temp. add methanol to the solution and the test will crystalize and fall out of solution. filter and wash well with methanol. collect the filtrate and filter again on new filter paper and dry all the filter papers. if the filtrate still has crystals, filter with another paper. i would dry the first filter paper out well for a few days and weigh it. if its more than 80% yield, i wouldn't waste time trying to get the rest. if not, then take the filtrate and refilter to get rest of crystals. you kind of play it by ear. that's pretty much it.....oh yeah, don't forget to discard the powder properly as this is an experiment

it is possible that much less MnO2 can be used. this will mean that the reaction will have to sit longer maybe a day or two, i don't really know. this will have to be found out. i want to try this in the lab where i can measure the ultraviolet spectrum to determine how long the complete reaction takes with different amounts of MnO2 and chloroform so as to minimize cost.

why did i not do it step by step? well if you can't figure it out, then you probably shouldn't be doing it.

THIS SHOULD WORK JUST THE SAME FOR 19nor4diol to NANDROLONE

ba-doop, ba-doop, that's all folks

cheers, pete
That should work to convert 1,4-diol to boldenone base, correct?

Anyone every tried it?

BV
 
BigVrunga

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Hmmm...isnt MnO2 the stuff in batteries? And can this be activated by boiling with dilute HCL (around 3%)?

Seems interesting.
 
DR.D

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Hmmm...isnt MnO2 the stuff in batteries? And can this be activated by boiling with dilute HCL (around 3%)?

Seems interesting.
It's not the same, 4ad is an alcohol and can be oxidized in many ways. I would probably try NaMeO first, but MnO would be cheap and you could get the powder online w/out the battery extraction. If you didn't hault the reaction in time, you might get a lot of andro as a by product. What you want to do is tricky because 1,4-dione is a ketone and requires reduction. Very mild, selective reduction.
 

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Someone else respond, this is a very interesting thread
 

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To the best of my knowledge, there aren't any real-world selective reducing agents. When I say "real-world" I'm talking about borohydrides, catalytic reductions, or even lithium aluminum hydride since these are all reasonably obôainable (LAH is pretty damn dangerous). There are a handful of well tòaveled routes to testosterone from the dione. They widely range in difficulty and practicality, but one aspect all of these routes have in common is the ability to differentiate the 3 end from the 17 end... One scheme makes use of the special reactivity to ethylene glycols at the 3 end. The 3 keto is transformed into an ethylene glycol derivative (a protective group) while the C17 C=O remains essentially unchanged (or so they say). The next step is the sequential reduction and acylation of the C-17 carbon from ketone to alcohol to acetate ester. Like the glycol derivative on the C3 end, the acyl group serves to protect the hydroxyl on C-17 from the ensuing oxidation of C3 to C=O.. This is typically and traditionally done with Jones' reagent (Cromic acid), although an array of oxidants exist that will do this job better (starting with chlorox bleach)..

Interested in more? Buy my book :)
 
DR.D

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Chromic oxidation is pretty harsh and you must know the kenetics and reaction time to terminate w/ a good yeild. You could always employ S. cerevisiae (yeast) to obtain about a ~70% yeild of the D-enatiomer. Also, although the 3-keto could be removed and later restored after reduction at the 17 position, the 3 position protection offered by an ethylene ketal group, after having prep'ed the 3-oxo, could give good yields.

Andy, you said you'd send me a special free autographed copy of your book! :wave:
 
BigVrunga

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Ok Andy what is the title of this book and where can I get a copy?:)

So is there a way that the kitchen chemist could convert 1,4 to boldenone? Sounds like the process might be more complicated than its worth...

As far as the method quoted in my post -has anyone tried this with 4AD? And would it work to go from 19-NOR to nandralone?

BV
 

Andy13

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Ok Andy what is the title of this book and where can I get a copy?:)

So is there a way that the kitchen chemist could convert 1,4 to boldenone? Sounds like the process might be more complicated than its worth...

As far as the method quoted in my post -has anyone tried this with 4AD? And would it work to go from 19-NOR to nandralone?

BV
It is possible (practical) to go from 4-Diol ---> testosterone ---> testosterone ester ---> boldenone..

Manganese dioxide accomplishes the first oxidation (tempormental--- side reactions are generally low, but sometimes yields are too.. no matter what, it will NOT oxidize C17 OH unless made first into a, b unsaturated alcohol.)

