Benzaldehyde and Other Questions

[Buster_Hymen]

A buddy thinks he may have a source of pure benzaldehyde from a local distributor. The stuff is sold in specialty cooking stores as "Oil of Bitter Almond". It's a "fancy-schmancy" brand, targeted for people who think they're gourmet cooks or something. It does not look or smell the same as the cheap shit you buy at Safeway, which is mostly alcohol. The ingredients say "Oil of Bitter Almond" only. Nothing else. No alcohol or propylene glycol or anything. The color is pale yellow, with MAYBE a slight, slight hint of green to it. It smells intensely of almonds (of course), and a tiny dab on the tongue made him gag with a nazty, bitter, burning taste.

His questions are:

1. He's reasonably sure this is pure Benz. (water solubility: <0.01 g/100 mL). If he assumes that likely adulterants would be ethanol (water solubility: >=10 g/100 mL) or propylene glycol (water solubility: >=10 g/100 mL), couldn't he just do a water wash of this material, and if he gets back very close to what he started with, he can assume it is highly pure Benz.?

2. Distillation is not an option for this guy. Can he expect to have any success creating P2NP (using that Benz. + NitroE + EDTA method Osmium wrote up), in combination with a Urishibara reduction, to yield plain old Amphetamine, WITHOUT having to distill anything? (seems like he could make it work without lab glass, based on Antibody's, Ritter's, and others' old threads, but just checking)...

3. How long will the P2NP keep before he should reduce it? (refigerated vs. NOT refrigerated)?

4. How long will the Urishibara catalyst keep before he should use it (assuming it's prepared same way as Ritter did), and what is best way to store it?

Thanking you in advance for any and all comments.


  \\|//
    ô¿ô     -- Free Spitball and give him a wedgie!
    \O/
      '''

[PolytheneSam]

Have you looked at this page?

http://www.geocities.com/dritte123/Nipat.html

http://www.geocities.com/dritte123/PSPF.html

[BieneMaja]

to2: there is no need to destill while producing p2np, but to reflux. swib made good experiences w/ benzaldehyde + nitroethane + butylamine. yields were in the 90%+ range and she need 3 hrs. to prepare a 110g batch p2np.
but she thinks there is a need to distill when using the urushibara way, but maybe she's wrong cause all three time she tried it via urushibara she fails
 
a few days ago she reduced via Pd/C and ammoniumformiat and was very happy to obtain white amphetamine sulfate in a good yield w/out destilling anything, so that and the LAH reduction are more in her favor.

to3: for the Pd/C thingie she used p2np which was prepared a month ago and which was stored in a dark glasbottle in the fridge. after all she's heard storing airtight sealed in a cool dark place is a must to avoid this f*cking red gakk which comes up when the p2np polimerizes/degenerates.

to4: although she failed everytime she used urushibara cat. she would recommend to produce it just before using it. after all she know the cat will lost lots of it's catalytic capability when stored.

(sorry for the screwy english, i did not use it for awhile now)
kallos kai agatos

[hest]

Did she reduce P2NP to Amph. with Pd/C and Am.Form.??
Iff so how mannye g of Pd/c per g P2NP did she use ??

[Osmium]

1) That should work. Aquire a graduated measuring cylinder or a syringe (10-20ml), introduce ~3-5ml of your supposed benzaldehyde, and about 2-3 times as much water. Close opening with your thumb, shake well, and let separate. If there's aclohol present the organic layer will be smaller than before. If the phase separation isn't good you could also add a few milliliters of DCM or toluene or other organic solvent and compare the respective volumes.

2) It's ethylenediamine diacetate, not edta!
In industrial pharmaceutical production distillation of products is rather uncommon. The intermediates and products are often purified by crystallization if possible. Can't hurt to recrystallize the P2NP, especially when you intend to store it.

