Antoncho (Official Hive Translator)
03-30-02 12:36
No 289973
      2-hydroxy-5-MeO-BA: the continuation of the saga.  Bookmark   

..... Once i saw a Devil in a flame of fire, who arose beefore an Angel that sat on a cloud, and the Devil utter'd these words:




Some dirty, dark-brown p-MeO-phenol was obtained by xtracting w/benzene a standard HQ/BQ/H2SO4/MeOH methylation, described in Post 269667 (Antoncho: "Re: P-MeO-phenol from hydroquinone: part II", Novel Discourse), evaporating the C6H6 and drying the melted product on a waterbath under fumehood in an enameled saucer. The product then stood in open air for some days.

12,5 g of this disgustingly looking shit was dissolved in hot solution of 32g NaOH/36ml H2O. 4ml MeOH was added. All was placed into 100ml FBF (SWIM doesn't have a 100 ml RBFsmile).

The flask immediately upon addition of phenol was flushed w/butane, and so was the efficient air condenser which was placed upon it. The latter was loosely corked to prevent air from getting in.

So... The flask was immersed into a water bath held at 70 C - that was achieved by taking the largest pot SWIM could find in the house and placing it, full of water, on a electric hotplate switched to "II" mode (of the three modes available smilesmilesmile). Surprizingly, it held the rxn at precisely 70 C all the timelaugh

Every 15 mins 1 ml of fract. distilled CHCl3 (well, i guess, distillation could bee omitted, but SWIM's chloroform boiled at 57 C, so he decided any other modus operandi would bee unwise) was injected in w/a syringe, and the rxn immediately energetically swirled by hand to allow for absorption of CHCl3 into the mixture (this way it doesn't boil much - but boiling progressively increases during the course of the rxn).

After 4 hrs, add'n was stopped and the temp was kept at 70 C for 1 more hour.

The rxn was then cooled, acidified w/~80ml 25% H2SO4 - some black oil floats on top - xtracted w/25x25x15x10 mls of CHCl3, xtracts stirred w/a little NaHCO3 (solid - can you xplain me why they use a NaHCO3 solution all the time??? Please?? It's messy, and tends to form emulsions, whereas solid NaHCO3 is very simple to decant from), decanted, NaHCO3 washed w/a little bit of CHCl3, all combined in a 500 ml RBF, CHCl3 evap'd. Some black oil remains.

The flask is filled w/water and steam-distilled for like fucken eternity (>7hrs), collecting 600 ml distillate - after the 1st 300 mls are distilled, ~60 gr NaCl + 300 ml H2O are added to the flask. A visible qtty of yellow oil is seen floating on top of the distillate. SWIMis rather certain there still remains quite a bit of the product in the water, but.....

The distillate is saturated w/170 g NaCl, xtracted w/50x50x25x20 mls CHCl3 (all the way SWIM used the same CHCl3 he distilled off bee4 (including previous runs) + adding some from the bottle as necessary), dried w/NaSO4, decanted, drying agent also washed w/a little CHCl3, and the solv't evaporated on a boiling waterbath in a 100 ml flask - after bubbling ceases, it's held for some time more, open - to remove any residual CHCl3. Some of it still remains in the product, as it seems, but not much at all (a sample tested).

Yield - 6,2 mls of a dark-yellow transparent liquid w/a funny, undescribable aromaceous odour, completely dissimilar to that of vanillin. Irritant to skin. Crystallizes in the freezer (ChemFinder says mp 4 C - is it true or a typo?)

The following notes should bee also in order:

1) Antoncho, on SWIM's beehalf, would like to thank very much Karl, who was the pioneer of this procedure. Thank you, Karl!

2) An pre-run w/a smaller qtty gave an identical result - ~1ml of product from 2g starting ... er... material.

3) The 'improved' procedure from the patent at Rhodium's - with semi-solid NaOH in chloroform - DOESN'T WORK (at least, with this dirty compound). Only 0,7 mls was isolated from 3 g starting material. The rest is tar... which would make a really cool window-pane hermetizersmile




The Angel hearing this beecame almost blue; but mastering himself he grew yellow, & at last white, pink and smiling and then replied:

"Thou Idolater! Is not God One?"


...... damn it, i think God is fucken Zero. But he does smile at times - like this: cool


Antoncho
 
 
 
 
    Rhodium
(Chief Bee)
03-30-02 14:36
No 290007
      Why NaHCO3 solution?  Bookmark   

An aqueous solution has an infinitely larger surface area than the solid NaHCO3 powder, which makes for a better contact between the phases. If this is necessary, I don't know, but that is the rationale behind it.
 
