Sciencemadness Discussion Board - 3,4,5-trimethoxy-beta-nitrostyrene synthesis

3,4,5-trimethoxy-beta-nitrostyrene synthesis

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a123x - 19-6-2005 at 14:46

I thought of another possible route to making 3,4,5-trimethoxybenzaldehyde, starting with anisaldehyde. Dinitrate the anisaldehyde to make 3,5-dinitroanisaldehyde. This is reduced with a reducing agent of choice to form the diamino compound. Diazotisation is then carried out in methanol. The methanol is then allowed to react with the diazonium salt to form methoxy groups. I did find reference to such a reaction being used to form methoxyninhydrin:

"Lennard and co-workers have synthesized many of the early substituted ninhydrin analogues, including 5-methoxyninhydrin (28).18 The synthesis began with commercially available dimethyl 4-nitrophthalate (23) (Scheme 6). Reduction of the nitro group to the amine 24, was followed by diazotization with nitrous acid in methanol to yield 4-methoxyphthalate (25). Reaction of this compound (25) with ethyl acetate and sodium hydride afforded the Claisen ester condensation product, which was treated with aqueous hydrochloric acid to yield the desired 1,3-diketone (26). Treatment with p-toluenesulfonyl azide in triethylamine delivered the 2-diazo intermediate (27) that was subsequently hydrolyzed with refluxing aqueous tert-butyl hypochlorite to yield 5-methoxyninhydrin (28). The reagent develops prints with a more intense fluorescence than ninhydrin-developed prints. Joullié and co-workers later developed an alternative route to 5-substituted ninhydrins. They used this method to synthesize 5-(methylthio)ninhydrin, which was shown to possess superior properties to those of 5-methoxyninhydrin.19"

Unfortunately that seems to be all the detail that I could find on the reaction. I myself am unaware of any reason why it can't be used to form 3,4,5-trimethoxybenzaldehyde starting with anisaldehyde but there may well be some reason why it won't work. I myself am quite curious as to whether it will work. Does anyone know of any reason it won't work or have more information on the specifics of carrying out the synthesis?

Sandmeyer - 28-6-2005 at 00:48

while true that i've not looked i find it hard to belive that there are examples in the litterature where 2 amino groups are turned into diazonium salt and displaced by nuceophile stimulaneously. another problem is the nitration of anisaldehyde, formyl is slightly deactivating and putting not one but two nitros could be difficult, maybe start from p-phenol (followed by methylation) instead of methylether would solve this. But even if the diazotization and everything did work, the route is not a good one, I would rather di-brominate (preferably p-hydroxy-benzaldehyde) and do a copper catalyzed substitution with sodium methoxide for syringaldehyde to be methylated... If a vast array of compounds is looked for it is better to start from vanillin, so it depends what and how much compounds you want to make of course... Again, I haven't looked up your proposal, it might work, but i would be surprised and regardless it is too much work.

EDIT:

As you see this is much easier and well documented:

3,4-Dibromo-4-hydroxybenzaldehyde:

To a stirred, cooled (0°C) solution of 122.0 g (1.0 mol) 4-hydroxybenzaldehyde in 1.0 L of methanol was added during 30 min 325.0 g (2.2 mol) of bromine at such a rate that the temperature was kept below 20°C. The mixture was stirred at room temperature for 1.0 h, 800 mL of methanol was removed by distillation (water aspirator) at 50°C, and to the warm (45°C) solution was added 2.0 L of water during 20 min. The mixture was stirred at 0°C for 1.0 h and the product was collected by filtration. It was washed with water (5 x 1.0 L) and then with 500 mL of cold, 30% aqueous methanol, dried in vacuo at 70°C for 18 h to give 264.4 g (95.5%) of 6 as a colorless powder, mp 180-182°C. TLC (silica gel, 30:60:1 ethyl acetate: hexane: formic acid) showed only one spot under short wavelength UV light.

Syringaldehyde:

A 165-g (0.59 mol) batch of 6 in 156 mL of methanol and 312 mL of anhydrous DMF was reacted during 4.0 h with 4.78 moles of freshly prepared sodium methoxide in the presence of 9.45 g (0.047 mol) of cuprous chloride under the conditions described previously for the conversion of 5 to give 153.3 g (88% yield) of 7, mp 105-108°C

Ref: Synthetic Communications 20;17;1990;2659-2666

3,4,5-trimethoxybenzaldehyde

10g 3,5-dimethoxy-4-hydroxy-benzaldehyde, 13.5g K2CO3 and 8.3g dimethylsulfate is dissolved in 80mL dry DMF, the solution is stirred for 2h and then poured into 800mL ice/water, the product is filtered off and xtalised from cyclohexane.

