P2NP to P2P rx vessel

[raffike]

Ok,raf got some benzaldehyde and probably will get some nitroethane soon.But there lies that problem with P2NP to P2P reduction step,it needs good vessel so raf thought,since SS rusts,he could make copper vessel for that purpouse.Copper should handle HCl acid just fine.Or is there any reason one should not make it from copper?Raf has 5 liters of benzaldehyde and it makes about 6 kgs of P2NP and 50 liter vessel should be ok.Raf has few questions more so if anyone is familiar with that method,it would be nice if he replied.
PS. i made 30000'th post to stimu forum
For those about to synth,we salute you

[Rhodium]

Copper is not compatible with concentrated HCl, I would really like to suggest that you perform the conversion in several smaller batches using normal glass, or that you use stainless steel and the Iron/Acetic Acid reduction instead.

6kg of P2NP from 5L benzaldehyde was pretty optimistic, how are you planning to perform this condensation? When you have so much starting material to convert, could you do the Hive collective a big favor and perform the condensation in several smaller batches varying the reaction conditions, so that you can help develop an optimized procedure? If you are interested, PM me and I'll give you a set of suggested variations.

How are you planning to isolate the product afterwards? Solvent extraction or steam distillation? At the scale you are suggesting, whatever you choose will involve an incredible amount of work.

Terbium is the person you'd want to consult in this matter though.

[raffike]

I've read many posts and hardest chemical for me to acquire would be that catalytic iron powder(laughs please).Steam distillation seems to be less messy than solvent xtraction but lots of electricity will be wasted to generate these big amounts of steam,although one could use propane for heating.Haven't found any nitroethane yet but it will be no problem for raf.Benzaldehyde will be converted to P2NP with cyclohexylamine.That's 20 bucks a litre from Fluka and it'll be enough for 4-5 kg's BzCHO.One could also electro-reduce P2NP to amph and it might be better way than via P2P.And there's also LAH reduction.I'll gladly help ya if i can.
For those about to synth,we salute you

[Rhodium]

You don't need to generate external steam to be able to perform a steam distillation, just dilute the organic phase with twice its volume of water, and then distill as usual. For every gram of P2P distilling over, 10 grams of water will co-distill, so use a sepfunnel as a recieving flask, and periodically return the water to the distilling flask.

[raffike]

Ah in that case steam is way to go.Sent you a pm already.Raf has some 12 liter roundbottoms so rx vessel will be no problem.Now he he orders some cyclohexylamine.Rhodium i'll send you a pm when cyclo arrives.
For those about to synth,we salute you

[WizardX]

raffike: Read the procedure below BEFORE you start. Just use 5 moles of nitroethane. I would suggest to do a small-scale run first.

NITROSTYRENE

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0413

[Hematite]

Wiz you mention nitroethane and yet the link says nitromethane in the synthesis? Just curious is all.

Raffike If you get hold of nitroethane, combining it with your benzaldehyde and a little dry ammonium acetate and then gently reflux for 5 or 6 hours and you have a simple high yielding route to P2NP that never fails despite my ever changing reaction specifics. (that's chemspeak for haven't got a fucking clue!)
The crude product once recrystalised from hot MeOH is beautiful pale yellow needles all about an inch in length that are so nice that they no longer have any effect on your eyes or sinuses....................ok, that's complete bullshit but they are pretty! 
Regards, Hematite.

[raffike]

No nitroethane needed?Nitromethane is common model racing fuel over here.Wow,WizardX you are the best.I'll dive deeper into that procedure.Thanks
That ammonium acetate procedure seems ok too since i could get hold of ammonium acetate easily.
EDIT:But styrene yields phenylethylamine when reduced,that makes it little harder overall.I see if i can get nitroethane and what were the yields when ammonium acetate was used?
For those about to synth,we salute you

[Rhodium]

WizardX probably mean that you should use the OrganicSynthesis procedure, but instead of the nitromethane use nitroethane, to produce phenyl-2-nitropropene instead of nitrostyrene.

