Author Topic: Peracetic in DCM - dreams of success  (Read 21478 times)

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Chromic

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Peracetic in DCM - dreams of success
« on: December 27, 2001, 09:17:00 PM »
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Post 250498 (missing)

(Chromic: "Re: Chromic's DRAFT peracetic (BIG MISTAKE)", Newbee Forum)
I mentioned having a dream about a peracetic in DCM with anethole. This dream had a happy ending…

A summary of my latest dream:

I watched a gray-haired old man with black-trimmed glasses add 100mmol alkene (14.8g), 150ml DCM to a 500ml flask. 76.1g of 15% peracetic acid (2) buffered with 3g sodium acetate (3) was dripped in over 10 minutes. A mild reflux was present for 5 minutes or so. Then subsided. The reaction was left to stir as the protagonist went off, apparently, into a deep sleep.
 
Perhaps, five or six hours later the main character awoke quite restlessly from his deep sleep, and there I observed him slowly add 150ml of 10% Na2CO3 (NaOH would work too, but Na2CO3 was apparently less expensive to the old man), allowed it to stir, transferred to a sep funnel, drained off organic, then repeated.

The DCM was distilled off (4), 18.8g of oxidation product remained (1), and the oxidation product was put into a standard rearrangement technique.

25ml MeOH were added along with 120ml 15% H2SO4. This was heated to reflux with stirring for 2hrs, extracted 3x with 20ml DCM, washed 2x with 5% NaOH.

After rearranging, a simple distillation was setup, the DCM distilled, then vacuum was applied and this yielded 0.3g clear and colorless forerun at 148C-168C (~5 drops) (likely anethole) and 9.2g slightly yellowish PMP2P at 172-76C. (56.1% yield)

I watched the old man smile with a slight chuckle as I came to consciousness, and decided to quickly jot down some these notes that he telepathically relayed:

(1) if it was solely the glycol this 18.8g of glycol would be 103mmol, which is impossible, and upon no-vac distillation the distillate smells of acetic acid (but the oxidation product does not have this smell), so he had  a good yield of the acetate ester as well. So the sodium acetate buffered version does not produce the epoxide, and in other trials it also appears that adding bicarbonate doesn't allow the epoxide to be formed either... but perhaps some other dreamer will get it to work. Maybe it would be best to try a stronger base like sodium carbonate for the buffering.

(2) 38.4g 35% H2O2, 36.9g acetic acid, 0.8g H2SO4 can be used to prepare 76.1g of 15% peracetic acid. This solution must sit for, preferably, 2-3 days. In fact, he had prepared a large stock solution in advance so he only had to do this once-an old man, but a smart old man. He DID NOT BUFFER his stock solution.

(3) A 2x molar excess of sodium acetate with respect to the sulfuric acid content in the peracetic acid was used to buffer the solution before addition to the flask.

(4) The internal temperature of the flask hit a temperature of over 100C, so I'm sure he distilled off all the DCM, this yield is correct.

(5) PMP2P sinks in water (rather than floats), smells nothing like licorice and tests positive to bisulfite.

Chromic

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Re: Peracetic in DCM - dreams of success
« Reply #1 on: December 28, 2001, 06:55:00 AM »
I just awoke from another nap, I watched that same pesky old man with the dark-trimmed glasses add 2.5g Na2CO3 (sodium carbonate), 5ml dH2O (distilled water), 23ml MeOH, 5.0g previously-made phenylacetone (pmp2p), and 3.2g (NH2OH)2.H2SO4 (hydroxylamine sulfate) to a flask. He then refluxed the mixture for 2 hrs on a water bath, removed from heat, then added about 15ml dH2O. He allowed it to cool, then moved it to the freezer and suction filtered using saran wrap to push out most all of the solvent possible. He then air dried it, and a white crunchy solid with a mass of 6.6g was obtained (obviously he had some impurities, as this yield is inflated, only 5.5g was expected).

I awoke, quite perplexed by the events in the dream. For what reason would he make anethole ketoxime? Never the less, I carried on through the rest of the day feeling quite refreshed by my nap.

psychokitty

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Re: Peracetic in DCM - dreams of success
« Reply #2 on: December 30, 2001, 12:43:00 AM »
For the record, acid hydrolysis of the epoxide to form the glycol which is then dehydrated to the ketone is NOT a rearrangement but a hydrolysis/dehydration reaction.  Rearrangement of the epoxide either through the use of heat or lewis acids does not occur via a glycol intermediate.  But I could be wrong.

