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Author: Subject: 3,4,5-trimethoxy-beta-nitrostyrene synthesis
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[*] posted on 4-1-2012 at 12:03


@ randolph_carter
Why go away over the 2,4,5-Trimethoxyphenyl-2-propanone ?

Quote:

2,4,5-Trimethoxyphenyl-2-nitropropene

100g asarone in 1 l ether was placed in a 3 l rb flask with a saturated solution of 500g sodium nitrite in water and setup on a mag stirrer. A pressure equalized addition funnel which was filled with 800ml of 25% sulfuric acid was then affixed to the flask and dripped into the solution over a period of 5 hours with magnetic stirring. After the 5 hours it was allowed to sit over night (about 14 hours...). In the morning the solution was filtered then the filter cake was washed with water then ethanol then ether. The resulting cake of crystals was dissolved in 500 ml ethanol with 50 g sodium carbonate in it with mag stirring and gentle heat (below 30 c). Once it was completely dissolved it was allowed to cool 1 hour then 1.5kg of ice was added then adding 1l dilute hydrochloric acid acidified it. It was allowed to sit about 1 hour at 0°C then filtered and washed with water and then let dry. This yielded 1/2 cm yellow needle crystals of the 2,4,5 substituted nitropropene with a mp of 100°C.

Yield = about 78 g

2,4,5-Trimethoxyphenyl-2-propanone

75 g of this nitropropene were placed in a rb flask rigged for reflux and addition funnel via claisen adapter with 60g iron filings and 1.2g ferric chloride in 100ml toluene. This solution was brought to reflux then 110g concentrated hydrochloric acid were dripped in over the course of 4 hours. Continue reflux for an additional hour after addition is complete then let cool to room temperature. Solution was then flushed with 2l water and subsequently extracted four times with 200ml ether. The ether extract was dried overnight over drierite filtered then the majority of the ether was distilled off before vacuum drying the ketone.

Yield = about 40g

2,4,5-Trimethoxyphenyl 2 aminopropane Hydrochloride (TMA-2 HCl)

40g ketone was placed in a rb flask setup for simple distillation with 35 ml formamide 4ml 90% formic acid (adjust as necessary to achieve 4.5 ph) and slowly brought up to about 140 c over 4 hours. (This is interactive at this point. what you are looking for is a few small streams of bubbles, kind of like a coke fizzing when about half flat...). Keep the temperature as low as the reaction will allow and raise the temperature only when necessary to keep reaction going. Check the ph about every 4 hours and add formic as necessary to keep ph about 4.5 after 28 hours the reaction temperature had reached the ceiling temperature of 180 c (about 25 ml water had distilled over by this point...). The solution was allowed to cool for 2 hours then extracted four times with 100ml benzene or toluene, then the benzene/toluene was distilled off and the solution is put in a rb rigged for reflux 35 ml concentrated hydrochloric acid is added and it is refluxed for 8 hours. The solution is then cooled for 1 hour and then chilled to 15c basified with 10% sodium hydroxide and extracted four times with 100ml ether. This extract was dried overnight over drierite and filtered in the morning before vacuum evaporating the amine oil. The oil was gassed in the normal manner to yield fine white crystals with an mp of 189°C.

Yield = 36.5g of high energy FUN! [ TMA-2 Hydrochloride ]


When you can go directly from 2,4,5-Trimethoxyphenyl-2-nitropropene to 2,4,5-Trimethoxyphenyl-2-aminopropane Hydrochloride (TMA-2 HCl) ?


Quote:

Reduction of 1-(2,4,5-Trimethoxyphenyl)-2-nitropropane to 2,4,5-Trimethoxyamphetamine

3g (11.7 mmol) 1-(2,4,5-trimethoxyphenyl)-2-nitropropane was dissolved in 20ml MeOH containing 2.5g (38.2 mmol) zinc powder (activated by stirring in 20ml 5% aq. HCl for two minutes then washed with 3x50ml water and finally 20ml MeOH). To the stirred mixture 1.9g (30 mmol) ammonium formate was added in one portion. The mixture became warm to the touch within one minute. After 15 minutes the mixture was filtered to remove the residual zinc and the solvent removed by distillation. The residual oil was dissolved in 25ml EtOAc and neutralized with dry HCl in IPA. The solution was heated to 60°C and vacuum applied to remove about 10ml EtOAc. The residual solution was slowly cooled to room temp and the walls of the flask scratched with a glass rod. Crystals begun to grow very quickly and within 1 minute the solution was a thick slurry. The crystals was isolated by filtration, washed with 50ml acetone and dried to constant weight.

