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enima
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Quick question: @ what temp does the aldehyde, either 3,4,5-trimethoxybenzaldehyde or the 5-hydroxyvanillin begin to decompose?
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Sandmeyer
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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]
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enima
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Sandmeyer, try the reaction with n-butylamine you you should have higher yields. EDDA only works well on a few nitrostyrenes,
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Sandmeyer
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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.
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Vitus_Verdegast
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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.
Sic transit gloria mundi
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xxxxx
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alternate route to desired compound
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.
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ctrlphreak
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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?
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arsphenamine
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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.
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randolph_carter
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my 64,382 cents worth on a tma2 sythesis....
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.
--------------------------------------------------------------------------------
\"......remember little ones, love is real not fade away, so pass some on today......\"
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randolph_carter
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NOT 2,4,5 eh???
ooooops "3,4,5" NOT "2,4,5" tma....
my bad but you may find some pointers anyhoooow......
\"......remember little ones, love is real not fade away, so pass some on today......\"
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zajcek01
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Would triethylamine catalyst work instad of cyclohexylamine, butylamine and methylamine for condensation of 3,4,5-trimethoxybenzaldehyde with
nitromethane or nitroethane?
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Nicodem
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| 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.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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SelfStarter
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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.
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Nicodem
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| 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. |
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]
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arsphenamine
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| 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.
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SelfStarter
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| 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.
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Picric-A
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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,
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DJF90
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If its blocked by your school then you probably shouldn't be doing it...
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Nicodem
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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.
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Picric-A
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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?
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Satan
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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
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Nicodem
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| 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.
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Picric-A
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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,
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Sandmeyer
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 Huh? I don't know whether to laugh or cry when I read this...
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Sandmeyer
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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...
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