 
 
 
    Antoncho
(Official Hive Translator)
03-30-02 22:43
No 290218
      Ha-ha!  Bookmark   

Thank you for clarification on the NaHCO3 issue!

Rhodium, you probably shiver with disgust every time you read one of my write-ups!laughlaugh

I understand you very well - i am very anal when it comes to chemistry, toosmile - however unimaginable that would seemwink; it is just the fact that i had absolutely no means to purify this crap that i had to go with it.

Sure, vac. distillation, column chromatography, blah-blah...  I'd dearly like to do all that - if i only couldfrown Otherwise i wouldn't have spent two weeks trying to rextallize the crap from everything i had in the house - with which i still had no luckblush

Antoncho
 
 
 
 
    foxy2
(Distinctive Doe)
03-30-02 23:03
No 290233
      write up  Bookmark   

antoncho
ya need to break those write-ups into sections with titles
It would bee more readable, as I can't bring myself to pick thru the one up there, and this is the third time i've opened this thread
smile


Those who give up essential liberties for temporary safety deserve neither liberty nor safety
 
 
 
 
    Rhodium
(Chief Bee)
03-31-02 07:37
No 290370
      Good work!  Bookmark   

Antoncho: Actually I like your writeups because you have some of the most important qualities there is when it comes to chemistry - dedication, curiousity and a desire to solve the mysteries of chemical reactions. It doesn't matter if you have a $1000 lab or a $100000 lab, it is how you work that is what makes it interesting. It is only a sad thing that people like you doesn't have inexhaustible financial resources, as you have nothing else that would halt your endeavours.
 
 
 
 
    Antoncho
(Official Hive Translator)
03-31-02 11:06
No 290423
      Um... Em...  Bookmark   

Foxy: hmmm.... Actually, i don't know how to divide this particular write-up into sections. Anyway - it wasn't meant for a casual reader, my goal was to create as much detailed description as possible, so those who repeat it won't have to fill in any gaps.

What i, basically, did want you to appreciate is - it turns out that one can get a decent (that is, suitable for a small-scale production) yield of rather clean 5-MeO-salicyladehyde from hydroquinone without purification of intermediate p-MeO-phenol, which is very difficult w/out a vac. distilling facility.

Rhodium - thank you very much for your compliments, i really needed thatsmile

Actually, i think of myself as of a purposefully ghetto chemist. The reasoning behind this is - if one makes psychedelics for his own consuption, without intent to have monetary profit from it (as SWIM does), he needs only small scale techiques and equipment, but can spare no extra money. OTOH, you can't do it on a larger scale w/out a proper lab, hence 'financial resources', but then you usually have those resourcessmile

Once again, thank you everyone for the positive input, i really appreciate this.

Antoncho
 
 
 
 
    foxy2
(Distinctive Doe)
04-01-02 00:06
No 290762
      Ok nevermind  Bookmark   

I guess its fine.
Just when i scan it initially for some reason it doesn't draw me in, but it is a good write-up.  Lots of details.
Sorry about my earlier post, I think it was more my attitude than your write-up. shocked
Foxy

Those who give up essential liberties for temporary safety deserve neither liberty nor safety
 
 
 
 
    Antoncho
(Official Hive Translator)
07-09-02 21:32
No 330714
      A patented improvement
(Rated as: excellent)
 Bookmark   

Look at this wonderful find!cool

Patent GB1377317, 2-hydroxy-5-methoxy-benzaldehyde by Reimer-Tiemann formylation of p-MeO-phenol.

To summarize shortly the point of the patent:

a) Improved yield (well, they say 48 to 53% of theory - not all that great as compared to Karl's 76% results, but still good, - take a note that Karl's product contained an unspecified amt of unreacted phenol, which also (slowly) steam-distills and was always detected in SWIM's and SWIVitsh's experiments in quite substantial qtties)

b) The main one - an isolation of the pure aldehyde without steam-distillation and bisulfite treatment!

BTW, they say that the originally published procedure gives a much worse result.

So, here goes:





200g of p-MeO-phenol were dissolved in a soln of 190g of NaOH in 550mls water and the resulting soln was heated to 50 C on a waterbath. to this soln maintained at 50-60 C there were added dropwise 420g of chloroform and a solution of 560g of NaOH in 500mls water from two separate dropping funnels and the rxn was heated for 1 hr at the same temp and atm pressure. after cooling the precipitated salt of 2-hydroxy-5-methoxybenzaldehyde was filtered and washed with 100mls EtOH.The sodium salt was dissolved in 800mls water and slightly acidified (1200 cm3 of 3N H2SO4 at RT) and xtracted w/200mls toluene. The solvent was dried w/CaCl2 and evap'ed and the residue distilled at reduced pressure to give 132g of the itle product, bp 110 C / 5 mmHg.