Yield: 2.1 grams (8.0 mmol, 68%) of 2,4,5-Trimethoxyamphetamine Hydrochloride (TMA-2·HCl)

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DrNoiZeZ
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[*] posted on 5-1-2012 at 05:01


It is easy to think things will work just using information from Rhodium but there are many things there that just don't work and I was never able to make a reduction with Zn/formate or formic acid. If you try to do it with a nitropropene it won't work, if you try to do it first reducing the nitropropene to nitroprapane with NaBH4 and them the Zn/formate it will fail too (at least to me). From my experience Zn/HCl for nitrostyrenes and NaBH4 and then Al/HCl for nitropropenes. Yelds always around 30 - 40%.
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biggrin.gif posted on 8-2-2012 at 20:25
Hate diggin up an old thread...


Hey lingerer's first post. Would the the one pot aldehyde-styrene synthesis also work on 2,5-Dimethoxybenzaldehyde?

Seems like it should work for any benzaldehyde, right?
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[*] posted on 9-2-2012 at 00:08


What's wrong with EDDA?
https://www.erowid.org/archive/rhodium/chemistry/edda.html:
Quote:
The procedure has been optimized for the preparation of 2,5-Dimethoxynitrostyrene, and the yield is typically very high for this product, usually exceeding 95%

2,5-Dimethoxybenzaldehyde (83.1g, 500 mmol) and ethylenediammonium diacetate (9.0g, 50 mmol) was dissolved with stirring in 400ml isopropanol with gentle heating until a clear solution was obtained. Nitromethane (36.6g, 600 mmol) was then added, and during the next hour the solution turned a deep orange, and stirring was discontinued. The solution was then allowed to stand at room temp for 36h, and the orange crystalline mass was broken up with a large spatula and was filtered with suction until no more liquid came through. The crystals was then washed with 100ml cold isopropanol in the buchner funnel, and sucked as dry as possible. After air drying overnight, the crispy and intensely orange 2,5-dimethoxynitrostyrene weighed 100.5g (480 mmol, 96%).


2,5-alkoxybenzaldehydes behave much nicer than 3,4,5-alkoxybenzaldehydes. But even those can be turned into nitrostyrenes in high yield - search for cyclohexylamine and butylamine, I think even on this site.
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[*] posted on 9-2-2012 at 09:00


The only problem with those processes are the hard to find chemicals. EDDA, cyclohexylamine and butylamine aren't commercially available, while methanol, K or NaOH and HCl are available everywhere. The yeilds on the cyclohexylamine method for 345TMnS is only a slight improvement on yeild over that old two-step. If 25DMB "behave much nicer" as you say, would it not, then, take to the two-step even better than the 345TMB?

Edit - Although, looking at my first post it was quite unclear which one-pot I was talking about. Give the newbie some time and he will surprise the senior members by how quick he will learn.;)

Edit2 - Found what I was looking for.

Quote:
2,5-Dimethoxynitrostyrene3

A mixture of 2,5-dimethoxybenzaldehyde (1.97 g, 11.8 mmol) and nitromethane (0.72 g, 11.8 mmol) in methanol (200 mL) was stirred at room temperature until the solids dissolved. The solution was cooled to 0°C and a 10.5 M NaOH solution (2 mL) was added dropwise over 20 min. The alkaline solution was added slowly to a 4% HCl solution (200 mL) maintained at 60°C. The pale yellow amorphous solid that formed was filtered and washed with water (200 mL). The crude product was recrystallized from absolute ethanol to give yellow needles (2.11 g, 85%).


http://www.erowid.org/archive/rhodium/chemistry/mdp2np.html

[Edited on 9-2-2012 by mrnye]

[Edited on 9-2-2012 by mrnye]

[Edited on 10-2-2012 by mrnye]

[Edited on 10-2-2012 by mrnye]
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[*] posted on 9-2-2012 at 09:34


Also, once the nitrostyrene is achieved, can THF and LAH be avoided via catalytic hydrogenation, much like the 345TMnS can be? Again, this isn't necessarily the easier process, but I'd rather deal with Pd/C and H2 than LAH any day, not to mention, yet again, that THF and LAH are much harder to get ahold of.

edit - Yet again I answered my own question

Quote:
Experimental

2,5-dimethoxy-β-nitrostyrene (5g) is dissolved in a mixture of glacial acetic acid (125 ml) and concentrated sulfuric acid (19g). Five grams of palladinized barium sulfate are added and hydrogen is passed through the mixture at room temperature. The mixture is shaken continually during the reaction. Ninety percent of the theoretical amount of hydrogen (4 moles) is absorbed in 10 minutes, after which no further hydrogen uptake is noted. Shaking of the mixture is continued for a half hour, after which the mixture is cooled and sufficient 5 N sodium hydroxide is added to neutralize the sulfuric acid. Methanol (250 ml.) is then added to complete precipitation of sodium sulfate. The salt is washed and filtered with methanol and the combined filtrates and mother liquor are evaporated in vacuo. The residue is made strongly alkaline and extracted with 100 ml. of ether. The extract is dried over potassium hydroxide after which the solvent is removed and the residue distilled giving 3g (68%) of 2,5-dimethoxyphenethylamine boiling at 148°C/8mmHg. The product is a pale yellow oil which forms a white hydrochloride melting at 139°C.


http://www.erowid.org/archive/rhodium/chemistry/2c-h.cathyd....

