06-10-02 00:51
No 319322
Hello,
Since I am a New"bee" and this is the Newbee forum i am going to ask a newbee question.
In terms of yield which is better Oxone or Performic/Peracetic. In terms of easiness which is better??
(Hive Bee)
06-10-02 01:00
No 319324
UTFSE. The performic yields ~85%, the peracetic according to Chromic can yield ~70%, the oxone route maybe 50%? Seems to me most people have been having problems with the oxone route.
A watched pot will indeed boil.
(Hive Addict)
06-10-02 01:42
No 319336
The buffered performic yields 65-75% of theory.
The buffered peracetic yields >60% of theory (likely 65-70%).
The oxone method yields 50-65% of theory (perhaps higher).
The main yield limiting step is the sulfuric acid hydrolysis, tosic acid may give higher yields. As of yet, no one has posted any information on the topic.
(Stranger)
06-10-02 02:04
No 319344
So im guessing here since Oxone uses loads of H2O that performic is the best option. Also i looked under the search engine and found the yields to vary. i just wanted some other bees opinions. Thankx!!
(Hive Bee)
06-10-02 03:18
No 319363
Swim's last three performics ran with 82%, 87% and 87% yield respectively (w ketone / w isosafrole). Swim was *very* careful with everying including a fractional distillation at the end, making sure to get out all water, dcm, etc., and toss the forerun which came over right under the ketone (which was about 30 drops of something very ultra-neon-green, coulda been ketone but...). The rest was bright yellow. 85% avg.
A watched pot will indeed boil.
(Hive Addict)
06-10-02 03:31
No 319367
> Swim's last three performics ran with 82%, 87% and 87%
> yield respectively (w ketone / w isosafrole).
come on! you know that yields are (actual / theoretical).
so your 85% is really only 77%. probably not ultra pure
and you get the values of chromic...
(Chief Bee)
06-10-02 04:21
No 319377
Hypo: Are you suggesting that greeter calculated a weight/weight yield instead of a mole/mole yield, or am I completely off?
(Hive Addict)
06-10-02 04:25
No 319379
yes, i think so.
at least that's how i interpreted "(w ketone / w isosafrole)"...
(Chief Bee)
06-10-02 04:32
No 319381
Oh, sorry - I didn't see those w's.
Why is it so hard to calculate the molar yield, everybody? The molecular weights of all the compounds we are using here are plastered all over the web, and is automatically calculated by programs such as ISIS-Draw... And all this just if you don't want to learn H=1, C=12, N=14 and O=16, and perform simple addition and division.
(Newbee)
06-10-02 11:10
No 319480
SWIM runs oxone at about 55% crude weight. Oxone is whaaay! easier IMO and gets cleaner products if you don't own a ketone distillation set up just yet.
SWIWS started out with a Performic and spent 3 weeks/$600 on chems n' sassy and for nothin' Tried the oxone and sucsess the first time! This was a lot of lab technique practice later and the amalgam is still tricky to get good yields. But hey it worked first time.
The Oxone route uses a shitload of methanol and dH2O but for the newbee the easy workup and easy aquisition of reagents make it a great choice (OTC). Even though the yields are about 35% less than other routes you are more likely to end up with fluffy yummy love powder at the end of the day.
IMO anyways.the 21st of the 12th 2012......
(Hive Bee)
06-10-02 11:52
No 319494
Sorry, didn't know to calculate molar yield. Duh. Will do in the future.
Thanks!
A watched pot will indeed boil.
(Stranger)
06-10-02 18:21
No 319609
OK, i figured out overall i believe oxone to be easier and cheaper but does not have as good of yield here are my calculations...
For the oxone route, reacting 50g iso-safrole --> epoxide requires (from my sources) $3.19 worth of chemicals and 5hours reaction time but requires a reaction flask of approx. 2L
For the performic route, reactiong 50g iso-safrole --> epoxide requires (from my sources) $5.10 worth of chemicals and 16hours of reaction time and only needs a reaction flask of less than 500mL.