Selenium dioxide.. Sounds like the something your parents might make you take to GROW STRONG! Either that, or next week's stock up item at the local hippie food store.. As harmess as selenium dioxide sounds (sounds harmless to me if I didn't know anything about chemistry... nothing like, say, "peroxyphosphoric acid".. which (to me) is a more 'dangerous' sounding name... like sodium cyano borohydride!.) The name is misleading... Selenium dioxide doesn't have an RDA.... and, Well, you won't be ordering any selenium dioxide with your organic tiramisu b/c this stuff is pretty nasty...


Easy reaction though!

Andy
 

growmore

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Here's one for you--
M-1,4ADoil + MnO2 in either chloroform or [font=verdana, arial, helvetica] dichloromethane solution = Methandrostenalone
Would this work? If so the only concern might be what is largerst pore size that will filter off excess MnO2 after completion of the reaction; you'de definately want to get rid of as much manganese dioxide as possible before adminstration to lab animals.
[/font]
 
DR.D

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Here's one for you--
M-1,4ADoil + MnO2 in either chloroform or [font=verdana, arial, helvetica] dichloromethane solution = Methandrostenalone
Would this work? If so the only concern might be what is largerst pore size that will filter off excess MnO2 after completion of the reaction; you'de definately want to get rid of as much manganese dioxide as possible before adminstration to lab animals.
[/font]
I don't think MnO2 is soluble in methylene chloride, I going to stick with the equalibrium reaction involving Sodium Methoxide in an abundance of ketone. I know it's selective.
 

growmore

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The idea comes from the same original reaction thats been posted at several boards. The original of coarse used 4AD for a final product of test but the principal is the same. From my understanding you would perposely use a solvent that only disolved the hormone and not the MnO2 so after the reaction (done on a magnetic stir) you could filter away the solid MnO2 particles. It's a fun idea, of coarse no one should ever try this where it may violate local laws... I'd be interested in hearing more about the the equilibrium reaction since I like to wrap my mind around this type of stuff once in a while. Also if you want a link to a thread at another board that goes more in depth on the subject shoot me a pm.
Original:
"1g 4AD + 100mL chloroform + 10g MnO2 = test base 100% after 2 hours shaking at room temp"
I don't think MnO2 is soluble in methylene chloride, I going to stick with the equalibrium reaction involving Sodium Methoxide in an abundance of ketone. I know it's selective.
 

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"1g 4AD + 100mL chloroform + 10g MnO2 = test base 100% after 2 hours shaking at room temp"

Where is this from?

Is this true, or hack chemistry?
 

growmore

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I'm not a chemist so I can't tell you how realistic it is with a methyl derivative in use but it sounds reasonable. Supposedly it works alright with estered doil. Check this thread out over at Superior Muscle. Pay attention to posts from spidey.
 
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BigVrunga

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It does mention in that thread that 1,4-diol can be converted to boldenone via dissolving in DCM and reacting with active MnO2...
 

growmore

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Definately would like to hear some input on this one from a chemist or someone who has at least a good grasp on chemical synthesis.
Hypothetically it seams the materials needed would be pretty easy to obtain; though none of the threads I've come across give any specifics on the best filterering material to use. Coffee filterers would probably be a poor idea for this but maybe a certain grade of lab filter paper or something similiar would suffice?
As far as solvent alternatives, from what I've gathered the process would not work in a methanol solution since the MnO2 would react with this leaving nothing behind for your desired reaction. Another thing that could speed the process is if there is something that would work to drop the final crystal hormone out of the chloro solution instead of waiting for evaporation (like is done with water drops in crystal tren.) it seams with H2O's poor soubility in chloroform that water would not work for this too well. Anyways this is just a little BUMP since I'm ejoying this thread.
 

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It does mention in that thread that 1,4-diol can be converted to boldenone via dissolving in DCM and reacting with active MnO2...
I have m questions about this.. It could work.. but how would you know if it did or not?
 
BigVrunga

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TLC? Test the melting point of the final product? Both methods are fairly simple and could be performed by the kitchen chemist. (with some decent equipment).

Im tempted to give this a try, although I dont really want to waste $100 worth of 1,4-diol and whatever the reactants cost.

BV
 
BigVrunga

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Hypothetically it seams the materials needed would be pretty easy to obtain; though none of the threads I've come across give any specifics on the best filterering material to use. Coffee filterers would probably be a poor idea for this but maybe a certain grade of lab filter paper or something similiar would suffice?
Buchner funnels are easy to find at online lab glass shops or ebay, and there's a wide variety of lab-grade filter available as well. It would be relatively easy to find the right filter for the fine MnO2 powder.