[raffike]

ah,why didn't i figure it out myself.Thanks rhodium
For those about to synth,we salute you

[Osmium]

I love it when people acquire a certain amount of a chemical and then wonder how to convert that stuff into something usefull all at once!

What if the reaction they intend to use fails?
What if the reaction they intend to do only runs in smaller amounts?
What if the writeup is incomplete, missing a few small but crucial details?
What if the workup will be very difficult?
What if the cook fucks up? Or a flask drops? Shit happens all the time.

It is usual to read stuff like "... extracting the product with DCM, washing the combined extracts twice with NaHCO3 followed by H2O, evaporating the solvent to yield crude product (VII)..." in chemistry journals. What that sentence doesn't tell you is that it might have taken the researchers a full day to perform this step on a small scale, and it will take you several days to do it big scale. Now imagine your product being somewhat sensitive and not handling the conditions it is under very well. Can you imagine the unexpected yield reduction when it will take you three days to do it?
Been there done that, and it sucks!

That's why I say plan your synth carefully, start small and work your way up slowly and deal with the problems as they arise. Only a fool would bet all his money, belongings, wife and children's destiny on a race horse he doesn't know.
I'm not fat just horizontally disproportionate.

[raffike]

Raf's planning to run synth described in Louis Freeh large scale benzaldehyde to meth story,just cyclohexylamine is used not n-butylamine.Freeh describes how to construct large vessel for Fe/HCl reduction too.Raf has some big glassware so he doesn't need to construct anything.Benzaldehyde to P2NP with cyclohexylamine is described in

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenyl-2-nitropropene.html

Scale-up should be no-problem.
For those about to synth,we salute you

[Rhodium]

Louis Freeh is an FBI director, and I don't find that alias in the user database. Could you point me towards the story you mention?

Just a cautonary note: While you may be able to synth phenyl-2-nitropropene on a large scale by just scaling up a lab procedure, the same is not true with the iron reduction to P2P. Try it using as little as 100g P2NP first and you know why it isn't fun to do on a multi-kg scale.

[raffike]

That procedure is on your website.In that zip file,4-th doc.

https://www.thevespiary.org/rhodium/Rhodium/archive/cookbook.zip

For those about to synth,we salute you

[Hematite]

Yield from the benz/nitro/ammonium acetate synth are extremly high and consistantly easy to obtain, never calculated it precisely however.
Rhodium is very correct in advising small beginnings with the iron/acetic acid stage to P2P, it has humble beginnings that quickly turn into a volumous messy shitfight of a workup sometimes and on a larger scale than I had expected, too big would really suck if one wasn't anticipating the necessary requirements, good luck.
Regards, Hematite.

[raffike]

Iron/acetic acid is very volume inefficient procedure.If one had 4 or 5 kgs of P2NP,he would need copious amounts of GAA.Fe/HCl seems to be the best way.There's some procedure with cromium(II)chloride too but that isn't tested yet.
For those about to synth,we salute you

[Rhodium]

It is not so much the GAA being the problem, more that you will have to dilute the post-reaction mixture so much after the neutralization to be able to do anything useful with it (regardless of choice of acid), the precipitated iron salts are extremely voluminous and gel-like.

[raffike]

Yeah,it needs lots more iron than HCl method.Ammonium acetate is a chemical i can get easily(reagent grade),just substitute cyclohexylamine with AmAc.Raf's probably going to some test runs soon,like 100 grams of benzaldehyde,80 grams of nitroethane and 20 grams of ammonium acetate and see what comes out.
For those about to synth,we salute you

[Barium]

on a small scale. If you have done it on a 10 mmol or a 100 mmol scale increase it to a 1 mol scale before you jump up to a 10 - 50 mol scale. Very strange things might happen when things are scaled up. This is the difference between research chemistry and production chemistry. Let me tell you that there is a huge difference between them.

Research chemistry never takes into consideration the necessary parameters for large-scale production. It is very common to find something new and interesting in the litterature but it is impossible to produce anything profitable from that description. So in order to go into production everything or close to everything has to be done from scratch again.