Cool, i really like that. Too bad SWIM has no time and money for dreaming during this summerfrownfrownfrown.

A side question of an utter importance that i haven't ben able to get/find an answer to:

IS IT POSSIBLE TO METHYLATE THE HYDROXYL ORTHO- TO ALDEHYDE WITH METHYL IODIDE
WITHOUT A PTC (the way Shulgin does).

It appears that that hydroxyl is too deactivated - at least in all examples i've seen DMS is used; also numerous failures/bad yields were reported in attempts to carry out that methylation the 'straight way'.
Please, bees, help if you cansmile




Yours,



Antoncho
 
 
 
 
    Mountain_Girl
(Hive Bee)
07-09-02 23:04
No 330752
      Good stuff  Bookmark   

Great find Antoncho!

In the coming weeks it is very likely that swim will dream this one (currently messing about with purification of p-meo-phenol).

Unfortunately I cannot help with your question of MeI methylation. In my dream I have some (not a lot) of DMS which will be used to make 2,5-DMBA. If this can get me to 2-CX at least once, I would then go back and investigate a more OTC method of methylation (the DMS won't last forever).
Hope other bees can give some input on this issue.
 
 
 
 
    Antibody2
(Bee without a Title)
07-10-02 07:21
No 330840
      otc dms  Bookmark   

dimethylsufite?

reducing DMSO in Al/Hg should work, i think
 
 
 
 
    Osmium
(Stoni's sexual toy)
07-10-02 08:09
No 330852
      DMS = dimethylsulfAte  Bookmark   

DMS = dimethylsulfAte

I'm not fat just horizontally disproportionate.
 
 
 
 
    Antoncho
(Official Hive Translator)
07-10-02 08:39
No 330859
      Dimethylsulfite.  Bookmark   

Yes, dimethylsulfite is a methylating agent, but not a really good one. I've one patent on HD where it's used to methylate vanillin and such - but the yields are never goodblush

Beesides, it can't bee made from DMSO , much less so by reduction of it - in DMSO there's only one oxygen, and DMSite has three; more importantly, in DMSO methyls are attached to sulfur directly, while in DMSite - via oxygen bridges.

Currently an investigation is being carried out at HyperLab to make DMSulfate by CuCl2/MeOH/SO2 route to confirm Half-A-Pint's findings, but there are still no conclusive results - at least purification w/out vac distillat'n seems difficult....




Antoncho
 
 
 
 
    Antoncho
(Official Hive Translator)
07-10-02 09:31
No 330874
      A very (IMHO) curious idea
(Rated as: excellent)
 Bookmark   

I've had a revelationsmile.

First, take a look at this procedure, from Patent US3962345:




EXAMPLE 1
n-Amyl-(4-methyl-3-propylthio) phenyl ether

12g (0.066 mole) of 4-methyl-3-propylthiophenol (bp 136.degree.-138.degree.C/3mmHg, n.sub.D.sup.25 1.5762), 3.6g (0.066 mole) of potassium hydroxide and 30 ml of dimethylformamide were mixed and the mixture was heated to a temperature above 90.degree.C to obtain a complete solution thereof. Then, the resultant solution was cooled down to room temperature and, while further cooling the solution in an ice bath, 9.5g (0.063 mole) of n-amyl bromide was added thereto. After the addition of amyl bromide, the ice bath was removed and then the solution was stirred for 5 hours at room temperature. After completion of reaction, the reaction mixture was poured into 200 ml of water. A brown oily layer formed on an aqueous layer was extracted with benzene. The extract was washed successively with 5 % (by weight) hydrochloric acid solution, 5 % (by weight) sodium hydroxide solution and water. After the extract thus washed was dried by sodium sulfate, benzene was removed by distillation to obtain 16.6 g (99.6 % of theoretical) of n-amyl-(4-methyl-3-propylthio)phenyl ether. After purification by distillation, colorless and transparent oil having a boiling point of 136.degree.C-139.degree.C was obtained.