Rhodium

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Re: Peracetic in DCM - dreams of success
« Reply #3 on: December 30, 2001, 01:05:00 AM »
According to the articles I have read, epoxide rearrangements using LiBr/LiI involve the lithium salt of the halohydrin, followed by elimination of the halide.

If lithium perchlorate is used, it is said that it involves the lithium alcoholate and a carbonium ion.

Chromic

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Re: Peracetic in DCM - dreams of success
« Reply #4 on: December 30, 2001, 01:31:00 AM »
Yes, and I also realize the net reaction includes epoxidation followed by acid-catalysed hydrolysis followed with some of the glycol going to form monoacetyl and diacetyls esters by acid-catalysed Fischer esterification, followed by acid-catalysed hydrolysis of some of the oxidation products and finally a Pinacol rearrangement (which probably includes the acid-catalysed dehydration of the glycol as an intermediate, but honestly I'd have to review the Pinacol reaction mechanism) to get the desired ketone (heheh, not to mention the side reactions and unstable intermediates!!!)... but why complicate the language... everyone here understands me, n'est pas? The damn thing worked!

I was very happy to be able to dream about a peracetic acid epoxidation going as it should! That old man had nothing but failures until this reaction, it really brought a smile to my face to see him so happy...  :)

Chromic

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Re: Peracetic in DCM - dreams of success
« Reply #5 on: December 31, 2001, 08:51:00 PM »
I just watched the old man slowly add 3.0g of NaOH dissolved in 9mL of water to 5.1g of MeAmCl dissolved in 5mL of water. Was he trying to liberate all of the MeAm before a Al/Hg? Interesting, I've never heard of any one doing that before. He put the solution in the fridge, and went off to work on other tasks.

It looked as if he added 35ml of MeOH, a tiny bit of HgCl2, and let that stir. Then added 2.3g of Al foil, until the solution turned cloudy and the pieces started to float. He then added that solution of freebase MeAm he prepared to the solution, and added 4.5g of PMP2P that I think he prepared in the first dream I had of him. It looked as if NaCl precipitated, and although he was a bit anxious of that interfering, he let the reaction run 5hrs with external heating to keep it at a light reflux, and added 80ml of toluene, washed it once with water, filtered the toluene to remove bits of Al sludge, washed two more times with water, then extracted with distilled water by slowly adding dilute HCl and checking pH as he went (until it was acidic to methyl orange). Before recrystallization, it appears that he got 3.6g of beautiful purple (PURPLE?) (PMMA.HCl, that's a 61% molar yield, the HIGHEST yield this bee has seen so far. The yields from this could have been easily improved by increasing the number of extractions, etc.

Btw, the molar yield of the oxime formation was actually closer to 5.8g after even more drying time.

Chromic

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Re: Peracetic in DCM - dreams of success
« Reply #6 on: December 31, 2001, 10:47:00 PM »
Another day dream, he recovered 2.8g after recrystallization (all of it went into solution) from 40ml of IPA. The purple color disappeared after recrystallization.

I think he accidentally contaminated the water solution with the slightest bit of methyl orange (by not washing the stir rod he was using to take out samples to daub onto tissue paper wet with methyl orange), and on heating it must have went purple.

psychokitty

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Re: Peracetic in DCM - dreams of success
« Reply #7 on: January 02, 2002, 03:53:00 AM »
Here's a relevant (old) post by dpHarma:


   dpHarma     [Image] posted 03-03-99 02:49 PM
   Member
               [Click Here to See the Profile for dpHarma]
               ----------------------------------------------------------
               The following is a dream transcribed during a seance
               facilitated by Elton John's road manager.

               A meagre 4.5 gms. performic ketone purified w/ bisulfite,
               was combined w/ 6 gms. MeNH2.hcl in 30ml. MeOH. (the
               MeNH2.hcl was NOT purified of all the ammonium chloride)

               this was stirred by hand until uniform suspension then
               added to prepared amalgam consisting of 6gms. 'pie
               plates' cut into 1cm. squares, 250 mg. HgCl2,
               magnetically stirred and heated for 15 min. in 150ml
               MeOH.

               The ketome/amine was followed by 3.5 gm. NaOH in 5ml. H2O
               and 10 ml. MeOH.

               An reflux condensor was attached to the flask, and
               magnetic stirring and low heat applied for about 18 hrs.
               at which time no Al remnants were visible.

               The soution was quenched with an equal volume of H2O, and
               poured through a plastic kitchen strainer, into a 500ml.
               sep funnel.
               (a small 'gob' of thick putty like Al amalgam was
               recovered in the strainer, and washed and stored under
               peth til next time.)