Ref: Hest's mesc writeup

[Edited on 28-6-2005 by Sandmeyer]

Sergei_Eisenstein - 29-6-2005 at 08:28

Quote:

Originally posted by Sandmeyer

Again, I haven't looked up your proposal, it might work, but i would be surprised and regardless it is too much work.

I'd be surprised if it would work. The carbonyl functional group will not survive this oxidation.

[Edited on 29-6-2005 by Sergei_Eisenstein]

garage chemist - 29-6-2005 at 11:38

Quote:

Originally posted by Sandmeyer

3,4,5-trimethoxybenzaldehyde

10g 3,5-dimethoxy-4-hydroxy-benzaldehyde, 13.5g K2CO3 and 8.3g dimethylsulfate is dissolved in 80mL dry DMF, the solution is stirred for 2h and then poured into 800mL ice/water, the product is filtered off and xtalised from cyclohexane.

[Edited on 28-6-2005 by Sandmeyer]

I have a question, not about this specific synthesis, but about methylations with dimethylsulfate in general (in DMF as well as in water): After pouring the mixture into ice water, is the dimethylsulfate entirely gone or might there be some residues (dimethylsulfate decomposes very slowly in water)?
And does it decompose into H2SO4 and Methanol, or into Methylsulfuric acid?
And how dangerous is methylsulfuric acid?

[Edited on 29-6-2005 by garage chemist]

Sandmeyer - 29-6-2005 at 13:54

Quote:

Originally posted by garage chemist

Quote:

And does it decompose into H2SO4 and Methanol, or into Methylsulfuric acid?
And how dangerous is methylsulfuric acid?

It decomposes into the anion MeSO4 (-) of methylsulfuric acid, material safty data sheet of potassium salt can be found here: https://fscimage.fishersci.com/msds/95639.htm

Should the post-reaction excess be destroyed with NaOH, then yes, MeOH would be produced as well...

[Edited on 29-6-2005 by Sandmeyer]

cyclohexylamine

transformer - 30-6-2005 at 04:32

If you are going to condense 3,4,5-trimethoxybenzaldehyde with nitromethane i definately suggest to use cyclohexylamine as a catalyst, providing consistent good yields.

To a solution of 150 mL of acetic acid and 40 mL nitromethane there was added 20,21 gram (103 mmol) 3,4,5-trimethoxybenzaldehyde and 20 mL cyclohexylamine. The addition of the cyclohexylamine caused the RBF to fill up with smoke.

The solution was heated to 95°C and after 90 minutes of heating the orange solution was allowed to cool down.

When the solution had cooled down to to 60°C it was decanted into a beaker for quicker cooling this left a lot of smoke in the RBF, after adding some H2O to the RBF the smoke cleared up and caused formation of some residue yellow crystals.

With good stirring the now 20°C decanted solution was diluted slowly using 325 mL H2O, this caused the formation of a thick yellow crystalline mass.

The crystals from the beaker and the RBF were combined, filtered and washed thouroughly with 3 times with 65 mL H2O. The filtered crystals weighed 23,44 gram after sucking them dry for 20 minutes.

The entire mass recrystalized in 192 mL MeOH (8 mL/g) with 3 ml ethyl acetate to dissolve the impurities that did not go into solution.

[Edited on 1-21-2011 by Polverone]

Sandmeyer - 30-6-2005 at 08:28

Quote:

Originally posted by samsung

...there was added 20,21 gram (103 mmol) 3,4,5-trimethoxybenzaldehyde and 20 mL cyclohexylamine...
[Edited on 30-6-2005 by samsung]

have you tried EDDA 10 mol % in GAA?

Easier still..A truly facile route to 5-iodovanillin

UpNatom - 30-6-2005 at 12:29

1) Vanillin (1g), ethanol (20 mL), and sodium iodide (1.2g) were added to a conical
flask furnished with a magnetic stir-bar and the solution was placed in an ice bath for approximately 5-10 minutes with vigorous stirring.

2) 12 mL of sodium hypochlorite solution -household bleach- was drawn into a syringe and then added dropwise to the stirred reaction mixture over a period of 10 minutes. As the sodium hypochlorite is added the solution will turn from a pale yellow solution to a light auburn color.