Researchers very often use Pt- or Pd black for catalytic hydrogenations. Production plants never ever use those catalysts. They are way too expensive. Ok, there might be a few exceptions to what I´ve just said. But those exceptions are always when there is no other catalysts which works and the product is like 50 times more expensive than gold.

What about GAA/Fe or HCl/Fe reductins then? Well some factories actually still use HCl/Fe for large-scale reductions of various aromatic nitro compounds. But those factories are always located somewhere where electricity is cheap because steam distillaton is the only way to separate the product from the nasty iron sludge.
Catalytic hydrogenation freak

[Barium]

Nitro alkene derivatives
H.B. Hass, A.G. Susie, R.L. Heider

J.Org. Chem. Vol 15, pp. 8-14 (1950)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/nitrostyrenes.fe-hcl.pdf)


1-Phenyl-2-nitropropene

One mol each of benzaldehyde and nitroethane, 5 ml n-butylamine and 100 ml EtOH were refluxed for 8 hours in a 1000 ml rb-flask. When the contents were cooled and stirred a heavy yellow crystalline mass formed immediately. After recrystallization from absolute EtOH the product weighed 105 g (conversion 64% of theory, yield 86,5%) with a m.p. of 65°C.

1-Phenyl-2-propanone

One-tenth of a mole of nitroalkene, 0,72 gram atom (40 g) of 40 mesh cast iron turnings, 75 - 100 ml of distilled water and 0,1 g of ferric chloride were placed in a 500 ml rb-three-neck flask equipped with a graduated dropping funnel, a mercury-seal stirrer and a reflux condenser. Fifteen ml of conc. HCl was added dropwise over 5-6 hours and the temperature of the surrounding oil-bath maintained between 85 - 95°C. The mixture was then basified with 25% aq NaOH and steam distilled. the distillate was extracted several times with ether, the ether distilled and the residue rectified through a Podbielniak column at reduced pressure.


--------Molar ratio--------ml/mole alkene--------Product--------
--Fe/alkene--HCl/alkene----Water--Solvent------P2P--P2p oxime---

---2---------0-------------500-----0----------0%------ 20,1%-----
---2---------0,06----------500-----0----------5,2%-----49,0%-----
---2---------0-------------500-----0----------0%-------0%--------
---2---------0,1-----------500-----0----------11,3%----32,5%-----
---2---------0,232---------500-----0----------24,6%----27,4%-----
---2---------0,464---------500-----0----------36,5%----23,1%-----
---2---------0-------------500-----0----------3,7%-----23,8%-----
---2---------0,06----------500-----0----------3,7%-----45,0%-----
---2---------0.06------------0---500(a)-------0%-------0%--------
---1---------0,06----------500-----0----------trace----34,6%-----
---2---------0,06----------250---500(a)-------10,5%----62,6%-----
---2---------0,06----------250---500(b)-------0%-------0%--------
---2---------0,06----------250---250(a)-------10,7%----45,6%-----
---2---------0,06----------250---250(b)-------0%-------0%--------
---1---------0,06----------250---250(b)-------0%-------0%--------
---2---------0,06----------250---250(c)-------9,9%-----64,2%-----
---2---------0,06----------250---500(c)-------9,7%-----63,0%-----
---2---------1,392---------500-----0----------41,1%----20,2%-----
---2---------1,74----------500-----0----------56,0%----13,4%-----
---2---------1,74---------1000---500(c)-------41,0%----30,2%-----
---2---------1,74---------1000---500(b)-------18,7%----40,3%-----
---7,15------1,74----------750-----0----------75%------0%--------
---7,15------1,97----------670-----0----------77%------0%--------
---2,5-------2-------------500-----0----------44,7%----20,2%-----
---2,5-------0,52----------500-----0----------10,5%----37,5%-----

(a)- MeOH
(b)- Benzene
(c)- EtOH



Catalytic hydrogenation freak