EXAMPLE 5

Methyl-(4-methyl-3-propylthio) phenyl ether

18.2 g (0.1 mole) of 4-methyl-3-propylthiophenol, 5.7 g (0.1 mole) of potassium hydroxide and 50 ml of dimethylacetamide and 17.0 g (0.12 mole) of methyl iodide were mixed and the resultant mixture was reacted at the room temperature for 5 hours. After completion of reaction, the reaction mixture was poured into 200 ml of water. A brown oily layer formed on an aqueous layer was extracted with benzene. Extract was washed with 5 % solution of sodium hydroxide and water, and dried with sodium sulfate. Then benzene was removed by distillation and 17.1 g (87.2 % of theoretical) methyl-(4-methyl-3-propylthio)phenyl ether, which was colorless and transparent oil having a boiling point of 114.degree.-115.2.degree.C/2mmHg, was obtained.





There are other examples where they use DMF instead of diMe-acetamide, while the alkylating agents are propyl bromide and such. For what reason they use acetamide in case of MeI, what do you think? I'm personally puzzled. I'd think that they were afraid of MeI somehow forming a qurternary amide (is this possible at all?) with DMF, but AcO-NMe2 should bee even more susceptible to this (more electronegative nitrogen atom), shouldn't it? Well, anyhow.

Certainly, the phenol being methylated in this case is much more easily alkylated than our target aldehydesmile. But. Note that the amt of alkali used is equimolar - hence there's no free KOH to hydrolyse our MeI.

Now, in all patented methyl halide methylations i've personally seen they are always carried at a controlled pH, the reason for that being specified as to prevent hydrolytic destruction of the Me halide. That leads me to suggest that a procedure similar to the stated above would bee especially good - it's not basic, and the conditions may bee easily made harder - like the rxn could bee carried for 24 hrs instead of 5, and the temperature can bee increased all the way to, say, 100 C - like in methylenations with DCM, the large amt of DMF brings the boiling point way above that of DCM. Which is a big advantage comparing to doing it in acetone.

Did i begin to sound like FMAN yet?smile

An important detail - do you think the small amt of water formed by interaction of KOH with the phenol should bee somehow removed? Like, simply by some drying agent like CaSO4?

Dear Hest, i know you've had some experience doing methylations in DMF - did you ever used MeI instead of DMF? What were the results?

Personally i have a feeling that methyl iodide in DMF at 100 C for 12-24 hours will methylate anythingsmile - at least, dichloromethane methylenates protocatechualdehyde in even shorter time. Please, let me hear what you think, bees. Any input is highly appreciatedwink



Antoncho
 
 
 
 
    Mountain_Girl
(Hive Bee)
07-24-02 00:19
No 336437
      R-T result  Bookmark   

FUCK.


Some dirty, dark-brown p-MeO-phenol was obtained by xtracting w/benzene a standard HQ/BQ/H2SO4/MeOH methylation, described in Post No 269667, evaporating the C6H6




So I took some of that dirty dark-brown p-MeO-phenol (using DCM instead of C6H6) & tried the R-T:

I used more NaOH than the procedure at Rhod's (~ 3.5 vs 2.6 g NaOH/g phenol).
Had trouble maintaining temp, so a major part of the time it was probably as high as 80C.
Afterwards there was a large amount of very dark-brown ppte which was filtered off.
I was pleased cos I thought that it must be the phenolate.
Wrong.
It dissolves readily in MeOH.
When dissolved in water and acidified there is very little oil floating. Far too little.
Fuck.
Is it possible to over-acidify, can it decompose the product ?
Too much NaOH used? (don't think so)
Was the temp too high maybe ? (probably)
Should I have used an inert atmosphere ?

Excuse the tone of the post - there's a lot of work in these words and it's frustrating to finally fail.

 
 
 
 
    GC_MS
(Newbee)
07-24-02 09:55
No 336585
      Tar  Bookmark   

Tried it as well. SWiM had alot of tar, made the product useless. He is rather sure he should have controled the temperature much better than he did...

(1) synthesis of p-MeO-phenol; SWiM knows there is a certain amount of p-anisic acid present, but not more than 5% of the whole. He didn't make an effort to remove it.
(2) tried the British patent, which says to keep temperature between 50-60C. As usual, SWiM forgot and when he saw the mixture boiling, he thought... ooo-ooooooo crazy. Temperature was almost 80C at that time. He noted some shiny yellow/white components in the heavily stirred mixture. When the mixture was cooled to room temperature, there was a problem... When emptying the reaction flask, it became clear there was alot of tar. The tar wasn't present during the reaction. Maybe the CHCl3 was evaporated (cooling took 3 hours) and tar settled down. When adding CHCl3, the tar dissolved. hmmm, "dissolved"... SWiM tried to filter it, but didn't work. The tar ruins all. Just threw everything away then.

