paccman278
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n-butylamine
anyone have or had any experience with n-butylamine, or a substitute. not i, wants to know for 1-phenyl-2-nitropropene synthesis. swip has read that
ammonium acetate can be a sub, true or not? can other primary amines be used? thank you all!!! btw what happened to the hive?
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Darkfire
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Its down for upgrades or just fixing errors.
Your doing a aldahyde and nitromethane condensation correct?
Methlyamine is a high yeild substitute which requires no reflux.
My favorite method is the aldol condensation, using NaOH to condense the aldahyde and nitromethane and then HCL to dehydrate it to the nitropropene.
\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I
will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
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paccman278
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benzaldehyde+nitroethane---n-butylamine---=1-phenyl-2-nitropropene+hcl/fe=P2P
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Darkfire
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How are you getting the nitro ethane?
MeNH2 is the best way ive seen so far, beats cyclohexamine, n-butlamine, NH4AcO, and most everything else is ease and in yeilds.
For certain aldahydes it wont work, such as tmba in which case i use NaOH and HCl, but for your experiment MeNH2 will be good.
[Edited on 28-11-2004 by Darkfire]
\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I
will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
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Nosferatu
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| Quote: | Originally posted by Darkfire
For certain aldahydes it wont work, such as tmba in which case i use NaOH and HCl, but for your experiment MeNH2 will be good.
[Edited on 28-11-2004 by Darkfire] |
Thst's strange, with 3,4,5-trimethoxybenzaldehyde the yields are nearly quantitative. Can you post your failure?
Grof Orlock
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Swedish Chef
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I have worked with n-butylamine. It is a clear liquid, boiling at around 56°C, has a strong fishy odor and fumes in air.
If you are gonna use it, you probably need a fuming cupboard. 
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Darkfire
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| Quote: | Originally posted by Nosferatu
| Quote: | Originally posted by Darkfire
For certain aldahydes it wont work, such as tmba in which case i use NaOH and HCl, but for your experiment MeNH2 will be good.
[Edited on 28-11-2004 by Darkfire] |
Thst's strange, with 3,4,5-trimethoxybenzaldehyde the yields are nearly quantitative. Can you post your failure? |
Even sasha only got ~75% from PIKHAL, yeilds with MeNH2 were very high for Barium at the hive, but analisis of the product showed
it to be something other than the nitrostyrene.
\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I
will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
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paccman278
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darkfire,
nitro ethane is from ethyl iodide+dmso+sodium nitrite
refluxed, extracted,and distilled (60%)
methlyamine someone told me wouldnt work because of its low boiling point so would be boiled out durring reflux. true?
im in cali, anybody ever the butylamine before, problems?
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Darkfire
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Same way i wanna make the Nitroethane. And the thing with the MeNH2 is that it doesnt need to be refluxed. If the hive is back up search for
methylamine catilist or something like that, its bariums thread, he had overwhelming sucess with over a dozen aldahydes.
\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I
will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
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paccman278
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yeah the ethyl iodide is pretty easily made in bulk, swip has had many sucessful runs with that. the hive is still not up buy ill give it a run.
thanks for the help.
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Darkfire
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The amount of MeNH2 is very low. I prepared 2.5 grams of MeNH2*HCl distilled it in MeOH with NaOH and that is a good amount for 7 grams of 345 TMBA,
use some math to find how much you need for your molar amount.
\"I love being alive and will be the best man I possibly can. I will take love wherever I find it and offer it to everyone who will take it. I
will seek knowledge from those wiser and teach those who wish to learn from me.\" Duane Allman
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paccman278
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darkfire,
the hive seems not to work anymore. swip's been searching for text using the methylamine substitute for my project. cant find anything on
barium's post anywhere. if you have a copy or any thing that you think might help me ( a nice writeup maybe)  i would greatfully appreciate it. seems the n-but is hard to come buy here, nobody
want to sell it ....
thanks a million
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solo
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Ref: P2P
| Quote: |
Bozakium
(Hive Addict)
07-30-04 12:06
No 522724
Decant the supernatant liquid! You forgot to decant the supernatant liquid! Fools! Fools!