3) Once the addition of the sodium hypochlorite solution was complete, the mixture was allowed to
warm to room temperature and stirring continued for 10 minutes.

4) 50 mL of sodium thiosulfate solution (10% aqueous) was added, then the solution was acidified with a 10% hydrochloric acid solution. Acidifying the solution to a pH level of approximately 4 should be adequate. The aryl iodide may precipitate at this point.

5) Once acidified, the solution was stripped of EtOH with the aid of a vacuum and gentle heat.

6) The remaining aqueous solution was placed in an ice bath for 10 minutes to allow the precipitate to form, then the ppt was collected by vacuum filtration, washed well with ice-cold water, then washed again with a few [!] mls of cold ethanol.

7) The crude product was placed into a vial and, with gentle heating, just enough IPA added to dissolve the solid. While continuing to heat, hot water was added slowly until the mixture became cloudy, then IPA was again added, just enough to return a clear solution. The vial was placed in an ice bath for approximately 10-15 minutes to ensure complete crystallization.

8) The crystals were collected by vacuum filtration and air drawn through for several
minutes to facilitate drying.

Yield 1.5g 5-iodovanillin (~80% of theoretical)

transformer - 30-6-2005 at 15:49

Quote:

Originally posted by Sandmeyer

have you tried EDDA 10 mol % in GAA?

No, how are the yields? and what is the polymer to nitrostyrene ratio?

garage chemist - 5-7-2005 at 06:47

Is it possible to methylate syringaldehyde with methyl iodide instead of dimethyl sulfate? I want to get an idea of the methylating power of MeI, as e.g. trimethyl phosphate is not strong enough to methylate syringaldehyde to trimethoxybenzaldehyde. Is methyl iodide strong enough?

wa gwan - 5-7-2005 at 07:35

From:US4453004

EXAMPLE 4

In an apparatus similar to Example 1, 15.2 g (0.083 mol) of syringaldehyde and 15.0 g (0.11 mol) of potassium carbonate were heated to 105 DEG C. under nitrogen and 15 ml (0.12 mol) of trimethyl phosphate were added over 10 minutes. The mixture was maintained at about 80 DEG C. for 3 hours then cooled to 45 DEG C. and quenched with 50 ml of H2 O. The tan solid which precipitated was collected, washed with 3.times.50 ml of water and dried to give 15 g (92%) of 3,4,5-trimethoxybenzaldehyde.

Of course MeI wil also work.......

trilobite - 5-7-2005 at 13:21

The reaction proceeds above the melting point of the compound to be alkylated. Syringaldehyde melts around 110-113°C, methyl iodide boils at 41-43°C, also the patent says that "In the process of the invention it is usually advantageous to choose an alkylating agent which has a boiling point several degrees higher than the melting point of the phenol being alkylated to control pressure surges during the course of the reaction."

Obviously the methyl iodide would most likely reside somewhere else than the same phase with the phenol. Of course it might be possible with suitable tricks, like a pressure vessel or continuously recycling the distilled methyl iodide and injecting it below the surface of the phenol... but not likely as simple as with the higher boiling alkylation agents.

garage chemist - 6-7-2005 at 01:55

I wasn't referring to the method of melting the phenol with TMP or DMS, rather to the method where the phenol is dissolved in DMF with K2CO3 and stirred with DMS at ROOM TEMP.
Would THIS also work with methyl iodide?

Thanks for the other info anyway, I didn't know that TMP is able to methylate syringaldehyde.

[Edited on 6-7-2005 by garage chemist]

Sandmeyer - 6-7-2005 at 03:05

Of course it will work, but let it stirr overnight instead of 2h. If DMF is unavailable, acetone can be used:

3,4,5-Trimethoxybenzaldehyde (1)

A stirred mixture of 153.0 g (0.84 mol) of syringaldehyde (7) in 1.0 L of acetone, was treated with 127.0 g (1.02 mol) of dimethylsulfate, 118.0 g (1.11 mol) of anhyd. Na2CO3, and 3.0 g (0.053 mol) of KOH in 32 mL of water. The mixture was stirred under reflux for 18 h. cooled to room temperature and filtered. The filter cake was washed with acetone (3 x 200 mL) and the filtrate and washings were concentrated to ca. 200 mL. The stirred solution was diluted with 500 mL of water during 30 min, followed by 1.5 L of water during 15 min. Stirring was continued at room temperature for 15 min and then at 0°C for 30 min, and the product was collected by filtration. It was washed with water (4 x 2.0 L) and dried in vacuo at 25°C for 24 h to give 150.2 (91.5%) of 1 as colorless crystals, mp 73-75°C (Lit.9 74°C). TLC (4:1 ether-hexane) revealed only one spot, Rf 0.57.