Conclusions:
- SWiM thinks he should have monitored his temperature much better than he did. His breath had an unusual EtOH odour that morning though.
- timing of adding the products: SWiM thinks he added the NaOH and the CHCl3 too quickly, hereby adding to the heat development of the reaction.

Note: SWiM used distilled CHCl3. Undistilled stuff contains too many phtalates.

Doped(TM) since 19.... euhm... a long time smile
 
 
 
 
    Antoncho
(Official Hive Translator)
07-24-02 10:43
No 336597
      LOL!  Bookmark   

Guys and girls, don't bee afraid. SWIM definitely performed this synth. If he could, you can as well. I mean, i'm not making up anything. Keep trying.

One thing i'm positive about is FOLLOW the directions. ESPECIALLY the temp and alkali conc'n - SWIM did see masssive tar formations when the directions were not followed. The pH is of a major concern.

SWIM tried the british patent he dug up and found it of no use. At least on the unpurified p-MeO-phenol. Do Karl's proc. It has been found to bee the best thus far.

Another thought - that deep yellow coloration of all the products SWIM's seen w/that Reimer-Tiemann (passes thru the steam-dist'n as well!!). Probably, SWIM thinks, it's the quinone. Will try to get rid of it the next time w/ a prior bisulfite wash.


The only problem SWIM now has is trying to alkylate that aldehyde with MeIfrownfrownfrown Three diff. solv'ts were used, with not much success.

If you have any q's - always at your service. I've had some xperience w/this rxn by this time, more that i care to admitlaughlaughlaugh




Antoncho

P.S. 80 C at some prolonged (like 30 mins) time even at the proper concentration of the alkali is a definite murdering of the rxnsmile
 
 
 
 
    Greensnake
(Hive Bee)
07-24-02 11:54
No 336615
      Methylation  Bookmark   

>The only problem SWIM now has is trying to alkylate that aldehyde with MeI Three diff. solv'ts were used, with not much success.

some excess MeI/excess of finely divided K2CO3 in acetone and prolonged (~12h) reflux with stirring generally methylates phenols well. Not too convenient to perform without hotplate-stirrer (without stirring K2CO3 sinks to bottom and mixture does not boil properly)
 
 
 
 
    GC_MS
(Newbee)
07-24-02 12:52
No 336645
      bwa...  Bookmark   

SWiM knows the reaction is achievable Antoncho, at least in theory. He only tried the British patent under EtOH-induced mental problems crazy. It's typically SWiM that he fucks up his first trial cum laude and that all following are more promissing. But really, that UK patent tar looked awfull tongue. Time for another procedure laugh.

PS: SWiM thinks Villsmayer is easier...

Doped(TM) since 19.... euhm... a long time smile
 
 
 
 
    Mountain_Girl
(Hive Bee)
07-24-02 22:49
No 336836
      Thanks  Bookmark   

Thanks for the input guys.
I generally also mess up v.1 of a reaction.
Your response was encouraging Antoncho - it's not so bad failing when you've got a good idea why.
So back to begin (order more hydroquinone, distill more DCM from paint stripper, make more CHCl3... - my cold & deadly determination worries me sometimes..)crazy
 
 
 
 
    Antoncho
(Official Hive Translator)
08-24-02 12:44
No 348592
      Methyl iodide methylation of 2-OH-5-MeO-BA.
(Rated as: excellent)
 Bookmark   

Due to a shortage of moneyblush, Antoncho has been lately unable to buy antipsychotic medication for his, young and temperamental, but unfortunately schizophrenic aunt. As a result, she re-developed some pretty unusual hallucinations, describing adventures of an imaginary character called  SWiHKAL. A truly notable person he is, albeit a hallucinationsmile. Here is one of her schizoid fantasies that touched Antoncho's heart so deeply that he couldn't resist the temptation of sharing it to his brethren beessmile.




4,7 g of crude dark-brown 2-hydroxy-5-MeO-benzaldehyde obtained by Reimer-Tiemann formylation (steam-distilled) was placed into a 150ml three-necked RBF. There was added 25mls dioxane (undried, but kept over FeSO4 to remove peroxides), 5g freshly fused potassium carbonate, 1ml MeOH (Note 1) and, at last, 2mls (4,6g = 25% molar xcess) methyl iodide. The central neck of the flask was fitted w/a condenser, one of the side-necks - w/a thermometer, and the 3rd one was plugged to bee later used for various tests and additions. The apparatus was flushed w/butane and all was brought to a very gentle reflux on a waterbath.

