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Author: Subject: Phenyl-2-nitropropene reduction
aldol
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[*] posted on 7-3-2005 at 22:56
Phenyl-2-nitropropene reduction


I recently had a dream of reducingp2np to the amine with sn and hcl
Procedure went like this.
in a 2 litre beaker was 30 grams of recristlized p2np , 120 grams granulated tin with just enough water to cover contents.
A mechanical stirrer was fitted and the contents was heated to 50c
added dropwise was 200ml of 37% hcl over a period of 8 hours
the contents upon conpletion of the reduction had gone from a yellow p2np colour to to clear water
I then carefully basified water to ph13 which percipertated out tin hydroxide whitch i filtered out
I then had a yellow as water phase with a little bit of sodium cloride in it from reaction
Next i evaperated down the water to yeild a yellow product mixed with sodium cloride
When it was dry i added 250ml dry ethanol which dessolved the organic phase but not the nacl i then had a nice yellow alcohol phase
Dropwise i added conc h2so4 which percipertated out a very white powder
I then filtered to collect 26 grams of product wich i thought was amphetamine sulphate but was not did it go to the oxime or some other intermediate could somewone with more knowledge tan me help
I would be much apprecaited thank you:o

Edit by Chemoleo: Changed title, you can't assume everyone knows what p2np is.

[Edited on 8-3-2005 by chemoleo]
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aldol
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[*] posted on 8-3-2005 at 12:45
phenyl 2 nitro propene


thank chemolio for the change although if they don t no about p2np they proberly would not no anything about the conplex chemistry involving p2np :cool:
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runlabrun
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[*] posted on 8-3-2005 at 19:04


Its not that complex.... and p2np is not a correct chemical descriptor, just a clandestine chem acronym...
More likely that you have the oxime after this method, what was your reference? source of info....

-rlr
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aldol
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[*] posted on 8-3-2005 at 20:04
reduction


HIGH RUN LAB RUN i had no referances to this method i new tin was selective towards nitro compounds so i worked out a method myself
not bad yeild pitty its not the goods
regards to phenyl 2 nitro propene any compound that can be rearanged into 4 or five compounds is not simple chemistry
if i had access to a mass spec i would have had it going a long time ago
if i new what the intermediate was i would no what to do with it regards
regards aldol
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runlabrun
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[*] posted on 9-3-2005 at 22:43


Rhodium backups have a nice page of this proceedure using easy materials..
im not going to post the method but look for it on one of the millions of backups online...
"Amphetamine from P2NP using Urushibara Nickel (NiCl2/Al) "

-rlr
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aldol
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[*] posted on 10-3-2005 at 01:45
p2np


hi lab run lab
thanks for the info i have played with urishabara catylist
made from zinc i have not used aluminium to percipetate the nickel
I did not try the reduction using it
i thought there would be a problem scaling up
thinking about the 8 time molar excess of aluminium
where in my tin reduction i can scale up huge have tryed it 2kg no problem
has any one scaled the urishabara method if so i would like to here
from you, and can you reduce the oxime with urishabara and can anyone help with a good reduction for the oxime

the more the frustration the more the reward:o ALDOL
,
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aldol
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[*] posted on 10-3-2005 at 14:57
reduction


shorly someone has thoughts on this lots of lookers the method is so clean
and the workup is simple
posting a good method like this deseves a response
i have a method for p2np no glassware
just a coke bottle sit on shelf for 2 weeks
depending on weather volla i have seen
this done with cyclohexylamine as catylist but have not seen a method for ammonium acetate my method is billiant low key but am reluctant to post it wy post it when you get no responce
or is it all the people o n this site dreamers or studants anyone can put refs on about methods you can get anywhere but when it comes to the crunch studants and dreamers think they can help but cannot i have heeps of exsperiance with production of p2p and methylamine lots of other procedures but why should i share my exspeariances
not dreams
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enima
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[*] posted on 10-3-2005 at 15:34


Take a look at the Al/Hg reduction of nitrostyrenes on rhodiums website, p2np is reduced to amphetamine with a 83% yield. All you need is some foil and some mercury salt. (you can scale this reaction to some degree)

I'm personally don't like metal + hcl reductions they are very unreliable and yields are piss poor.
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aldol
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[*] posted on 10-3-2005 at 16:20
reduction


thanks anima have used hgsalts in reductive aminations bot i am trying to get away from nasty hg salts now i am using different precurses
have you done na metal in alcohol reduction of the oxime is it a good clean method i no vogul uses it but i would like to no
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[*] posted on 10-3-2005 at 17:58


You can get away from the Hg salts and still do a Hg/Al reduction by sticking to using elemental mercury, which is significantly less toxic. Measure out your mercury in the reaction flask, then add the proportional amount of HNO3 and wait for the mercury to be turned to its salt. This save you from storeing, measuring, and messing around with the salt until its in your reaction vessel ready to go.