[Edited on 6-7-2005 by Sandmeyer]

joe_aldehyde - 6-7-2005 at 04:10

what about substituting cyclohexylamine for butylamine(acetate) or methylamine(acetate), are those 2 worth a try being used as catalysts?

KidCurry - 6-7-2005 at 21:27

Yes, methylamine works.
You could also do a Henry Reaction, base catalysed to an alcohol then dehydrate it with an acid. Works good for 3,4,5-TMNS with decent yields.

http://www.organic-chemistry.org/frames.htm?http://www.organ...

[Edited on 7-7-2005 by KidCurry]

Sandmeyer - 8-7-2005 at 03:43

Quote:

Originally posted by KidCurry
Yes, methylamine works.
You could also do a Henry Reaction, base catalysed to an alcohol then dehydrate it with an acid. Works good for 3,4,5-TMNS with decent yields.

http://www.organic-chemistry.org/frames.htm?http://www.organ...

[Edited on 7-7-2005 by KidCurry]

To the solution of 5.5 g 3,4,5-TMBA in 25 ml of GAA was added 3.5 g of nitromethane and 0,5 g of ethylenediamine diacetate. Obtained mixture was heated with reflux for 1 h, diluted with 150 ml of water, obtained crystals were washed with water, minimal amount of cold IPA and hexane and dried. Yield – 5.6 g (84%). I mean, 1 mL of butylamine or cyclohexylamine instead EDDA will work too.

Ref: priv. communication.

Obviously, any reasonable primary amine works, and, as far as 345 goes GAA should be used as a solvent. If one can't afford ethylenediamine then ethanolamine might be an option, although I have no refs for this statement.

I have also seen examples from litterature when secondary amines are being used under MW irradiation (e-flask in a domestic MW-oven) giving also very good results in no-time, but for now I'm away from my refs.

[Edited on 8-7-2005 by Sandmeyer]

Sandmeyer - 8-7-2005 at 06:21

Quote:

Originally posted by joe_aldehyde
swim has too little 3,4,5-TMBA to go experimenting with the catalysts, but still he has methylamine, butylamine, ethanolamine.

i wonder if ethanolamine is any good in knoevenagel condensations.

Not only is it clear from my last post that butylamine has been tried and works, but it seems like replying is a total wate of time. If you wonder whether etanolamine works try it now that you have chemicals, or is it to complicated?

[Edited on 8-7-2005 by Sandmeyer]

joe_aldehyde - 8-7-2005 at 10:01

oh SAM...

enima - 20-7-2005 at 09:11

joe, the ethylenediamine can be found at photo suppliers. It is pretty cheap. The freebase is in liquid form.

To make acetate salt use 2x molar acetate per 1 mol ethylendiamine. DCM works as the solvent. Use an ice bath, keep the temp around 15C.

S.C. Wack - 20-7-2005 at 10:58

Methyl iodide is specifically mentioned in Vogel. Methyl bromide can methylate pyrogallol and syringol, volatility is not an issue as the reaction is fast. An interesting alternative is diazomethane, though not on the aldehyde.

Of course this is on the phenols or acids, how well the original Williamson works on benzaldehydes, and what can be done to minimize Bad Things, I don't know.

IPN - 24-7-2005 at 08:55

Quote:

An interesting alternative is diazomethane, though not on the aldehyde.

You mean it wouldn't work on the aldehyde?

Also, how well does diazomethane compare with other methylating agents? Say with dimethylsulfate? Would be nice if it would work as a substitute as diazomethane is - atleast for me - the most easily made methylating agent.

S.C. Wack - 24-7-2005 at 10:44

I'm not even sure that it would work on pyrogallol, I have no refs.

This is something that I've always been meaning to look up further but never have. I was going to spend some hours at the library today anyways. I've never seen it used on phenols in a journal, I've only seen passing mentions without references to it being done on phenols, here and there. There is an example in OS on a cyclohexanol. Note the catalyst, which is a typical one for this. CH2N2 converts benzaldehydes to acetophenones, and interesting but in this case undesirable epoxides and 2-propanones.