               The grey liquid was extracted 4 times w/ toluene, the
               aqueous layer set aside, & the toluene extracts washed w/
               H2O, and several sat. NaCl/H2O washes. The washes were
               set aside, and the cleaned tolune was extracted w/ 3 x
               20ml. conc. Hcl in 30 ml H2O.
               The 'spent' tolune was set aside, and the acid sol'n
               washed w/ 3 x 25 ml. DCM.
               the DCM washes were set aside, and the acid sol'n
               basified w/ 25% NaOH until cloudy white ppt. remains. pH
               confirmed w/ bromothymol blue.
               Sol'n. extracted w/ 3 x 25 ml. DCM. The aqueous sol'n.
               was set aside, the DCM extracts washed w/ 1 x 20 ml. H2O,
               2 x sat. NaCl sol'n. dried w/ MgSO4, stripped of DCM by
               boiling off, til nearly gone then adding 25 ml. Toluene.
               about 6 drops of H2O were added, then 1 drop of
               bromoythymol blue as indicator. Conc. hcl was then
               dripped in by eyedropper, with swirling. the small
               aqueous layer changes from 'darkish' to light yellow w/
               each additon and back to dark w/ swirling. Also, as the
               'drop' of acid at the tip of the dropper approaches the
               surface of the tolune mix, 'smoke' (ammonium chloride)?
               appears above the surface. As the end point approaches,
               this effect disapears, and the aq/ layer stays bright
               yellow. stir and swirl vigorously, to ensure all base has
               reacted, then place on heat. boil off all the tolune,
               which should distill most of the water. when the temp of
               the beaker rises, (above 110^C) a slight smoke should
               appear as the toluene vapour ends. remove quickly from
               heat, cool and add an equal volume of cold dry acetone,
               followed by a similar amt. of etO2 (also dry and cold).
               place beaker in dish filled w/ snow (got surplus), and
               stir vigorously. In moments, the layers should cease, and
               a pinkish 'mush' occurs. stirr abit longer, add a bit
               more acetone, stir, decant, repeat. transfer to buchner,
               add acetone, stir, and filter. reapeat til snow white.

               yeild of snow white product from 4.5gm ketone, 3 gms.
               (plus ~200 mg dirty white stuff).

               All of the 'process' solutions were retained, and
               appropriate extractions done, and minimal product
               recovered.

               The extraction of the entire Al sludge provided an
               exceptionally easy and tidy cleanup. Instead of spending
               several hours filtering and re-filtering, the stuff went
               from rxn vessel to xtals under 1.5hrs.

               performing the acid/base routine has two advantages.
               1. it removes any non-basic materials, such as unreacted
               ketone, iso alkene, aldehydes etc., when the acid
               extraction is washed w/ polar solvent.

               2. it removes the base from the relatively large volume
               of tolune used to extract it from the Al/sludge, and
               allows the amt. of solvent boiled off to be kept to a
               minimum.

               3. It provides another level of purification from the
               insidious mercury toxin.

               Thanks to Ritter for his amalgam extraction, and to
               sunlight for his toluene xtallization tip. This is a
               great combination which takes a lot of the drudge out of
               Al/Hg reduction, & workup.

               Now all Elton's roadie's dead uncle has to do is improve
               ketone prep.

               This ? is off topic, but anyways,...

               during the hydrolysis stage of performic, no mention is
               made of stirring. early exps. never stirred during acid
               hydrolysis reflux. the oil kinda swirled and bobbed and
               the dil acid boiled. last time, mag stirring was applied
               about 1/2 way and the mix changed character. w/o
               stirring, it was basically clear. after stirring (and
               heating) for another 1.5 hrs., the acid stayed 'red'!
               even after sitting in the cold for many hours. some
               miscibility occured w/ stirring that didn't without!

               trying to find the point(s) in this process where the
               yeild goes to shit. isoalkene was twice distilled @ atm,
               pressure and 248-252^C.
               Formic acid was concentrated from 65% to >80% by repeated
               treatment w/ anhydrous copper sulfate followed by
               distillation.
               SG went from 1.170 to 1.195. H2O2 was 35%
               40ml acetone used as solvent w/ 32.4gms. isoalkene.

               anybody got the SG of 80, 88 and 90% formic (at 20^C of
               course)???

               dpHarma

psychokitty

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #8 on: January 02, 2002, 04:03:00 AM »
"Extracted with distilled water"?  I don't get it.  How did you isolate your final product?  Evaporation of the water?  How was this accomplished?  And what were the conditions?  (Time, temp, etc.,etc.)