\"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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[*] posted on 10-3-2005 at 19:08


yea, I understand why you'd want to avoid mercury salts. I'm so paranoid that I go through 4-5 pairs of gloves from removing the salt from its container to putting it back in the container.

Anyway, you might have an oxime, I know that Lead in Acetic acid reduced nitroalkenes to oximes. You could try the reduction with zinc. Mix the nitropropene with the zinc and slowly add it to an HCL ethanol solution. I'm not sure on the precise proceedure. But I attempted this a long time ago (with 3-methoxy-4-hydroxynitrostyrene) and I did get a product. Not very much but I product. I didn't have equipment to test it and I'm not quiet sure of the effect of 3-methoxy,4-hydroxyphenethylamine. Nor would I like to be the first to find out.

Too bad vitride isn't avalible it would make things easier.
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[*] posted on 10-3-2005 at 19:31
reduction


thank for the info on the murcury salts that would help but you still have to do a filtration somewhere thats the problem
i would like some info on the reduction of the oxime i think two stepping is a larger scale way of doing it direct reduction is way to small for me i didnt put all my efforts for small amounts regards aldol
thank heps for the tips shorly someone has done a large scale reduction from the oxime i will love you heeps
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[*] posted on 11-3-2005 at 17:00


You originally said you ran the method using 30 p2np.... which is not large scale...
The method i posted can be scaled up but as far as i know not as far as a normal Al/Hg.... I think the only concerns you would have with scale on the urushibara would be stirring and temperature control, to far and it might get nasty... The footnotes on the page mention the yield can be increased a bit by using heavy overhead stirring, this would be essential if you were to scale it up at all...

What size batch(s) are you refering to when you say large scale??? With any reduction path there is a certain limit...
-rlr
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[*] posted on 11-3-2005 at 18:09
reduction


hi lab run lab
the 30 gram method i posted was the amount used to work method out
i have since done the tin reduction on a 2kg amount the results were the same
this reaction happens at a fairly lo temp
just keep adding acid until all the nitro is gone you will have a clear water layer when finished i have tried this with alcohol the results were the same
after basifiying you wont beleave how clean things are you will think were is the mess , there is none the bigger the amount the longer it takes
i think it is the same as the stanous chloride method to the oxime the only
difference is you are producing stannous chloride in sitsu slowly from the reation
which i think gives a lot less polermerization.
than stanous chloide
it is a brilliant way to the oxime
basifiying the oxime allowes you seperate the oxime from the salts and the hydroxides
i just need a reliable reduction of the oxime i have done the urashabara method on a small scale very messy
benz- NITRO - HUGE
NITRO - OXIME -HUGE
OXIME HELPPPPPPPPPPPPPPPPP


THANKS FOR THE CHAT LAB RUN LAB
REGARDS ALDOL [ COOL NAME ]
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enima
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[*] posted on 12-3-2005 at 03:21


Al/Hg is good for reducing oximes. :)

Also Ammonium Formate and Zinc work ok.
I think you may get higher yields from Ammonium Formate and Magnesium.
For these proceedures make sure your oxime is recrystallized and pure as possible.

I'm gonna go ahead and say it, I personally don't condone the synthesis of amphetamines or their nastier n-methyl brother, but to each their own. This is chemistry after all :)

Btw. the ammonium formate is easily made via ammonium carbonate and formic acid. Titrate to a nice pH of 7 and remove the water.

Ammonium carbonate is sold as Bakers Ammonia.



[Edited on 12-3-2005 by enima]
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aldol
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[*] posted on 12-3-2005 at 12:34
reduction


thanks enima
i no tat most people on this site dont like
amphetamins
if i had as much piperanol as i have benz i would not be using benz
but when i get the oxime reduction working i will be looking out for piperanol
i would much rather do the reduction
on p2np than muk around with pills
if you muk with pills you will get court
i can go to p2p but the procedure is to long
enima thank for the refs on the oxime reduction havent seen that way before
regards aldol
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enima
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[*] posted on 12-3-2005 at 15:32


Synthetic Communications 34(4), 599-605(2004)
for the magnesium catalyzed reduction. I believe its also aval. on rhodiums website (one of the mirrors)


Typical Procedure

To a solution of the substrate (10 mmol) in methanol or in any other suitable solvent (20 mmol) was added ammonium formate (30 mmol) and magnesium powder (1g, 0.041 mol). The mixture was stirred under nitrogen atmosphere at room temperature. The reaction was exothermic and effervescent. After the completion of reaction (monitored by TLC), the reaction mixture was filtered through celite. The organic layer is evaporated and the residue was dissolved in chloroform or dichloromethane or ether and washed with saturated sodium chloride solution to remove excess ammonium formate. The organic layer was dried over anhydrous sodium sulphate and evaporation of the organic layer followed by purification either by preparative TLC or by column chromatography to yield the desired product.
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[*] posted on 12-3-2005 at 17:38
reduction


thanks enima
the method looks good
isnt amonium formate the by product of the ammonium chloride and formilin condensation [ methylamine ]
i think i no that nasty smell it disstills of first
correct me if i am wrong :cool:
regards aldol
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[*] posted on 12-3-2005 at 19:00


I'm not sure exactly, hehe but methylamine is a foul smelling chemical.