Again, whether or not the aldehyde could be protected/hydrolyzed back to the aldehyde I don't know.

With gallic acid this would be very interesting if it could be made to work, as the resulting trimethoxy methyl ester could be reduced to the alcohol.

Sergei_Eisenstein - 24-7-2005 at 12:46

I've seen references here and there where phenolic benzoic acids where permethylated with diazomethane, so it should work indeed. Also, the homologation reaction of benzaldehydes with diazomethane usually stops at acetophenone. P2P and corresponding oxiranes are only found in trace amounts. I thought piperonal to be one of the few exceptions, and it still is solvent dependant.

S.C. Wack - 24-7-2005 at 21:51

Yes, phenylacetaldehyde is more interesting for some, not benzaldehyde itself. I too have read the Org. Reactions chapter, and have Mosettig's 1928-9 Ber. articles. The dissertation is a little harder to find from here.

There are many references on tannin methylation with diazomethane, but I still have nothing on pyrogallol, etc. I've only scratched the surface.

The plain hydroxybenzenes should be less acidic IIRC, especially with partial methylation. I'm not sure what the cutoff is, where you have to start using catalyst as in the OS article. It seems that with gallotannin, conversion is OK, the procedure simple, and partially methylated acid can be recovered and used again.

Most of the refs on tannin that I came across today were in obscure journals, Chinese patents, and/or not in English. It seems that the usual DMS/KMnO4 to the methylated benzoic acids doesn't suit everyone, but the CH2N2/alcoholic KOH is definitely less common. Various dry solvents have been used for the methylation. Tannin/diazomethane interests me, so here is the best of the few refs that I could find today, like it or not. This one uses acetone as solvent and of course is in German, only a small part of a larger, badly microfilmed article:

Attachment: ber_47_2485_1914.pdf (721kB)
This file has been downloaded 1149 times

enima - 24-7-2005 at 22:41

Quick question: @ what temp does the aldehyde, either 3,4,5-trimethoxybenzaldehyde or the 5-hydroxyvanillin begin to decompose?

Sandmeyer - 8-8-2005 at 07:51

I don't know if the yield I gave in my above post is reproducible, I have got only 30% yield of 3,5-dimethoxy-4-ethoxy-nitrostyrene with EDDA as catalyst. I have used car-fuel nitromethane as it is -- don't know if this had something to do with the bad yield, but the product was very pure and had identical mp to that reported in litterature.

Also, it is best to try to provoke crystals (can take time scratching) before adding water or else it will simply oil out.

Good luck.

[Edited on 8-8-2005 by Sandmeyer]

enima - 8-8-2005 at 08:13

Sandmeyer, try the reaction with n-butylamine you you should have higher yields. EDDA only works well on a few nitrostyrenes,

Sandmeyer - 27-8-2005 at 04:43

Using ten molar per cent EDDA gives in my experience only 30% on 3,4,5-pattern. Under the same conditions, when 2,5 mL ethylenediamine freebase was used for 10 g 4-allyloxy-3,5-dimethoxybenzaldehyde the yield of 4-allyloxy-3,5-dimethoxynitrostyrene was 66%, obvioulsy a lot more ethylenediamine than originally suggested is needed. Well, I will try some other catalysts, but I have so much to do now school-wise.

Vitus_Verdegast - 10-8-2006 at 11:04

Preparation of 5-iodovanillin

12.6 g iodine was added in 4 portions during 30 minutes to a rapidly stirred suspension of 7.5 g vanillin in 200 ml demineralized water containing 5 g NaHCO3 and 9 g NaI.

During the addition the mixture darkened in colour and a heavy yellow solid precipitated.

Stirring was continued for 5 hours, and the mixture was left overnight. The crude 5-iodovanillin was filtered off and washed thoroughly with a dilute aqueous NaHSO3 solution (this way eyeballed, it could not have been more than a couple %). The reddish brown motherliqour is saved for iodine recovery.

After drying, 13 g 5-iodovanillin was obtained, which corresponds to a 94% yield.

The product will be recrystallized from aqueous ethanol, although I don't think this is really necessary.