So i figure the reaction with oxone may be better but which method produces cleaner epoxide??
Thanx bees for all the help so far.
(Stranger)
06-10-02 18:24
No 319613
Oh yeah and... I care ALOT about the time it takes to convert to epoxide, the oxone rxn is 3 times quicker so that helps me a bunch.
(Hive Addict)
06-10-02 21:43
No 319692
The Oxone in MeOH takes LONGER than the peracetic in dcm or performic in dcm. Choose the oxone method only when you do not have access to other superior methods (ie benzo wacker due to its high cost and availability of reagents, performic due to availability of formic, peracetic due to availability of acetic, etc).
(Stranger)
06-10-02 22:45
No 319712
hmm according to rhodiums site reaction for oxone to convert to epoxide is roughly 5hours and the reaction for performic to convert iso-safrole to epxoide is 16hours with buffered performic. Am i mistaken somwhere?? and why is performic superior? Does it produce more pure epoxide than the oxone method?? SWIM need answers before SWIM goes out and buys the chemicals....
(Hive Addict)
06-10-02 22:54
No 319718
Uh, dude... I think you should do more research. You want ketone, which will mean that you have to take the epoxide from the persulfate method (oxone) and treat it with 15% H2SO4 just as in the performic and peracetic methods.
(Stranger)
06-11-02 00:46
No 319738
SWIM have done his research and SWIM plans to distill every step of the way. THAT means SWIM distilled his sassafras oil to get safrole, he then distilled that safrole again to obtain a purer fraction of safrole. Isomerized and distilled to collect two different fractions iso-safrole and safrole. Distilled the iso-safrole another time. SWIM wanted the best quality everything but doesnt like to distill because it takes forever, that is why i asked for the purity of epoxide so SWIM can skip the step of distilling epoxide. SWIM wants the highest yield (but he still wants it to be OTC) and the cleanest product possible. Because the purer your product the higher your yield will be when you do the reactions. Am I not correct?
As for the performic and oxone i was asking which produces a more pure epoxide so SWIM can just skip the step of distilling epoxide and just hydrolyze it with 15% H2SO4 to Ketone then distill the ketone straight. He dont want to go through the process of sodium bisulfite adduct if not necessary.
Thanks Chromic for all your help i think you were just mis-interpreting my question/knowledge. Yes SWIM knows the full process to make safrole--->MDMA.HCL by memory so you shouldnt doubt his knowledge.
I just want to have pure ketone without extra steps.
(Hive Bee)
06-11-02 02:03
No 319767
You don't need to do this. Hydrolyse it then carefully vac distill the ketone. Are you planning to distill your freebase as well?
A watched pot will indeed boil.
(Stranger)
06-11-02 09:34
No 319842
Hey just a quick question I have been wondering about but havn't seen the answer to: If both the performic and the oxone routes both yield glycol/epoxide in roughly 95% yields, then the only difference should be the hydrolysis. But the hydrolysis is the same in the two methods, then why are there such different yields in the two methods? Please could someone clear this up, it has confused me for the longest time. (Swim however is going the O2 wacker route w/ custom built reactor, clean, small, and easy imo)
On the 6th day God created man. On the 7th day, man returned the favor.
(Chief Bee)
06-11-02 12:43
No 319887
Chromic: How can you say the oxone route takes longer time than the modified performic?
Have you done trial runs in shorter time with the modified performic and found that letting it react overnight is not necessary?
(Hive Bee)
06-11-02 13:27
No 319898
Hope nobody minds if I pop in from out of nowhere with a question, but.....
What are the potential differences in using ethanol instead of methanol in the oxone route? Now this probably sounds idiotic but I have a friend who has not experienced much success after switching from smaller methanol reactions to larger ones using ethanol. He suggested that the differing bp's of the solvents was perhaps to blame, as the exothermic reaction would run too hot. Would the solvent indeed be a factor or is the reaction just very sensitive to scale up? A friend of mine is ready to abandon this method after recieving only occasional success. What other factors might be involved in the success of the oxone run?