The temp, measured inside the boiling liquid, at first was ~77 C, increased to 85 C in ~30mins, and went up to 92 C over the next 3 hours. Boiling was cont'd overnight (Note 2)

An aliquot of the liquid was taken w/a syringe, acidified, evaporated under draught to remove carcinogenic dioxane and smelled. The specific smell of unreacted starting material was apparent, mixed w/a somewhat similar, but sweet, aroma of p-diMeO-benzene (Note 3).

So 0,7mls of MeI were added and reflux recommenced. After 4 hrs (internal  temp 92 C) another test was taken which again indicated the presence of the starting material. Another 0,7 mls MeI were added and refluxed for several more hours; the third test revealed the completion of the rxn.

The rxn was flooded w/60 mls of 20% KOH, saturated w/NaCl and xtracted w/30+15 mls of IPA. Alcohol was separated, some 10g of Na2SO4 were added in a faint attempt of dryingsmile, followed by 90mls of saturated aq. metabisulfite. The mixtr was subjected to vigorous mech stirring for 7mins and the precipitate (which ended up in the alcohol layer) was filtered, washed twice with a lil IPA to almost completely remove yellow coloration (Note 4), pressed between filter paper and somewhat dried under draught. Still containing some IPA, it weighed 8,7 g.

Thus obtained adduct was thrown into 50mls of pre-chilled in the freezer 20% KOH, stirred and left for 30 mins in warm water(Note 5). Precipitated aldehyde was filtered, washed with water 3 times, pressed between filters as dry as possible, chopped on a plate and left to air-dry. Still containing a little water, it looked like not-quite-white, but still pretty, fine vanillin-like powder w/out any noticeable smell and weighed 3,6 g (Note 6). After drying it was 2,7 g - smile.


Notes.

1. Dioxane was chosen for the following reasons: a) a much higher bp as compared to acetone; b) unreactivity towards the carbonyl group, which is a
possible disadvantage of using acetone and c) ability to dissolve both MeI and, to some xtent, alkali.

The rationale beehind addind MeOH was the following: K2CO3 reacts w/it to form KHCO3 and KOCH3. The latter, being more soluble than K2CO3, was supposed to act as sort of a PTCsmile. Unfortunately, it later turned out that SWiHKAL's MeOH was VERY wet (not to mention water in dioxanecrazy), so the effectiveness of this additive remains to bee researched.

In any case, the two-fold amt of MeI that was required for the rxn, warrants further investigation. Probably, unhydrous conditions would bee better. Maybee, methanol shouldn't bee added at all - to minimize hydro/methanolysis of MeI, which is the major side rxn.

2. Probably, there is no need to reflux the mixtr more than 30-60 mins after the internal temp reached maximum. SWiHKAL just wanted to bee suresmile.

3. p-MeO-phenol is a major impurity contained in the hydroxyaldehyde isolated by steam-distillation from a RT formylation. It's hard to estimate, but there is quite a bit of it in there, probably not less than 20%.

4. This intensely colored yellow impurity is, probably, benzoquinone which survives all the transformations since its usage in methylation of hydroquinone. The next time SWiHKAL does that, he'll 1st try to remove it with bisulfite from the crude p-MeO-phenol.

5. SWiHKAL wanted to make sure all adduct decomposed. Since the appearance of the substance virtually doen't change, several tests were needed to confirm that. However, decomposition of the adduct seems to proceed fast even w/cold KOH.

6. The mp was measured and found to bee circa 45 C, whereas the lit value is 51 C. Could anyone suggest to what kind of (im)purity that corresponds?










Antoncho
 
 
 
 
    GC_MS
(Hive Bee)
08-24-02 13:16
No 348601
      helpful hint?  Bookmark   

Maybe this is helpful to get rid of your pMeO-phenol: from experience, SWiM found out that the latter easily solidifies when it comes in contact with air and is free from solvents as DCM and likes. Maybe Antoncho could remove all solvent and allow his benzaldehyde to stand for a bit (about 1 hour) and see if the pMeO-phenol solidifies. If it does, it might be usefull to reduce the amount of pMeO-phenol impurity in your sample in an easy manner. Remember: it is just a thought based on experiences SWiM had, never tested. He can also imagine that the benzaldehyde is easily oxidized by air...