5-iodovanillin only has a faint vanilla-like odor.

alternate route to desired compound

xxxxx - 25-8-2006 at 09:42

i was kind of thinking about condensing 3,4,5 trimethoxy benzoic acid ethyl ester with ethyl acetate to form 3,4,5 (CH3)3C6H2COCH2COOH then hydrogenating the ketone to a methylene group by some method to form 3,4,5 (CH3)3C6H2CH2CH2COOH then adding ethanolic ammonia to form 3,4,5 (CH3)3 C6H2CH2CH2CONH2 then adding NaOCl. i was kind of wondering what the yields for each step would be and the overall yield.

ctrlphreak - 15-10-2010 at 09:29

I think that going the route of Vanillin is better, because of less usage of the Methylating agents.

Going the route of Gallic Acid -> TrimethoxyBenzoic Acid, you have to use THREE Equivelants on the methylating agents side.

But either case, Have ya ever checked into the Stephen's Aldehyde Synthesis?

I just discovered it recently and it looked pretty nifty.

Carboxylic Acid is converted into the Nitrile. (I would suggest refluxing in Sulfaminic Acid and Urea), and then reduced with Sn(II)Cl2 I believe it was.

Anyone have any thoughts on that?

arsphenamine - 31-10-2010 at 06:47

Quote: Originally posted by Sandmeyer

To the solution of 5.5 g 3,4,5-TMBA in 25 ml of GAA was added 3.5 g of nitromethane and 0,5 g of ethylenediamine diacetate. Obtained mixture was heated with reflux for 1 h,

No need to rush.

Many aromatic aldehydes and Henry rxn reagents, if stoppered in the dark for a day or three, condense to the β-nitrostyrene at room temperature.

Same goes for the methylation of phenols by dimethyl sulfate: RT and dark.

my 64,382 cents worth on a tma2 sythesis....

randolph_carter - 16-11-2010 at 07:35

So what would any discussion of TMA-2 on the internet be without this lil rave originating from europa in the distant past.....

hope it is of help in your current experiments

enjoy swarm......
-----------------------------------------------------------------

TMA-2 from Sweet Flag Root (Acorus Calamus)
By Randolph Carter - The Perennial Dream Questor

--------------------------------------------------------------------------------

Introduction
Sweet flag grows throughout most of north amerika east of the rockies in the wild state in wet areas where wild rice and reeds would feel at home. I found immense stands in Tennessee and northern Mississippi.Therefore my granola-head sensibilities were not offended by the copious gathering, for extraction and transplanting of this aquatic plant to the wilds of extreme north Georgia. It's most prevalent constituents are asarone, eugenol and esters of acetic and heptic acids. Even though this treatise includes my full dreams from the plant roots, I would be remiss if I did not point out that calamus oil is readily available from most of the usual suspects who deal in essential oils. I have found that this is a MUCH more attractive from scratch type of synthesis than sassafras / safrole ever dreamt of being. That is my impetus for doing this research, to wit what can I use that is VERY prevalent in my area to produce a most dreamy not-drug. My experiences with the results of this procedure have been VERY favorable received in most tests (which have been VERY extensive). Field testing indicates that dosages in the 25 to 50 mg range result in some VERY fine psychedelic dreams that are quite facilitative to sexually enjoyment with single or multiple sexual partners unlike many heavy psychedelics.

Anyways here is the rest of the story as paul harvey sez...

Steam Extraction Technique
The extractor is about 2' in height and about 16" in diameter made of stainless steel and has tight fitting "connections".Imagine a large pot with a drain spigot on the bottom, on top of the pot is an approx 1 1/2 gal "steamer" with sealing lid and a bottom of preforated holes. (i lined the bottom of this with fine gauge stainless steel screen finer than pipe screens..from industrial sources to minimize grit and small pieces of root fibers...) To operate i dreamed that i charged the "basket" with all the ground roots (ground by a small hammer mill used on the farm for other herbs we sell...chopped root would work equally well we feel...)the top was sealed on with silicone stopcock/joint grease and it was heated to boiling and maintained there for about 6 hours per load (7 loads required for 10 kg...). After cooling down the top is removed and the water with an oil layer was drained into a nalgene carboy with spigot which allowed for a "crude" seperation of the oil and a small amount of water. Then it was shook in the carboy with the applicable washes mentioned below before being put in a "real" 2l sep funnel for final seperation.

Calamus Essential Oil
Approximately 10 kg of dried calamus root were steam distilled with the help of the above mentioned stainless steel juicer/extractor obtained through cumberland general store. (This item is commonly found in seed catalogs from several companies as well). This yielded 330 g of viscid light yellow oil with a bitter taste, which was only slightly soluble in water. After separating the oil, the oil was washed with first a water solution of sodium carbonate then water then it was seperated from the water layer then dried over drierite overnight before further usage.