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #9 on: January 02, 2002, 05:50:00 AM »
It makes sense to me, but I'll clarify. Distilled water was added to the organic layer (mdma freebase and toluene), mag stirring started, dilute HCl was added until a sample would turn methyl orange to red. The water separated, and openly boiled off. Then, the product recrystallized.

psychokitty

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #10 on: January 03, 2002, 01:41:00 AM »
Did you separate samples to test or did you simply add the methyl orange directly to the stirred biphasic mixture?

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #11 on: January 03, 2002, 02:18:00 AM »
I watched him add drops of a solution of 1% methyl orange in methanol to filter paper.

He drew out a sample with a stir rod (from the emulsion containing toleune and distilled water) and daubed it to one of the dots of methyl orange on the filter paper. He then titrated some dilute hydrochloric acid, then drew another sample, etc. Obviously he wasn't careful enough to rinse the stir rod off thoroughly as it appears some methyl orange from the filter paper got transferred back into the beaker containing the emulsion. Anyways, after recrystallization all was well.

Good thing it was just a dream, I wouldn't have the faintest idea of what to do with even that little amount of PMMA (other than throw it in the garbage).

I hope he checks into using a similar technique with asarone to attempt tmma-2. If Goiterjoe's peracetic oxidation on asarone did work (which is unknown), then it gives me some hope of his dreams at making tma-2 (sounds good) and tmma-2 (probably a compound just as exciting as pmma... but who knows... gotta try everything once or twice..).

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #12 on: January 15, 2002, 05:09:00 AM »
Just took a quick nap, and noticed the same man attempting the reaction with asarone. He must be crazy to do something like this, I'm almost sure he will fail... but, hey, at least it will answer the question once and for all.

Vibrating_Lights

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #13 on: January 15, 2002, 10:28:00 AM »
any one know the concentration of H2O2 that comes in the wood bleaching kits that also contain the bottle of NaOH solution.
VL_

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #14 on: January 15, 2002, 05:43:00 PM »
Upon waking from a dream about the oxidation, I noticed the man removed lots of reddish-brown crap through 3x 10% NaOH washes. Likely phenolic compounds... let's hope some of the trimethoxys are ok... the suspected product (the monoacetate/diol) is a very viscous oil, looks nothing like his asarone...

VL, wood bleach is usually 30-35%, check the MSDS or call the company.

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #15 on: January 17, 2002, 07:53:00 PM »
It appears that after H2SO4 hydrolysis, the old man had a suspected 64mmol crude yield, after simple (and not-careful) vacuum distillation there remained 48mmol of suspected ketone. A very viscous canary yellow oil.

After carefully observing the actions of that man, I believe that it can be said that:

1. the peracetic in dcm does not destroy asarone to tar (as the performic does)
2. the methoxys on asarone are not severely affected by the peracetic acid (they are affected than anethole, but they are not all destroyed).
3. h2so4 hydrolysis does not rip apart the remains from a peracetic to tar or rip off all the methoxys.

The biggest question remaining is, is the suspected ketone truly a ketone, and can it be aminated? We'll have to wait.

noj

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #16 on: January 17, 2002, 07:56:00 PM »
That sounds like what someone has sitting in the freezer. Much more viscous that what someone recalls MDP2P being. Really interested in what you can dream of it.

crucify the ego before it's far too late
and you will come to find that we are all one mind

goiterjoe

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #17 on: January 18, 2002, 12:47:00 AM »
I think asarone ketone is supposed to be a solid, but you would only get that with careful fractional distillation.

If Pacman had influenced us, we'd run around dark rooms eating pills and listen to repetitive music

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #18 on: January 18, 2002, 05:04:00 AM »
Qualified Success!

TMMA-2.HCl should also be a solid, but I watched in the dream the man extract what appeared to be about 6g of a highly viscous oil (with an acid extraction) that was most definitely TMMA-2.HCl (very bitter taste)... I hate it when that happens. Tried to recrystallize, nothing fell out of solution. argh... I hate watching product oil out.

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #19 on: January 19, 2002, 02:46:00 AM »
I watched the man try and form the TMMA-2.sulfate in acetone... the stupid TMMA-2 stayed in the acetone. Oh well, I'll evap it, and add to water and give 40mg to some guinea pigs.

So, is no one interested by this? Peracetic acid, with H2SO4 hydrlolysis works on asarone!? I'm surprised.