_flip_@hushmail.com
(Hive Addict)
06-11-02 13:33
No 319899
Sorry, I stand corrected. I assumed that since formic acid is a stronger oxidizer than acetic acid, the write up for the performic acid surely couldn't be greater than 5hrs.
Turns out it is, for whatever reason. Might be unnecessary too.
(Can't SWIM)
06-11-02 16:08
No 319956
Also, swim would like to know the sucsess ratio, for those
that have been trying the oxone route.
CG I miss you sweety, I really do.
(Greenhorn)
06-11-02 17:03
No 319972
Humid, Pickler uses the oxone on a regular basis and it works fine.
We'll soon find out if I'm a chemist or not!
(Stranger)
06-11-02 19:18
No 320013
Yes, ethanol can be used read the article on rhodiums site thoroghly about oxone. "Oxidation of propenylbenzenes to P2P's using Oxone" by Chromic (THANKS CHROMIC FOR THE WONDERFUL RIGHT UP)
Addendum by Psychokitty...
"Old paper detailing the oxidation of many substances using Oxone hints strongly that ethanol can be used in place of methanol as the solvent in this reaction. Use of isopropanol is also possible. All solvents seem to react to some degree with the Oxone in solution."
SWIM plans to use ethanol of methanol for his oxone run and it should work according to theory....
(Hive Bee)
06-11-02 22:58
No 320076
pickler-
are there any specific modifications swiy is using for oxone runs? Swim see's quite a few bee's having difficulties. In swiys opinion, what is the reason for this? (other than not strong enough vacuum).
when someone asks what the sound of one hand clapping sounds like, you should smack them in the ear.
(Greenhorn)
06-11-02 23:16
No 320088
The only thing Pickler does is filter the oxone to make an oxone solution. That's it. Swim just follows the synth after that!
We'll soon find out if I'm a chemist or not!
(Hive Bee)
11-01-02 14:14
No 375489
so, as Flip stated, ethanol can it bee exchanged for methanol? and it seems that it can, then, can the other bee true as well?
methanol bee used instead of ethanol?
Why?
(Chief Bee)
11-01-02 14:38
No 375497
Not for all reactions, but in many instances.
(Hive Bee)
11-01-02 14:52
No 375506
can it bee substituted there? that's the only place that it suggests using it.
500mL ethanol in a flask with 400mg of HgCl2 (669mg of HgI2?), etc.
can 500mL of methanol bee used?
Why?
(Chief Bee)
11-01-02 15:37
No 375519
Yes. HgI2 will take much longer to amalgamate though, as its solubility is so low (regardless of solvent).
(Old P2P Cook)
11-01-02 17:38
No 375550
Actually the Merck says that mercuric iodide has very good solubility in alcohol and also the equimolar amount of potassium iodide found in Tincture of Iodine should greatly improve its solubility in water.
Merck Index entry:
5932. Mercuric Iodide, Red.
Mercury biniodide. HgI2; mol wt 454.40. Hg 44.14%, I 55.86%. Scarlet-red, heavy, odorless, almost tasteless powder; sensitive to light; at 130 deg becomes yellow, and then red on cooling. Poisonous! d 6.28. mp 259 deg. bp =350 deg and sublimes. Soly in water (25 deg) 0.006 g/100 g. 1 g dissolves in 115 ml alcohol, 20 ml boiling alcohol, about 120 ml ether, about 60 ml acetone, 910 ml chloroform, 75 ml ethyl acetate, 260 ml carbon disulfide, readily in alkali iodides, HgCl2, Na2S2O3; sol
in 230 ml olive oil, 50 ml castor oil. Protect from light.
USE: In anal. chemistry for preparation of Nessler's Reagent (alkaline mercuric potassium iodide solution).
THERAP CAT: Antiseptic (topical).