One of the key things in this reaction is that the MnO2 has to be active, so finding a good source for active MnO2 would be necessary. I found a little blurb on the net that said MnO2 could be made active by boiling in dilute HCL, but I couldnt find any references to back it up.

As far as extraction - you could always distill off the chloroform rather than wait for evaporation. Once you arrive at a low enough volume where the chloroform/boldenone base solution is super saturated, it should cystalize as it cools. (let it cool slower for bigger crystals). The base could then be filtered off and purified via recrystallization.

Check this page out-its a great read on purification of a compound via recrystallization.

http://wulfenite.fandm.edu/labtech/recryst.htm

BV
 

growmore

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As far as MnO2 being active, I've checked into this about a hundred times over at different sites on the web. From what I've gathered all that "active" MNo2 really is, is just a relatively pure MnO2. Since it seams this stuff can oxodize over time this is the reason you see different purity or "activity" levels in what's available. As far as I can tell, if you're buying a regeant or lab grade powder that is meant for oxidizing reactions than you should be pretty safe.

I may be wrong here, but as far as testing for purity of the final product, as long as I knew all of the MnO2 was filtered off I probably wouldn't be too concerned with this if I was going for a reaction with Methyl 1,4-- since the impuritiy would just be unconverted M-1,4add (although melting point might be worth it since it's so simple.) I like the link you gave for distillation but would heating to lower the solution volume be a concern for damaging your product?

Some lab grade MnO2 i've seen states 98% < 10 Micron-- this translates into very fine granules. I see all kinds of lab filtration paper for sale but not much about how small of particles it picks up. Glad to see we're making some progress here.:thumbsup: Now who wants to take the plunge:D

Not a bad deal considering for the initial investment of about $150-$200 you could get what would be equal to about 800 5mg dbol tabs with even a poor conversion...
 
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BigVrunga

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I like the link you gave for distillation but would heating to lower the solution volume be a concern for damaging your product?
Good point. I couldnt find info on the melting point of boldenone, but the boiling point of DCM is only 40C (104F), that's not that high at all. Doubtful if it would degrade the product at that temperature.

I may be wrong here, but as far as testing for purity of the final product, as long as I knew all of the MnO2 was filtered off I probably wouldn't be too concerned with this if I was going for a reaction with Methyl 1,4-- since the impuritiy would just be unconverted M-1,4add (although melting point might be worth it since it's so simple.) I like the link you gave for distillation but would heating to lower the solution volume be a concern for damaging your product?
Now you're talking methylated PH's here - will the MnO2 oxidation work for them as well?

So lets break down at the cost:

Say (hypothetically speaking) you want to go with boldenone base in a transdermal, with ~300mg absorbed per week. That's roughly 900mg of boldenone a week x 8 weeks = 7200mg. Might as well get 20g and take advantage of bulk pricing:)

20g 1,4 diol $50
DCM $10
100g MnO2 $40
Magnetic Stirrer ~$80 used on Ebay.

Total: $180

Can anyone with a bit more chemistry knowledge chime in and validate this method? Chemo?

BV
 
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Andy13

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Don't forget the centrifuge!!

I'd say this is more of an essential than a stirplate!



Good point. I couldnt find info on the melting point of boldenone, but the boiling point of DCM is only 40C (104F), that's not that high at all. Doubtful if it would degrade the product at that temperature.



Now you're talking methylated PH's here - will the MnO2 oxidation work for them as well?

So lets break down at the cost:

Say (hypothetically speaking) you want to go with boldenone base in a transdermal, with ~300mg absorbed per week. That's roughly 900mg of boldenone a week x 8 weeks = 7200mg. Might as well get 20g and take advantage of bulk pricing:)

20g 1,4 diol $50
DCM $10
100g MnO2 $40
Magnetic Stirrer ~$80 used on Ebay.

Total: $180

Can anyone with a bit more chemistry knowledge chime in and validate this method? Chemo?