Yield = about 320 g clean calamus oil.

Asarone
Next this oil was fractionally distilled to yield a fraction at 185 to 200°C which was chiefly asarone.

Yield = about 210g

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 ]

--------------------------------------------------------------------------------

Ritter:

Take it from someone who knows: Randolph Carter has been around here since day 1 but it appears his writing skills (when you can actually read what he wrote) are far advanced compared to his proficiency in organic synthesis. There is no way he produced the ultra-high yields of TMA-2 via Leukart reaction as claimed in the writeup at Rh’s. Phenylacetones simply do not work as well as other ketones with this rxn. If the rxn. is run as Randolph described, you will be lucky to isolate anything greater than a 30% yield of primary amine.

--------------------------------------------------------------------------------

NOT 2,4,5 eh???

randolph_carter - 16-11-2010 at 07:39

ooooops "3,4,5" NOT "2,4,5" tma....
my bad but you may find some pointers anyhoooow......

zajcek01 - 16-11-2010 at 15:14

Would triethylamine catalyst work instad of cyclohexylamine, butylamine and methylamine for condensation of 3,4,5-trimethoxybenzaldehyde with nitromethane or nitroethane?

Nicodem - 17-11-2010 at 07:40

Quote: Originally posted by zajcek01

Would triethylamine catalyst work instad of cyclohexylamine, butylamine and methylamine for condensation of 3,4,5-trimethoxybenzaldehyde with nitromethane or nitroethane?

No. The use of triethylamine or other tertiary amines as catalysts only gives the Henry reaction product (beta-nitroalcohol). You need ammonium acetate or a primary alkylamine or its acetate to obtain the Knoevenagel condensation product (beta-nitrostyrene). Supposedly secondary amines, which are otherwise generally used in the classic Knoevenagel condensation on other acidic methylene compounds, also work on nitromethane in some cases. Otherwise, if you have no suitable primary amine, you can always use the classical two step beta-nitrostyrenes synthesis employing NaOH and HCl. There are a couple of high yielding examples for 3,4,5-trimethoxybenzaldehyde in the older literature. Check them out. If I remember correctly, the yields are as high or higher than the amine catalysed Knoevenagel condensation.

SelfStarter - 22-11-2010 at 21:54

I can tell you from personal experience that the two step NaOH and HCl synthesis works just fine for synthesizing 3,4,5 trimethoxynitrostyrene my highest yield was 89.5g from 100g of the benzaldehyde. I would be interested in finding out how well i works on other substituted benzaldehyes.

Nicodem - 23-11-2010 at 13:49

Quote: Originally posted by SelfStarter

That is a 73% yield which is consistent with literature reports using KOH and HCl:
79% yield in DOI: 10.1002/prac.19331370907
80% yield in DOI: 10.1007/BF01524590 (this journal has currently free access for all, so grab the article before Spr*nger changes its mind - there is some interesting chemistry described therein)

Quote:

I would be interested in finding out how well i works on other substituted benzaldehyes.

The review DOI: 10.1021/cr60141a002 covers dozens of old references using this methodology on all kind of substituted benzaldehydes. The aplication on the unsubstituted benzaldehyde is covered in Organic Syntheses.
For some reason people tend not to use this method any more. I guess it is considered antiquated, or perhaps because it looks too much like a "two step" synthesis, which is not true as it involves no isolation of the intermediate hydroxynitronate salt. Whatever the reason is, in the newer literature you will hardly find any examples, even though in the old times it used to be the method of choice. In the amateurish field, I do remember there is a thread on this topic at the Hyperlab forum. I think it reports successful tests on a couple of 4-alkoxy-3,5-dimethoxybenzaldehydes. I think there were also reports about application on 3,4,5-trimethoxybenzaldehyde in some other threads there.

[Edited on 23/11/2010 by Nicodem]

arsphenamine - 24-11-2010 at 06:29

Quote: Originally posted by Nicodem

The aplication on the unsubstituted benzaldehyde is covered in Organic Syntheses.
For some reason people tend not to use this method any more. I guess it is considered antiquated, or perhaps because it looks too much like a "two step" synthesis, which is not true as it involves no isolation of the intermediate hydroxynitronate salt.