But is there a way to optimize the yield here? Would Pd/C be a better catalyst? It doesn't seem that this is done under much pressure,(like 45 PSI as opposed to the normal 60-80) would it be advantageous to add more pressure?

[Edited on 9-2-2012 by mrnye]

[Edited on 9-2-2012 by mrnye]

[Edited on 10-2-2012 by mrnye]
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[*] posted on 9-2-2012 at 12:27


Quote:
EDDA, cyclohexylamine and butylamine aren't commercially available

You must be kidding. Ethylenediamine is produced in the megaton/year range and totally unwatched. Just order it.
Quote:
Also, once the nitrostyrene is achieved, can THF and LAH be avoided

Al/Hg with acetic acid in isopropanol. Yields are moderate but it doesn't get more OTC than that. Others are quite fond of Zn/HCl, I never tried it.

This information is all over the place - UTFSE!
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[*] posted on 9-2-2012 at 14:05


Mrnye, since you are new here, I will warn you, that if continue copypasting unreferenced quotes, you will soon became highly unpopular here! Now, go edit your posts correspondingly. This is a science forum, so use references and cite the original sources!
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[*] posted on 9-2-2012 at 18:03


Thanks for the notice Nicodemus. Posts now include sources.

I found sources for ethylendiamine but they will only send to official businesses. If the same process can be done with easier to find chemicals, with comparable yields, then why go through the fake business name/address song and dance?

Anyway, its not like I have DMB or plan on doing this, I just find it interesting. 25DMB can be made from anise oil, decent yield and no really scrutinized chems(except DMS but maybe MeI can be substituted) To me that is the point of home chemistry, finding easy to access routes to hard to access things. That may just be my POV tho.

And btw, I can UTSE, and did so to get above ref's. I was really asking "what do you think of this route?" Not "please do my research for me." I was simply bringing up other methods in hopes that it might help someone, and as I asked these things I was also "UingTFSE" and posting work ups right behind the questions.

Anise oil to 2C-B
www.erowid.org%2Farchive%2Frhodium%2Fpdf%2Fanethole.2c-b.pdf

[Edited on 10-2-2012 by mrnye]
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[*] posted on 10-2-2012 at 03:33
Unfrying your brain from LSD And Marajuana


You have to make sure you eat the minimum suggest calories per day and drink nothing but water.
[Edited on 11-2-2012 by TopTrader]

[Edited on 11-2-2012 by TopTrader]

[Edited on 11-2-2012 by TopTrader]




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[*] posted on 10-2-2012 at 07:25


Quote: Originally posted by mrnye  
I found sources for ethylendiamine but they will only send to official businesses.

If you look closer you will also find sources selling to individuals.
Quote:
Anyway, its not like I have DMB or plan on doing this, I just find it interesting.

How boring! What's the point of the whole discussion if you're not even going to try it? It says "amateur experimentalism" not "intellectual masturbation" at the top.
Quote:
25DMB can be made from anise oil, decent yield

Terrible method. Search for the mono-methylation of hydroquinone described by Klute.
Quote:
and no really scrutinized chems(except DMS but maybe MeI can be substituted)

Search for OTC methylation reactions described by Ullmann.

Quote:
1700 for adult males 1600 for adult females

Dude, 1700 μg of LSD is waaaaaay too much. No wonder you have to unfry your brain. It all depends on set and setting, but 200 μg is enough for ultra-cosmic trips. No point in completely shattering your ego (which can also happen on 200 μg).
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[*] posted on 10-2-2012 at 09:07


Quote:
If you look closer you will also find sources selling to individuals.

Care to share one? ES doesn't carry it does he? Don't anwser that, just thinking out loud.

Quote:
How boring! What's the point of the whole discussion if you're not even going to try it? It says "amateur experimentalism" not "intellectual masturbation" at the top.

Is a synonym for that "probable incrimination" ;)

Quote:
Terrible method. Search for the mono-methylation of hydroquinone described by Klute...

...Search OTC methylation reactions described by Ullmann.


I should have seen that first process before, but thanks for showing me what was right under my nose!

Having trouble finding the methylation reaction you speak of. I searched by user Ulmann exactly what you said.

Quote:

Dude, 1700 μg of LSD is waaaaaay too much. No wonder you have to unfry your brain. It all depends on set and setting, but 200 μg is enough for ultra-cosmic trips. No point in completely shattering your ego (which can also happen on 200 μg).