BV
 
BigVrunga

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Why a centrifuge? The original method posted by spidey at SuperiorMuscle calls for stirring the mixture at room temp for 24 hours. You could use a glass stir rod if you wanted to stand over it for that long:)
 
DR.D

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I still say use aluminum isopropoxide or sodium methylate w/ an oppen. equalib. reaction(cheap, easy and reliable), the MnO2 is old school sloppy, I/ve been a chemist for over 10yr's now, but nobody wants to listen! Bold MT ~ 165 deg
 
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BigVrunga

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Dr.D,
thanks for the info - How are the aluminum isopropoxide or sodium methylate superior to MnO2 in this reaction, if they're accomplishing the same end result? (assuming the MnO2 oxidation of 1,4-diol has decent yields)

Im not a chemist - Ive done a lot of reading and some succesful acid/base extractions and recrystallization purifications, but I dont have any formal training. Could you please explain the "oppen. equalib. reaction" and outline the method that your talking about in your post?

Thanks,
BV
 
DR.D

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Dr.D,
thanks for the info - How are the aluminum isopropoxide or sodium methylate superior to MnO2 in this reaction, if they're accomplishing the same end result? (assuming the MnO2 oxidation of 1,4-diol has decent yields)

Im not a chemist - Ive done a lot of reading and some succesful acid/base extractions and recrystallization purifications, but I dont have any formal training. Could you please explain the "oppen. equalib. reaction" and outline the method that your talking about in your post?

Thanks,
BV
Check these out, then let me know if you want specifics. I've oxidized compounds successfully with this one, but not steroids. However, it was originally designed for steroids.

http://www.chattemchemicals.com/Oppenauer%20Oxidations.pdf
http://themerckindex.cambridgesoft.com/TheMerckIndex/NameReactions/ONR286.htm

I developed a hydroxide version of this too that shouldn't work but does w/ secondarys, although w/ lower yields
 

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Dr.D,
thanks for the info - How are the aluminum isopropoxide or sodium methylate superior to MnO2 in this reaction, if they're accomplishing the same end result? (assuming the MnO2 oxidation of 1,4-diol has decent yields)

Im not a chemist - Ive done a lot of reading and some succesful acid/base extractions and recrystallization purifications, but I dont have any formal training. Could you please explain the "oppen. equalib. reaction" and outline the method that your talking about in your post?

Thanks,
BV
There are hundreds of oxidation reagents, they each have their own time and place...


The Oppenauer reaction is frequently employed from the oxidation toolbox. This oxidation (also MnO2 and others) have a degree of elegance since 'oxidation' ain't nearly as sexy as "selective oxidation." The Oppenaur type of oxidation would convert 5-ene- 3OL to a 4-ene 3-one (migration of the double bond occurs here). The reaction specs are more rigorous than MnO2 oxidation. Additionally, protection of the 17-ol once again becomes an issue.

Andy
 
DR.D

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OK, look ... I've thought about this whole issue again and now I'm leaning to a simple chromic acid ox. Why not? It won't take secondary alc's past ketone and w/ a 17a-alkyl compound, you have required OH protection. You can milk the reaction and be sure that it's complete w/out side products.
 

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OK, look ... I've thought about this whole issue again and now I'm leaning to a simple chromic acid ox. Why not? It won't take secondary alc's past ketone and w/ a 17a-alkyl compound, you have required OH protection. You can milk the reaction and be sure that it's complete w/out side products.
What is protecting the 17-OH?

A 17-methylated PH with 3-OH?
 
DR.D

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What is protecting the 17-OH?

A 17-methylated PH with 3-OH?
Yeah, they're quite prevalent these days. 17a-alkly,17b,3b-OH, just methylated versions of DBall, methyltest, etc. but the diols. So what do you think about the CrO3?
 
BigVrunga

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Thanks for the links, Dr.D

So are you guys saying that selective oxidation via MnO2 wont work? And if it will work, then why over-complicate the process?

BV
 
DR.D

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It will work, I was just trying to think of a cleaner, cheaper way. Believe me, I've considered it before too, but now that methyls are so available in pure reagent grade, it could really save money. If you decide to get serious about this, and you can find all of the starting materials, PM me and I'll help you through it if A13 or someone else doesn't.
 

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Been a couple days since I checked this thread. I'm glad to see things have together a little more clearly.

Dr.D, are you saying the MnO2 oxidation process would work for not only a normal doil, but also a methyl doil?

Is it realistic to use 100ml solvent, either chloro or DCM per gram of base product or could more be processed in this amount?

It's also still unclear as to what grade of filter paper would be sufficient at picking up excess Mn02 (although minor, I feel this is an important detail.)

Other than than these few things it seams this could be relatively simple and cost effective process...
 