You could use ammonium chloride to reduce the oxime. If you are going to be using the zinc method dont forget to activate the zinc via stirring it in dilute [hydrochloric] acid (5-7% generally) otherwise yields will be very low.



[Edited on 13-3-2005 by enima]
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aldol
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[*] posted on 13-3-2005 at 01:47
reduction


i no whae you mean about foul smell
been a long time but never forget the
smell , like stail pussy
getting back to the reduction the amalgam way sounds ok
i cannot use hcl because of the formation of p2p whitch rules out a clemenson reduction or any reduction involving acid
is this theary correct ?
i would like to no your thoughts
and can you use nicl instead of hgcl for the amalgam
regards aldol:cool:
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enima
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[*] posted on 13-3-2005 at 11:39


The zinc ic activated in the hcl solution, which is then filitered and washed with water to remove the acid. 2-3 washes with 100-200ml of water on 20g of zinc generally gets rid of most of the acid.

Unfortunately, no, you cannot replace the mercury salt with NiCl2.
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[*] posted on 14-3-2005 at 20:20
reduction


thank enima i did,nt think you could

There must be someone out there that has done sodium in alcohol reductions of oximes HAVE LOT OF N/A METAL
i used to have 3 edition vogul
the method is in there but lost it
if it works for vogul it will work for me
and does the oxime have to be in base form for reduction
and can it be scaled
i would much rather use sodium metal than mercury salts
it looks like no one is comenting
i will have to try and tell
:(
regards aldol
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[*] posted on 15-3-2005 at 14:56
reduction


hi enima
the ammounium formate method looks good i thought that the formate had to be used with pd/c for direct reduction to the amine
my research said that it will reduce oximes to amines on a large scale
could you show me the mechanism
of this reaction
? between oxime magnesium and ammounium formate
and any tips to do this
any help would be appreciated

Edit: merged this with the existing thread.

[Edited on 3-16-2005 by Polverone]
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people eater
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[*] posted on 25-3-2005 at 00:29
some oxime reductions from rhodium's site


I imagine you could base your work on Sonson's Na reduction of mdp2p oxime or on another oxime reduction mechanism his references describe-

Step 2. Reduction of the oxime.

3.86g (0.02 mole) oxime was dissolved in 50 ml dry ethanol (fresh 99.5% is OK, otherwise look in Vogel for a procedure for making anhydrous EtOH with Mg and I2) in a two-necked 250ml roundbottomed flask equipped with a condenser, a cork and a stirring magnet. The reaction mixture was heated to reflux, the heat was turned off and 5g elemental sodium was added in such rate that a steady reflux was maintained (make 20-30 pieces and store under hexane). The first additions is conviently kept small. (NOTE: Hydrogen evolution). At the end the reaction was slower so the heating mantle was turned back on to speed things up. The waterwhite, clear postrxn mixture was then slowly treated with 16g H2SO4 in 200ml cold water. The EtOH was removed under vacuum, and the resulting water phase was washed twice with DCM. The aq. phase was made basic by addition of 25% NaOH. The freebase was extracted with 3x30ml DCM. The pooled organic extracts was evaporated under vacuum to constant weight leaving a pale colored residue (3.36g, 94%).

The freebase was dissolved in 20ml IPA, neutralized with 1.6ml HCl and percipitated by the addition of 40 ml Et2O. The crystals was filtered and washed with a small amount of Et2O. Yield: 3.4g of white MDA-HCl. Mp 187.5-188.5°C. (Litt: 187-188°C)

This reduction can also be done in n-BuOH according to [5], and with quite a few NaBH4 reduction systems (NiCl2[6], TiCl4[7], MoO3[8], Co-PC[9], amberlyst-15+LiCl[10], and even with plain NaBH4 in EtOH according to [11]). Adding NaOH to a suspension of Ni-Al is also said to reduce oximes[12] as is SnCl2-Sn-HCl[13].