[BieneMaja]

she followed the instructions on rhodiums page

https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitropropene.cth.txt

(http://) with a few changes:
she had only lab-grade Pd/C 10% so she used only half of the amount given in the procedure and followed cherrie baby's advice and used some more am.form. (this stuff is cheap).
she used eth-o-eth to xtract and formed bright white crystals w/ conc. H₂SO₄.
next time she'll use home made Pd/C 5% i let you know how it turns out.
hope this helps
bm

kallos kai agatos

[PolytheneSam]

See this post

Post 208702

(Antoncho: "The easiest synth of benzaldehyde from toluene", Chemistry Discourse)
http://www.geocities.com/dritte123/PSPF.html

[BieneMaja]

hmm this post sounds good.
to bad that swib has a source for lab-grade, but who knows for how long..
thx

kallos kai agatos

[Dr_Sister]

i know of at least two bees who have successfully synthed amphetamine from P2NP with Urushibara Nickel precipitated on Al. The precipitation conditions make a large impact on the activity of the catalyst, as does the method of activation.
7.10.01

[Rhodium]

Sister: I know I have one of those successful attempts archived at my site - what about the other one? Could someone compile a list of successful Urushibara reductions (post numbers and/or new writeups of trials) to me so that I can make a better review of the procedure on my page. Has it been used on phenethylamines, or only amphetamines?

[foxy2]

Buster
Try this

Post 231955 (missing)

(foxy2: "Nitrostyrene or Nitropropene electrochem reduction", Chemistry Discourse)
Read all the pdf's at

http://l2.espacenet.com/dips/bnsviewer?CY=ep&LG=en&DB=EPD&PN=GB2122617&ID=GB+++2122617A++I+

This electroreduction of nitropropenes and nitrostyrenes really looks good.  All the materials can bee easily found or made.  The only thing I am unsure of is what to use as a divider in the cell?  Condom?

Foxy

Fully Informed Jury!

(http://www.fija.org/)

[Dr_Sister]

i'm not aware of anyone triing with phenethylamines, but i can say that the yeilds fluctuate dramatically among different nitropropenes. the other thought on these catalysts is that Al foil probably isn't the best way to go, as the initial precipitation is very vigorous, but then quickly slows it produceds catalysts of inconsistent activity. An Al or Zinc powder of uniform mesh size that could be added all at once, would be a good way a catalyst of more uniform activity could be produced. i'll pm you the name of the other bee.

Has any bee triied the Zn precipitated Ni yet? Hata's book implys it to be less selective.
7.10.01

[Rhodium]

Do you mean that the yields fluctuate between different nitropropenes, but are consistent between runs with the same NP?

[Dr_Sister]

yes, the best yeilds 60%, were reported with P2NP, followed by TMP2NP at 55%, p-MP2NP at 25% and both MDP2NP and DMMDP2NP failed altogather with acidic activations. in most cases at least two rxns, in some like MDP2NP several times with a whole spectrum of variations.
7.10.01

[ChemicalSolution]

Distillation is not an option for this guy

You could use the bisulfite addition to isolate the aldehyde.

xoxo-Julia

[Lino]

Buster, hope you find the following useful.

To a 2 1/2 litre brown glass winchester, on a stirrer, add in the following order:1060g aldehyde, a 3" stir bar, 750g nitroE, 99g cyclohexylamine. Begin stirring, hopefully the stir bar will not go walk about. Continue stirring for around 20 mins.

Screw the cap on the winchester and put it in a dark place. SomeBee, being pernickity, takes out the winchester every couple of days and pipets off the water which will have formed. He doesn't know if this helps as the water is not actually in the rxn, it floats on top.

After 20-ish days a crystalline yellow layer will start to form on the bottom of winchester, it will grow upwards and eventually fill the winchester with yellow xtals. When it nears the top it's best to decant off the lacrymatory liquid into a smaller 1l winchester. Keep the big winchester upside down for 1/2 hr to drain off all the eye stinging liquid from the yellow mass. It may be nessessary to add more base catalyst to the remaining yellow oil at this time, say 10% of it's volume, and mix well.

Cover the xtals in the big winchester with cold IPA or MeOH and shake. You can then leave it in the fridge until required for further experimentation.

To retrieve your product, you must slowly heat the winchester in a water bath to 60ºish, having first decanted off the OL, which you boil up and return to the now hot winchester. This part of the operation is very, very eyewatering.

The cold condensation results in a clean product which does not require re-xtalization... but you can if you want.

Ohhhh! Your yield of yellow stuff, should you dry and weigh it, will be 1-1.3 Kg.

Lino

ps  you will find it far more rewarding to make ketone from the yellow stuff. Then follow Os's Al/Hg advice.
Linoleum: the 13th element!  Now available at all good DIY stores... & Walmart.