DR.D

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Been a couple days since I checked this thread. I'm glad to see things have together a little more clearly.

Dr.D, are you saying the MnO2 oxidation process would work for not only a normal doil, but also a methyl doil?

Is it realistic to use 100ml solvent, either chloro or DCM per gram of base product or could more be processed in this amount?

It's also still unclear as to what grade of filter paper would be sufficient at picking up excess Mn02 (although minor, I feel this is an important detail.)

Other than than these few things it seams this could be relatively simple and cost effective process...
I still have yet to see the method, can you send it to me? Then I can help with the volumes and ratios. You are probably going to be fine w/ a whatman #1 or 4 fiberglass or ash-free filter paper. Maybe 2 doubled up a few times. It depends. I'm thinking with methylene chloride, an end extraction may be better. Your going to need a 500-2000ml sep funnel though (kinda expensive) but worth it.
 
BigVrunga

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I still have yet to see the method, can you send it to me? Then I can help with the volumes and ratios. You are probably going to be fine w/ a whatman #1 or 4 fiberglass or ash-free filter paper. Maybe 2 doubled up a few times. It depends. I'm thinking with methylene chloride, an end extraction may be better. Your going to need a 500-2000ml sep funnel though (kinda expensive) but worth it.
Are you suggesting a standard A/B extraction to clean up the final product if using DCM? What byproduct would DCM introduce into the reaction? Chloroform can be made fairly easily from some common ingredients, although DCM is quite easy to find.

I second growmore's question as well - will MnO2 work to convert methylated diols as well? If it selectively oxidizes the 3-OH does the methyl group stay intact throughout the reaction?

BV
 

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I still have yet to see the method, can you send it to me? Then I can help with the volumes and ratios. You are probably going to be fine w/ a whatman #1 or 4 fiberglass or ash-free filter paper. Maybe 2 doubled up a few times. It depends. I'm thinking with methylene chloride, an end extraction may be better. Your going to need a 500-2000ml sep funnel though (kinda expensive) but worth it.
The method is basically the one quoted by BigVrunga at the beginning of the thread. Minus dropping the final product from solution with methanol; I don't think this part would work. It's also covered pretty well by spidey at This Link about two-thirds way down the page.
 
DR.D

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I looked at the method on the link you provided, GM. If a Whatman low ash filter would work, and I think it would, that would be fine. Especially if you want to collect the Mn and use it again. If it's cheap enough, I'd say just do an acid extraction to solubilize the Mn02 and Mn3O4 after the reaction. The BP for DCM is low, about 40, and evap would be fast and easy. It's not flamable, so a stove top or good steam bath would work, but you'd need a hood for the strong vapors. Vac. oven not needed but helpful once you have crystals. Spidy suggests 5:1 oxidant ratio, but that sound kind of high to me. Maybe the first time, but if you got good at this, I'd say less oxidant and more stir time. How available is the MnO2?
 

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MnO2 isn't listed as a hazardous material for usps so it's pretty readily available all over the web without special shipping requirements. Someone buying it would just have to be sure to get a lab or reagent grade.

DCM is used as paint stripper, but I don't think you can get it in its pure form this way... One website suggested craft stores may carry it. The paint strippers also generally contain methanol, and you definitely wouldn't want that in the mix if it does indeed react with the MnO2. Any other more viable solvents?

I'm just exploring this out of curiosity of coarse-- it would be nice to see someone with proper equipment for testing the final product and as well as the time it takes for completion of the reaction give this a shot. I'm really surprised no one has put this together yet, considering the relative simplicity...

I'de like to hear more about the idea of an acid extraction, since I don't think you'd want to reuse the the left over MnO2 anyways. Also if anyone chemically inclined reading this knows how the MnO2 would react on a methylated doil, feel free to chime in...
 
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I'de like to hear more about the idea of an acid extraction, since I don't think you'd want to reuse the the left over MnO2 anyways. Also if anyone chemically inclined reading this knows how the MnO2 would react on a methylated doil, feel free to chime in...
Sorry, forgot to mention that 17methyl diols are not a problem. The MnO2 isn't going to touch it. The link I read was kinda old and these probably were not as available then. As for the sep acid extraction, why not? In the presence of H2O2, the unreacted oxidant becomes sol in dil H2SO4. So extraction is clean & easy and loss is neg. CHCl3 might be easier to obtain, CH2Cl2 is on the EPA protocol like Freon was, so even though it's not flammable, it's a health and enviro risk. I'll investigate alternate solvents.
 