Here's the original synth, with all the details as it appeared in the Journal Bibliothek fur chemie von der Fremdenverkersburo:
(Proper German-English translation by Bozakium)
To a 25 litre crock nestled in a dry ice/acetone bath is introduced 4 litres of liquid(substituted) BzCN dimer. Dropwise with stirring 8 litres of
equimolar (25.223%) sodium methylate in anhydrous acetone is added. The stirring is continued until all the emulsion disappears into solution.Allow
to stand until no more emulsion forms, stirring each time to disperse it. Add 4 litres of cooled ethyl acetate as a co-solvent. Remove from the
dry-ice bath and allow to warm to room temperature. At room temp(20C), the solution will be seen to separate ito two separate, but hard to see layers.
Decant the supernatant liquid and discard it. This will pollute the product if allowed to remain,as it contains many Bz2 moieties which will thrust
their way into the crystal lattices; however the small amount (<50mL) left behind actually helps catalyze the crystallization. This is why we
decant.
Warm slowly (10-15C/Hr), with stirring to 60C. Crystallization will commence at 55-58C and cease before 62C. Any wider a range indicates a
polluted product or improper stoichiometry.Collect accordingly. Be sure to use the BzCn dimer, as even with adjusted stoichiometry, the momomer is
unstable and will cause polymerization in the end product (sticky goo). Gillmann /Blatt (1903) used (monoisobutyl)ether to assist forcing
crystallization, but diglyme is found to be better as it does not tend to force dirty crystals against their will as does ether. Vacuum filter through
a #69(really)Buchner funnel with 120-bore or smaller escrima paper. Drying may be done at STP, but is aided by a combination infrared/ultraviolet heat
lamp. Do not use a regular light bulb, as excessive photons in the 589 to 589.4 nM wavelength range(yellow) excite the electrons on the androgyne
carbon of the alpha-acetyl group and can cause explosive decomposition. Keep this intermediate out of direct sunlight for the same reason. Failing to
decant the supernatant liquid in the earlier step GREATLY exacerbates this danger! The white, needle-like prisms(other crystals indicate failure, an
incorrect product)are the sodium salt of n-acetylacetonitrile. Bung the salt at a rate of 450g /500mL of 40%(by wt. not vol.) sulfuric acid in a large
beaker with rapid stirring. "Bung" translates best into "refresh, with shooshing", this is done in practice as one would spread
rock salt on an icy sidewalk out of a scoop, with sweeping horizontal motion. I believe it is to allow the reaction with the sulfuric to proceed upon
maximum unimpeded surface area, to prevent diphenylacetone formation. Stir rapidly during bunging to break up the effervescence(or beaker will
overflow), until all effervescence(you should see the German word for that!) ceases. Proto- and final hydrolysis as well as the subsequent
decarboxylation should now be complete. Check by TLC eluted with 60/40 tin/lead dichromate(at 2% wt/vol dilution in deionized, distilled dihydrogen
oxide. Develop the plates with iodine vapour to visualize. If not complete, a SMALL amount of concentrated acid may be added dropwise wit very fast
strring, rechecking TLC after every .22 drops/mole of crystals used. Heat on an electric mantle(NO flame), with rapid stirring to 75C for one hour to
allow deracemization.
Add water to an acidity of 20%, checking with pH paper. The organic layer containing the product will float. Extract with light
petroleum(pentanes), wash 3x with a 10% sodium bicarbonate solution. Eveporate the solvent in vacuo. Yield should be 80-90%. Mp should be +/- 2 deg.
of reference product. Total synthesis time(minus workup) is ca. 2 Hr. This is a pretty small-caliber synthesis and should be easy for anyone to
compleat sucessfully. |
.....I searched my files and this is all I found so far....I hope it helps...
Here is a post by Rhodium , which covers a patent , in which they substitute with the butyl that you 're inquiring about....solo
http://home.ripway.com/2004-11/211899/anewsyntheticMethodofP...
[Edited on 3-12-2004 by solo]
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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paccman278
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thank you solo.
unfortunetly it was no help for swip, swip was reading and found in u. festers s.o.m.m. he says that" ammonium acetate would be OK. J.A.C.S vol.
56 pages1556-8 (1934) usnng ethanol as a solvent vs. toluene. if anyone has any writeup's on p2p via knoevenagel reaction i would be most
grateful.
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wertfun
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Darkfire could you little bit more detail this one you told before
Your doing a aldahyde and nitromethane condensation correct?
Methlyamine is a high yeild substitute which requires no reflux.
My favorite method is the aldol condensation, using NaOH to condense the aldahyde and nitromethane and then HCL to dehydrate it to the nitropropene.
[Edited on 3-12-2005 by wertfun]
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