Doped(TM) since 19.... euhm... a long time smile
 
 
 
 
    Antoncho
(Official Hive Translator)
08-25-02 02:01
No 348772
      An update.  Bookmark   

After drying, the product weighed only 2,7 g crazy.
However, it can bee fairly certainly said that the actual yield is much better - the chief reason to blame is the impurity of the starting material (it also contained some CHCl3, which's hard to remove completely on a waterbath).

Obviously, the main loss of yield happens at the formylation stage. SWiHKAL is fairly certain that the way to go is to use Karl's original proc., but for longer time, to react the starting phenol completely.

Monomethylation of HQ also needs to bee improved - it yields 60% at BEST, as of today. Bisulfite purification fof it would bee a good idea.

2 GC_MS: no, it doesn't crystallize out, SWiHKAL tried that. It could bee cleaned thru bisulfite (that's the way SWI-Vitsh did), but SWiHKAL decided not to bother w/this yet and "kill both hairs with a single shot" in the final bisulfite purification.

Vitsh reported his yield of bisulfite-purified 2-OH-5-MeO-BA to bee ~40% of the unpurified cmpd's weight - which gives you an idea of how pure it wassmilecrazyfrown - however, SWIVitsh didn't use inert gas protection during formylation so probably the loss of the product was partially due to its oxidation w/air.



Any ideas, commentaries? Questions? C'mon, friends, gimme some inputsmileblushwink




Antoncho
 
 
 
 
    Mountain_Girl
(Hive Bee)
08-26-02 07:39
No 349188
      Good work once again  Bookmark   

Antoncho
Um..sadly I've no intelligent comments or suggestions cos my psychotic aunt is still 2 steps behind yours and not so focussed at the moment.
(she itches to methylate and formylate
but instead rants and raves
the hydroquinone hasn't been delivered yet)
However I can congratulate on work done so far. Im really pleased your aunt is pursuing this righteous path, please tell her to keep it up.
 
 
 
 
    Antoncho
(Official Hive Translator)
08-27-02 09:33
No 349682
      Further adventures of SWiHKAL.  Bookmark   

The latest notes from my crazy aunt's diary:





Into a test tube there were placed:

a) 1g of 2,5-diMeO-BA

b) 0,5mls MeNO2 (distilled, but not quite dried  - half of it distilled over at ~90 C - MeNO2's azeotrope w/water, 76% MeNO2)

c) 3,5mls MeOH


And the solution was placed into an ice/salt bath at -7 C, where it shortly turned into a fine suspension.

In the same bath 0,9mls of 40% NaOH soln in a small syringe were pre-chilled.

Also one should prepare bee4hand the following things:

a) A 2-5cm3 syringe fitted w/a pipette long enough to extend to the testtube's bottom; chilled in a freezer.

b) Ice-water and a freezer-chilled 10cm3 syringe (chill syringes' parts separately!)

c) A soln of 7mls HCl in 13mls water, kept at RT.



When the temp of the mixtr in the bath falls to -5 C, alkali was gradually added in 3 portions, with vigorous hand-stirring w/thermometer - the 1st time the temp jumps up by ~10 C - make sure that temp falls back to -5C each time.

The mixtr beecame homogenous. It was left in another icebath - temp rising from 6 to 10 C - for an hour.

Then it was chilled back to -5 C and 10mls of ice water is added thru syringe - all turns cloudy-white. As fast as possible, it was dripped thru the pipetted syringe into the acid soln with vigorous stirring.

Contrary to the documented on Rh's site similar prep'n of MDP2NP, no 'spectacular color shift' was observed - yellow color appeared immediately, and by the end of the add'n the mixtr represents a slurry of bright-orange nitrostyrene xtals of very fine consistency. They are filtered, washed w/water 3 times and air-dried on a saucer to give 0,7g (56%) of product, which has indeed a SPECTACULAR color - each time SWiHKAL looked at it his heart smiled, so cheerful and bright it wassmile






Maybee, somebee will have SOMETHING to say about this?laugh

Any ideas on why the yield was so crappy? Well, still acceptable for a hallucinatory kitchen chemist, i guess.



Yours truly,


Antoncho
 
 
 
 
    yellium
(Hive Addict)
08-27-02 10:07
No 349695
      Congratulations! I hope that you can make it to ...  Bookmark   

Congratulations! I hope that you can make it to the end compound (probably 2cb, although the 2cc and 2ci are just as interesting), and post a bioassay here.
 