BigVrunga

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Nice to see this thread is getting so in-depth. Thanks for all your input so far guys!

Dr.D - so if you used a methylated diol in this reaction (m1,4, for instance) you'd end up with d-bol as your final product? Interesting...

As far as the reagents, pure DCM is available from at least one place I know of online and its dirt cheap. Reagent grade MnO2 is also available from several chem suppliers, and I dont think it would be that difficult to obtain. The most expensive part of this reaction is going to be the inital investment in a magnetic stirrer and some glassware, both easily obtainable from good 'ol ebay.:)

Dr.D - about the acid extraction - your saying to dissolve your final product in H2O2, mix with H2SO4 and separate the H2SO4 layer via seperatory funnel? Will the converted diol-base dissolve in H2O2? If so, would it have to be evaporated off to obtain pure crystals?

BV
 
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"whew", im no where near as much of a chemist as some of you.,this is way to involved for me to do, but the results sound great. to bad i didnt go to college[damm ADD]"LOL"
 
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"whew", im no where near as much of a chemist as some of you.,this is way to involved for me to do, but the results sound great. to bad i didnt go to college[damm ADD]"LOL"
Don't sweat it buddy! It looks like BV or GM will work out the details first, then once they have it down, you can PM them for the whole formula. Hey wait... you've gotta be a lot smarter than your pretending to be with a plan like that ;) ADD is actually what got me into organic chem, if you know what I might be saying. :blink:
LOL
 
DR.D

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Dr.D - about the acid extraction - your saying to dissolve your final product in H2O2, mix with H2SO4 and separate the H2SO4 layer via seperatory funnel? Will the converted diol-base dissolve in H2O2? If so, would it have to be evaporated off to obtain pure crystals?

BV
No, your extracting the oxidant and leaving the product in the DCM or Et2O or whatever solvent you can get that's chemically acceptable and water insoluble. With DCM, your organic layer is on bottom. But with Et2O, it's on top so that would favor water washes. After the reaction is complete add some H2O2 and the whole reaction mixure to the sep funnel. Unreacted MnO2 is poorly sol in sulfuric or nitric. HCl or HI would be fine, but some free halogen would be evolved, it might be just a little or truely toxic to breath, it depends on how much excess oxidant you use (which might be a lot the first time or two.) But, in the presence of oxalic acid or H2O2, MnO2 becomes sol in dilute H2SO4 or HNO3. Of these choices, H2O2 w/ sulfuric is what I'd favor. Shake it a few min's, remembering to invert and vent often, then drain and decant the water layer and repeat extraction till it's all clean, probably 3 to 6 more, you'll know. Then run the organic layer through a drying tube w/ a little glass wool on the botton and packed w/ MgSO4, anhy. This leaves your filtered DCM w/ no water or left over oxidant in it, collected in a flask and ready to evap. If you use ether, drying is even more important. Am I making any sense, it's Thursday and I'm ususally pretty sleep deprived at this point, keep contemplating and I'll get back with ya later this w/e on the evap details. I know your not really going to make all that highly grade, crystalline DBol, but it's fun to talk about though! Nobody at AM would eeeever do stuff like thaaat. Right? OK, good. Oh yeah, the validation could be by HPLC if you have access to one, and TLC would work too, I'll think of a good, separating mobile phase, or spidey may have listed one on that link, I don't remember, but a KBr pellet by IR scan would be best. Any way, your going to need a std or know some retention times. That will take some figuring or your product may be pure enough that you feel val. is not needed. Oh well, to bad it's all just a couple of guys talkin about stuff they're NEVER planning to do anyway. :drunk:
 
BigVrunga

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ADD is actually what got me into organic chem, if you know what I might be saying
:D