I opine that unless you have an intimate connection to the costs of your laboratory efforts,
you will use what is handy irrespective of its preciousness.
The OrgSynth procedure requires inexpensive reagents and, though post-WW2,
harkens to its Great Depression era roots.

For the parsimonious, reactants and n-BuNH2 could sit in the dark
for a few days without further attention.

The last worked well for R-PhCHO's + EtNO2, although polymer formed
if it was allowed to run too long.

Perhaps this is dating myself, but I heard Dauben of basketane/cubane
fame comment on RT+dark+time reactions using methylation of gallic acid
as a specific example.

SelfStarter - 26-11-2010 at 14:18

Quote: Originally posted by SelfStarter

I can tell you from personal experience that the two step NaOH and HCl synthesis works just fine for synthesizing 3,4,5 trimethoxynitrostyrene my highest yield was 89.5g from 100g of the benzaldehyde. I would be interested in finding out how well i works on other substituted benzaldehyes.

Actually there is a typo in what I wrote. I achieved a 89.5g yield from KOH and HCl not NaOH and HCl. When I used an equimolar amount of NaOH I always got a yield somewhere in the 60-70g range. I triple checked my math and the quality of the NaOH was fine I don't know why KOH works so much better for me.

Picric-A - 28-11-2010 at 13:51

Could somebody please outline the KOH and HCl method for me as i am not familiar with it and when i try to search for it here at school all the sites are blocked due to accociation with drugs. Thanks,

DJF90 - 28-11-2010 at 15:30

If its blocked by your school then you probably shouldn't be doing it...

Nicodem - 29-11-2010 at 09:52

My suggestion is to change school. This is the first time I hear about a school blocking access to Org. Synth, ACS, Wiley and/or Springer. Sounds completely insane to associate scientific publishers with drugs. Are you sure they are actively blocking access? Perhaps the internet connection was only temporarily malfunctioning.

Picric-A - 29-11-2010 at 11:17

Org Syn is blocked for some reason... not ACS or Wiley and/or Springer. I cant find any reference to this method on any of those though... could you point me in the direction of where i should be looking?

Satan - 29-11-2010 at 12:09

Found on gigapedia:

Organic Synthesis Archive - full version from orgsynth.org
organic_synthesis_archive.rar
size: 37.98 MB
MD5: b41a3131660df030c58a90d4f91b6522

PASSWORD: chem4all.vn

http://ifile.it/0atc23s/organic_synthesis_archive.rar

Nicodem - 29-11-2010 at 12:21

Quote: Originally posted by Picric-A

Org Syn is blocked for some reason... not ACS or Wiley and/or Springer. I cant find any reference to this method on any of those though... could you point me in the direction of where i should be looking?

Yes, I can point you here, where you can find one reference from Wiley, one from ACS and one from Springer.

Picric-A - 1-12-2010 at 23:24

Thanks for the direction, i am in the process of getting the school to unblock org syn.

In the final methylation of 5-methoxyvanillin i would like to use bromomethane as the methylating agent. Could i simply use a solution of bromomethane in acetone for the methylation? Does anybody know how soluble it is in acetone?

Thanks,

Sandmeyer - 2-12-2010 at 00:09

Quote: Originally posted by Picric-A

Thanks for the direction, i am in the process of getting the school to unblock org syn.

Huh? I don't know whether to laugh or cry when I read this...

Sandmeyer - 2-12-2010 at 01:28

Quote: Originally posted by Nicodem

For some reason people tend not to use this method any more.

Why would they when they can simply mix aldehyde, nitro and catalyst (and sometimes solvent) and filter the yum-yum?

Quote: Originally posted by Nicodem

I guess it is considered antiquated, or perhaps because it looks too much like a "two step" synthesis, which is not true as it involves no isolation of the intermediate hydroxynitronate salt.

Actually, it is a two step, one pot method...

Chevron7 - 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)

DrNoiZeZ - 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%.

Hate diggin up an old thread...

mrnye - 8-2-2012 at 20:25

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?

turd - 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.

mrnye - 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]

mrnye - 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]

turd - 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!

Nicodem - 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!

mrnye - 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]

Unfrying your brain from LSD And Marajuana

TopTrader - 10-2-2012 at 03:33

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]

turd - 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).

mrnye - 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:

Yeah idk what that guy was talking about.

[Edited on 10-2-2012 by mrnye]

Nicodem - 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.

mrnye - 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.

How To Unfry Your Brain

TopTrader - 22-2-2012 at 10:55

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]

peach - 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.

turd - 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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