THERAP CAT (VET): Has been used as a topical antiseptic, counterirritant, vesicant.
Baseline Does Not Exist.
(Newbee)
11-13-02 22:41
No 379550
Swim tried adding I2 crystals (made from NaI + HCl + H2O2, dried 4h over CaCl2) to elemental Hg. 0.32g I2 was added to 0.25g Hg. It did not turn to a red powder as hellman describes. The substances were mixed with a strip of Al (bad choice...)
It remained a pile of purple I2 crystals with little Hg blobs buried in it.
4h later it looks the same, if anything the pile is more black, the end of the Al strip has turned black and gooey (yuck, why didn't swim use glass).
Swim also put .5g Hg in 30ml of 2% I2, 2.4% NaI, 47% alcohol 4 days ago. Swim has shaken it 2-3x per day but the Hg is very slow to react and dissolve. Annoying, swim wants to amalgamate things!!!
(Hive Bee)
11-14-02 13:32
No 379715
when swim puts the mercury in 2% tincture it actually doesnt seem to dissolve much of the Hg (visibly) but the 15mL of the solution will amalgmate around 25g of foil :)
From my experiments 1g of mercury can make ~100mL of tincture/hg solution which is enough to amalgamate up to 150g of foil.
Sink or SWIM
(Hive Addict)
11-14-02 16:12
No 379780
So basically you're saying to dissolve as much mercury as possible in 2% tincture, then use 15ml of the resulting liquid in a reaction with 25g of aluminum foil, not 25g of ketone?
Who is that masked man?
(Hive Bee)
11-14-02 17:20
No 379807
Yep! It works perfectly. First the solution with the alcohol/aluminum/tincture mixture is red then after 15minutes faint bubbling will be noticeable. This is when the color goes clear and then after 45min the aluminium is eaten up and it turns to a grey sludge and bubbling is pretty fast.
Sink or SWIM
(Hive Addict)
11-14-02 18:20
No 379829
Have you tried it with a larger quantity of Al than 25g?
Who is that masked man?
(Bear With Me)
11-14-02 18:21
No 379831
This is where it all started (sort of):
All aminations were of the al/hg variety, using methanol as a solvent (isopropanol was never used successfully), with ~.5 gram blobs of hg dropped into I2 tincture, allowed to react for a few days, and then used to amalgamate.
~unnilhexium
Post 248601 (unnilhexium: "Re: When substituting GAA for Formic acid...", Chemistry Discourse)
"All aminations were of the al/hg variety, using methanol as a solvent (isopropanol was never used successfully), with ~.5 gram blobs of hg dropped into I2 tincture, allowed to react for a few days, and then used to amalgamate.
Swim recorded an actual amalgamtion time, it took 17 minutes(.5g mercury blob, 30g Al). The basic procedure is to put a plastic dish on the old balance, zero it, and poke at a mercury blob until about .3-.5 grams is weighed out, then dump it into some 2% I2 tincture, the kind you buy at walmart. I can't verify that HgI2 is formed, but I have successfully amalgamated using this procedure."
~unnilhexium
Post 266225 (PoohBear4Ever: "Re: MM Nitro/Al-Hg variation: No HgCl2", Methods Discourse)
...ISO-SWIM decided that instead of using HgCl2, he would try Hg(2?)I2 instead(mercury blobs dropped into I2 tincture, ala unnilhexium). The batch was done at a half scale, 12.5g ketone, 10ml MeNO2 and 13.7g aluminum foil. The tincture, .24g Hg from a thermometer dropped in a 30ml 3% I2 tincture 1 week earlier, was dissolved in 400ml MeOH, and dumped into a 2L RB flask, to which the aluminum and a 2.5 inch stirbar had already been added. Amalgamation took approximately 35-40 minutes, and once complete, the ketone/nitro was dripped in....
~unnilhexium
Post 263260 (isohuman: "MM Nitro/Al-Hg variation: No HgCl2", Methods Discourse)
That should answer all you question on HgI2...
PB
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