No, your extracting the oxidant and leaving the product in the DCM or Et2O or whatever solvent you can get that's chemically acceptable and water insoluble. With DCM, your organic layer is on bottom. But with Et2O, it's on top so that would favor water washes. After the reaction is complete add some H2O2 and the whole reaction mixure to the sep funnel. Unreacted MnO2 is poorly sol in sulfuric or nitric. HCl or HI would be fine, but some free halogen would be evolved, it might be just a little or truely toxic to breath, it depends on how much excess oxidant you use (which might be a lot the first time or two.) But, in the presence of oxalic acid or H2O2, MnO2 becomes sol in dilute H2SO4 or HNO3. Of these choices, H2O2 w/ sulfuric is what I'd favor. Shake it a few min's, remembering to invert and vent often, then drain and decant the water layer and repeat extraction till it's all clean, probably 3 to 6 more, you'll know. Then run the organic layer through a drying tube w/ a little glass wool on the botton and packed w/ MgSO4, anhy. This leaves your filtered DCM w/ no water or left over oxidant in it, collected in a flask and ready to evap. If you use ether, drying is even more important.
I see what you're saying. To get out ALL the MnO2, rather than just filter, dissolve it in H2SO4 via reacting with H2O2 to make it soluble. Should these 'washes' be done after filtering. then? Or does it make it possible to eliminate the filtering step all together?

Does it matter if you get all the H2O out of the DCM/final product mix? If its going to be air evap'd anyway, wont it pick up moisture from the atmostphere? Or, does removing as much water as possible make for better crystal formation? (rather than just a dish of boldenone goop):)

BV
 
DR.D

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:D



I see what you're saying. To get out ALL the MnO2, rather than just filter, dissolve it in H2SO4 via reacting with H2O2 to make it soluble. Should these 'washes' be done after filtering. then? Or does it make it possible to eliminate the filtering step all together?

Does it matter if you get all the H2O out of the DCM/final product mix? If its going to be air evap'd anyway, wont it pick up moisture from the atmostphere? Or, does removing as much water as possible make for better crystal formation? (rather than just a dish of boldenone goop):)

BV
Yeah, the extractions take care of the filtering. If your solution still looks hazy after the washes, the drying tube will filter it for sure. DCM works very well for this kind of set up. MgSO4 sucks the water right out of it, what little is there. And atmo. water is fine, it's the Mn contaminated water your worried about. It might not hurt, but Parkinsons, and kidney damage are to be avoided. Your body needs a little Mn though. As for the final product, you may need to recrystalize from alcohol or EtAc maybe, you'll have to see. Low heat evap might be fine, with an acetone flash at the end. I was also thinking, if your Mn settles out after the reaction, you could just drain off your solvent right into a filter paper filled with siliceous earth or MgSO4, anhyd. and skip the extraction altogether. Then you wouldn't even need the sep. funnel. That would cut a step and save you 100$ right there.
 
BigVrunga

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So a little extra effort refining the final product will definately be worth it...

Even with filtering you might not get out ALL the Mn, so in order to obtain a nearly pure product, the proper thing to do is to extract out all the Mn and recrytalize...

What exactly is an acetone flash and how is it performed?

Thanks,
BV
 
DR.D

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So a little extra effort refining the final product will definately be worth it...

Even with filtering you might not get out ALL the Mn, so in order to obtain a nearly pure product, the proper thing to do is to extract out all the Mn and recrytalize...

What exactly is an acetone flash and how is it performed?

Thanks,
BV
Hey BV, maybe a hybrid method. Like let it sit till all the Mn has fallen out after the reaction. Then pour the solvent off of the top, and maybe wash it 2x w/ the H2O2/acid combo. just to get the traces. I'd only do this if it was cloudy, otherwise, a fluted whatman filter or two with some MgSO4, anhydrous in them should be fine. Pour the solvent in and let it drain slowly through the salt loaded filter. This should work well. The acetone flash is waiting till your warm solvent has almost evap'ed off and ctystals have started to form, then you add a small amout of cool acetone to it and it will often finish the crystal formation. If you end up with goo, you could dissolve it in miminal acetone or alc. and then add DI H2O to that in large volumes (like 10:1). Your crystals will crash out fast and you can put it in the frig over night to finish growing them out fully. Then filter that with a whatman filter paper or even a few coffee filters if your crystals are large enough. Dry over silica or low heat in the oven and then your done.
 

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I like the idea of a filtration through MgSO4. Does filtration through magnesium sulfate or siliceous earth have intrinsic properties that pick up Mn or is it just good filter media? If it does pick up Mn would the rest of the MnO2 have to be reacted before hand? I assume there wouldn’t be any H2O present when skipping the acid extraction.



Would it be possible to rinse solidified crystals with an HCL solution for a purification step?



I noticed Et2O mentioned as a solvent, it seams that this would be relatively difficult to come by; has anyone come across any other more viable options?


Thanks Dr and BV for all of the great posts so far, I’ll be ½ to a degree after deciphering all this chem. talk:thumbsup:
 

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