Yeah idk what that guy was talking about.

[Edited on 10-2-2012 by mrnye]
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[*] posted on 10-2-2012 at 11:03


Quote: Originally posted by mrnye  
But is there a way to optimize the yield here? Would Pd/C be a better catalyst? It doesn't seem that this is done under much pressure,(like 45 PSI as opposed to the normal 60-80) would it be advantageous to add more pressure?

If you would UTFSE more efficiently and beyond what is served to you on a silver plate called The Rhodium archive, you could find articles describing the use of Pd-C for this type of reduction:
Bulletin of the Chemical Society of Japan 1990, 63, 1252-1254.
Synthetic communications 1971, 1, 47-50.
Quote: Originally posted by mrnye  
And btw, I can UTSE, and did so to get above ref's. I was really asking "what do you think of this route?" Not "please do my research for me."

You overestimate your searching skills and search in the wrong places. For example, we already have a thread on the topic of hydrogenation of nitrostyrenes. Also, there are plenty of practical examples of hydrogenation of various beta-nitrostyrene over Pd-C at the Hyperlab forum. Sometimes all it takes is to search in the right place.




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[*] posted on 10-2-2012 at 14:46


No, like I said, I have looked around and even found a process using something similar, I was asking what some here might think would help increase the yeild. I know it would have to be experimented with to actually find out the best conditions for the best yeild. Looking at the Pd/C threads I don't know how well it would work, and the process did list a specific catalyst so they tried other combinations first and this was most likely the best. I'm sorry if I came off sounding like a smart-ass, that wasn't my intended tone. I just didn't feel like I was being understood, which was probably my fault.

I was simply looking for some ideas on how to increase the yeild, and also use the most OTC route possible. Like the hydroquinone route that I somehow overlooked, way better than my idea of starting from anise oil. But as far as getting from there to the pea, it seems a little easier to make a hydrogenation apparatus than playing with LAH etc. I will look into the alluminum amalgam reduction as well. Please understand that I don't have constant internet access and am sometimes forced to use my phone to search and a lot of links won't open, its hard to type on this little screen, etc. I'm not really looking for anything on a silver platter, just a little input or insight on what I put up.
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[*] posted on 22-2-2012 at 10:55
How To Unfry Your Brain


Quote: Originally posted by TopTrader  
You have to make sure you eat the minimum suggest calories per day and drink nothing but water.
[Edited on 11-2-2012 by TopTrader]

[Edited on 11-2-2012 by TopTrader]

[Edited on 11-2-2012 by TopTrader]


I was wrong about how much you have to eat. You have to calculate your daily caloric needs and eat that until its unfried. For an adult male 227lbs with no excercise is 4000 calories/day according to the daily caloric needs formula found in the book, 'Men's Fitness Total Body Plan '
written by the editors of Men's Fitness Magazine. Here is the formula for calculating your daily caloric needs.
A. Your weight in pounds.
B. Multiply A by 11 to get your resting metabolic rate.
C. Multiply B by 1.6 to estimate your caloric expenditure through basic daily activities.
the rest of the formula adds excercise in which you don't need to do if your trying to unfry your brain.
It worked for me. I hope it helps someone else. God bless.

[Edited on 22-2-2012 by TopTrader]




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[*] posted on 26-5-2012 at 17:34


Quote: Originally posted by turd  
Quote: Originally posted by mrnye  
I found sources for ethylendiamine but they will only send to official businesses.

If you look closer you will also find sources selling to individuals.


Ammonia + acetic -> ammonium acetate

Always use product high in polyunsaturates when unfrying your brain.
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[*] posted on 27-5-2012 at 02:28


Quote: Originally posted by peach  

Ammonia + acetic -> ammonium acetate

Fair enough, but liquid ethylenediamine is so much easier to handle than gaseous ammonia. Moreover the ethylenediammonium diacetate does not seem to be very hygroscopic. I had some in an open container show signs of decomposition though.

Anyway, either ethylenediamine or ammonium acetate can easily be sourced by the astute amateur. There are many different bases suitable for the Henry reaction. One I'm planning to use is the Me2NH2.HCl/KF combo with a Dean-Stark trap (https://www.erowid.org/archive/rhodium/chemistry/345-nitrost...). Sounds too good to be true, but who knows. And first I need an appropriate substrate.

Quote:
Always use product high in polyunsaturates when unfrying your brain.

Oh yes, the power of imagination, a.k.a. placebo effect. I'd say stay away from meat products for spiritual cleansing, but unfortunately I don't believe in such mumbo-jumbo. Anyhow, I definitely envy you Brits for the numerous curry eateries with the extensive vegetarian options. :(

[Edited on 27-5-2012 by turd]
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