 
 
 
    Antoncho
(Official Hive Translator)
08-27-02 11:01
No 349706
      Oh, Yellium, thanks....  Bookmark   

I hope so toosmilesmile

Well, the experience shows that SWiHKAL is habitually unable to do smth the 1st time and not to fuck upsmile This was one of the very few occasions when it started working right away, so....smile

It was to compensate for this sudden luck, i guess, that the destiny presented another, shall i say, 'surprise' for him: while preparing to run that same rxn w/the remaining 1,7g of his aldehyde, he broke the test tube w/the thermometer while stirringblushcrazymadmadmad and the contents, naturally, flowed into the ice-bathsmilesmilefrown

...hehe - what would you say if that happened to you? - right, that's what the stupid hallucination said too, among many, many other words - fortunately, Russian language is extremely rich and flexible in its means of constructing really obscene and dirty cusswordslaugh


Anyway... less than a gram was recovered from the catastrophe, it was reacted w/MeNO2 right away w/out prior drying - w/the only differences that:

a) The mixtr was incubated for an hor at -5-0 C rather than 5-10 C.

b) The end product was washed w/20mls IPA on filter - and, DAMN IT - there was an evident dissolution, the filtrate turned yellow and cloudy (mixed w/water), some fluffy solids pptated....

WTF? I thought it wasn't soluble in IPA.... Does that mean SWiHKAL's totally fucked?

Or - is this an admixture of undehydrated nitroalcohol (seems possible since stirring wasn't very good) - ?

Or maybee, the nitrostyrene was so soluble beecause of its very fine consistency? Can anyone share his/her experiences regarding this nitrostyrene's solubility in IPA, PLEASE!



Sincerely,


Antoncho
 
 
 
 
    yellium
(Hive Addict)
08-27-02 13:42
No 349755
      Too bad. I've had my share of stupid mistakes too ...  Bookmark   

Too bad. I've had my share of stupid mistakes too :=)

Nitrostyrene is soluble in IPA. Some more than others; when I worked with some 3,4,5-trimethoxynitrostyrene, half of the stuff would dissolve instantly in IPA. Snce I didn't want to lose to much by recrystallizing the stuff, I skipped the filtering stage, and simply reduced everything with xs LAH, then did an AB (followed shulgin to the letter). NMR showed about 99.5% clean mescaline.

So, basically, if you're so lucky that you can use LAH, don't waste your yields on making perfectly clean nitrostyrene; instead, clean everything at the A/B stage.
 
 
 
 
    Beaker
(Stranger)
08-27-02 22:10
No 349945
      IPA solubility  Bookmark   

At room temp that nitrosyrene is slightly soluble in IPA, but not very much so. 20mL was maybe too much to wash 1g in, or your nitrostyrene was very impure. Also, yellium is right, rigorously purifying the nitrostyrene is usually a waste of time. How are you going to reduce?
 
 
 
 
    Mountain_Girl
(Hive Bee)
08-27-02 22:11
No 349947
      SWiHKAL has past the 1/2 way mark Antoncho!  Bookmark   

SWiHKAL has past the 1/2 way mark Antoncho! I'm pleased and inspired by this.

Just one Q/idea:
Cold temps were maintained throughout SWiHKAL's procedure. In Post 320904 (Rhodium: "2,5-Dimethoxynitrostyrene w/ NaOH catalyst", Methods Discourse) conditions were different, allowing the mixture to eventually reach 60C. I haven't really studied this reaction yet so I'm not sure what the reason for low temps are, but is it possible it may have adversely affected your yield ?
 
 
 
 
    Antoncho
(Official Hive Translator)
08-28-02 09:45
No 350121
      FUCK! FUCK! :-( :-( :-(  Bookmark   

Well, guys, just as i said, SWiHKAL is, in his essense, a retarded dumdfuck, who can't do anything properly the 1st time and not to fuck it upsmile Which he did.

Sadly, the cause of failure was just the same that in the previous accident. Only this time, a mechanical stirrer blew a hole in the flask's sideshocked and the contents,  note this - again - floated freely in the icebathfrownfrownfrown


An attempt to resque the remnants of the orange shit was made, but judging from the previous xperience, a qtty less than necessary for reduction amt will bee recoveredfrown.


So i guess the next chapter of this story will have to wait for some time.... First SWiHKAL will repeat this all over again, starting from hydroquinonewink.



Fuck!

Oh, well..... Worse things have happened.





wink,


Antoncho
 
 
 
 
    Chimimanie
(Newbee)
01-16-03 15:20
No 398852
      another CHCl3 formylation  Bookmark   

see https://www.jatox.com/jat.mar02.pdf

p 61 contain info on metabolism of 2c-b and a reimer tielman on the benzyloxy derivative from benzyloxy phenol