Different synthesis of oximes starting with nitroalkenes should be looked into, as this could be a good alternative to the existing methods for reducing nitroalkenes. SnCl2 reduces nitroalkenes to oximes under both acidic and basic conditions[14, 15, 16). Zn(BH4)2 in 1,2-DiMeO-ethane does reduce 3,4-MD-phenyl-2-nitropropene to the oxime in good yields [17]. Another promising route is the use of Pb in DMF [18]. This seems to reduce most nitroalkenes to the corresponding oximes.
References:

1. J. Pharm. Sci. 69; 2; 1980; 192-195
2. CA 1955;10595
3. Chem. Ber. 114;12;1981;3813-3830
4. J. Chem. Soc. Perkin. Trans. 2;2;1997;249-256
5. JACS 56, 487 (1943)
6. Chem. Pharm. Bull. 36;1988;1529-1533
7. Synthesis 9;1980;695-697
8. Chem. Ber. 117;2;1984;856-858
9. Angew. Chem. 93;5;1981;477-479
10. Syn. Lett. 4;1999;409-410
11. J. Chem. Soc. Perkin. Trans. 2; 1980; pp83-86 (very sparse information)
12. Aust. J. Chem 34; 1;1981;45-56
13. JACS 67;1945;496
14. Tetr. Lett. 26;49;1985;6013-6014
15. Synth. Commun. 18;7;1988;693-698
16. Heterocycles 24;9;1986; 2581-2586
17. Tetrahedron 48;25;1992; 5317-5322
18. Tetrahedron 48;21;1992; 3313-26 among others

Or you could adapt Antibody2's Al/Hg/AcOH reduction of mdp2p oxime-

Experimental

In a 4l beaker with mag stirring, 0.75 moles of activated Al (19.5g) [1] is added to 1l 95% EtOH and 100mls dH2O, followed by 0.33 moles oxime of MDP-2-P (65g) [2],and 3 moles HOAc (180g). The Rxn is heated to 60C and heat removed. There follow three additions of 0.75 moles of activated Al at 30 minutes, 1 hour, and two hours. Temperature was maintained at 60C by placing beaker in a cold water bath as necessary. There is a vigourous evolution of hydrogen as the rxn progresses, care must be taken the rxn vessel does not overflow. An additional 150mls 95% EtOH and 15mls dH2O is added at 2hours. At 3 hours the rxn is a viscous gel which has stopped the stir bar. An additional 300mls 95% EtOH and 30mls dH2O is added . The rxn was allowed to stir until it has returned to room temperature, during which time 1 l of 15M NaOH was prepared and cooled. The rxn vessel was placed in a cold water bath and the basic solution was added slowly over 20 minutes, with care being taken the tempertaure did not rise above 60C. 500g of NaCl was added, much of which precipitated after stirring. 500mls toluene is added with stirring. The toluene/EtOH/amine layer is separated and decanted into 750mls of dH2O, causing the EtOH to migrate to the aqueous layer. The toluene layer is separated and the aqueous/alcoholic layer is extracted 2 times with 250mls toluene. The pooled toluene extracts are washed once with 400mls dH20 and once with 400mls brine, then dried through MgSO4 and gassed w/ dry HCl gas, furnishing 54g MDA HCl (0.267 moles, 81%) .

1. Activated by refluxing in 19.5g Al in 800mls of 50/50 dH2O/MeOH, with 1g Hg2Cl2 for 15 minutes, the mercuric solution was decanted, and Al was washed once with 400mls 95% EtOH, which was also decanted. Same mercuric solution was used for all four activations.
2. Prepared according to Sonson's instructions

Note from zee pourple people eater-

You can simply amalgamate the aluminum in situ for convenience and 1g of Hg salt would be huge overkill I think. HgI2 is easily prepared by briefly stirring .5g Hg, .66g I2, 1-2ml MeOH. it can be used immediately or allowed to evaporate to a uniform red powder. Conc h2so4 is the best for getting the post amalgam grap out of yer flask. If you use toluene/xylene for extraction, you have to add enough water (with base) to make the acqueous layer denser than the toluene/xylene, or it won't separate properly. With this in mind it's idiot-proof, persuming your oxime is as good as ours. Not that we ever had p2np, but p2np should easily hold up to the conditions that its ring-substituted relatives can.

Can someone tell me more about the ease and scaleability of nitropropene reduction systems which use Ni- urishibara, base catalyzed, and raney nickel? Also info and the refs for the NaBH4/metal oxime reductions are of interest.
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[*] posted on 25-3-2005 at 02:38
reduction


hi people eater
just some thought for you i have played with all sorts of p2np reductions all the desolving metal ways to the amine are not going to be very big
just a bit more work to 2 step either to the nitroalkane or via the oxime or make p2p far eisier to go to the oxime and then reduce the oxime to the amine.
LOOK at my ,oxime procedure very good no bullshit it works
i have sonsons reduction method of the oxime i am going to use it.
it is the same method i had in my 3rd edition vogul untill it got lost
thanks heeps people eater for the trouble you went to, I hope my method helps you .
dont overlook it
regards aldol
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