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

Page 1 of 2 12 Last
  1. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

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


    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

  2. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

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

    Seems interesting.
  3. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    Quote Originally Posted by BigVrunga
    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.
    •   
       

  4. Board Supporter
    Sgt. Ownage's Avatar
    Join Date
    May 2004
    Age
    28
    Posts
    132
    Rep Power
    194
    Level
    11
    Lv. Percent
    14.64%

    Someone else respond, this is a very interesting thread
  5. New Member
    Andy13's Avatar
    Join Date
    Feb 2004
    Posts
    24
    Rep Power
    143
    Level
    4
    Lv. Percent
    52.79%

    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 ob˘ainable (LAH is pretty damn dangerous). There are a handful of well t˛aveled 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
  6. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    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!
  7. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
  8. New Member
    Andy13's Avatar
    Join Date
    Feb 2004
    Posts
    24
    Rep Power
    143
    Level
    4
    Lv. Percent
    52.79%

    Quote Originally Posted by BigVrunga
    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
  9. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    http://ptcl.chem.ox.ac.uk/MSDS/SE/selenium_dioxide.html

    Dosent sound like something I want to be around any time soon!
  10. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    Here's one for you--
    M-1,4ADoil + MnO2 in either chloroform or 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.
  11. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    Quote Originally Posted by growmore
    Here's one for you--
    M-1,4ADoil + MnO2 in either chloroform or 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.
    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.
  12. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    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"
    Quote Originally Posted by DR.D
    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.
  13. Banned
    Brodus's Avatar
    Join Date
    Mar 2004
    Age
    38
    Posts
    765
    Rep Power
    0
    Level
    23
    Lv. Percent
    46.37%

    "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?
  14. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    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.
    Last edited by growmore; 07-12-2004 at 08:59 PM.
  15. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    It does mention in that thread that 1,4-diol can be converted to boldenone via dissolving in DCM and reacting with active MnO2...
  16. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    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.
  17. New Member
    Andy13's Avatar
    Join Date
    Feb 2004
    Posts
    24
    Rep Power
    143
    Level
    4
    Lv. Percent
    52.79%

    Quote Originally Posted by BigVrunga
    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?
  18. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
  19. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
  20. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    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. Now who wants to take the plunge

    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...
    Last edited by growmore; 07-15-2004 at 05:01 PM.
  21. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
    Last edited by BigVrunga; 07-16-2004 at 07:56 AM.
  22. New Member
    Andy13's Avatar
    Join Date
    Feb 2004
    Posts
    24
    Rep Power
    143
    Level
    4
    Lv. Percent
    52.79%

    Don't forget the centrifuge!!

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



    Quote Originally Posted by BigVrunga
    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
  23. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
  24. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    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
    Last edited by DR.D; 07-16-2004 at 08:16 PM.
  25. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
  26. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    Quote Originally Posted by BigVrunga
    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/Oppe...Oxidations.pdf
    http://themerckindex.cambridgesoft.c...ons/ONR286.htm

    I developed a hydroxide version of this too that shouldn't work but does w/ secondarys, although w/ lower yields
  27. New Member
    Andy13's Avatar
    Join Date
    Feb 2004
    Posts
    24
    Rep Power
    143
    Level
    4
    Lv. Percent
    52.79%

    Quote Originally Posted by BigVrunga
    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
  28. New Member
    Andy13's Avatar
    Join Date
    Feb 2004
    Posts
    24
    Rep Power
    143
    Level
    4
    Lv. Percent
    52.79%

    Quote Originally Posted by DR.D
    MnO2 is old school sloppy,
    Why do you say this?

    Is there a better way for the selective oxidation of allylic alcohols?
  29. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    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.
  30. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    Quote Originally Posted by Andy13
    Why do you say this?

    Is there a better way for the selective oxidation of allylic alcohols?
    selenium dioxide, maybe
  31. New Member
    Andy13's Avatar
    Join Date
    Feb 2004
    Posts
    24
    Rep Power
    143
    Level
    4
    Lv. Percent
    52.79%

    Quote Originally Posted by DR.D
    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?
  32. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    Quote Originally Posted by Andy13
    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?
  33. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
  34. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    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.
  35. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    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...
  36. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    Quote Originally Posted by growmore
    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.
  37. Elite Member
    BigVrunga's Avatar
    Join Date
    Nov 2002
    Age
    38
    Posts
    5,063
    Rep Power
    2683
    Level
    49
    Lv. Percent
    26.7%
    Achievements Activity ProPosting ProPosting Authority

    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
  38. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    Quote Originally Posted by DR.D
    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.
  39. Elite Member
    DR.D's Avatar
    Stats
    6'0"  228 lbs.
    Join Date
    Dec 2003
    Posts
    6,779
    Rep Power
    307853
    Level
    56
    Lv. Percent
    45.21%
    Achievements Activity ProPosting ProPosting Authority

    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?
  40. Board Supporter
    growmore's Avatar
    Join Date
    Jul 2004
    Posts
    105
    Rep Power
    178
    Level
    9
    Lv. Percent
    19.88%

    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...
  

  
 

Similar Forum Threads

  1. Replies: 23
    Last Post: 03-03-2012, 06:47 PM
  2. Replies: 25
    Last Post: 01-17-2011, 11:42 PM
  3. Replies: 17
    Last Post: 06-24-2005, 04:22 PM
  4. is there a PH similar to winny ??
    By lxorl in forum Anabolics
    Replies: 1
    Last Post: 03-18-2003, 08:50 AM

Posting Permissions

  • You may not post new threads
  • You may not post replies
  • You may not post attachments
  • You may not edit your posts
  •  
Log in
Log in