Lem (Stranger)
10-20-00 05:52
No 61690
      Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

Well? Has anyone? I have seen this around for a long time, but I have never heard of anyone actually trying it. It just looks so easy, but SWIM has no lab access, and only 1/2 of a semester of intro  to chem, and so has very little(no) knowledge of these subjects.

In case you wondering what the hell I am babbling about:

The only right we have is to believe that we have rights.
(Hive Bee / Eraser)
10-22-00 23:10
No 62457
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

Yes I did, I posted about it on the "old" hive using the nickname "Zorohustra", I will post it again below:

"Wow, what a complex dream I had last night!

In this dream I dreamed that I tried Eleusis’s ”Proposed nitro -> amine reduction for general use” (which can be found at Rhodium’s outstanding page, check it out!).

13g of GOOD phenyl-2-nitropropene was dissolved in 150ml Glacial Acetic Acid in a 500ml 3-neck RB.

55g of tech. Zinc powder was ”purified” as in Vogel’s 5:Ed. (washing with 10% HCl, then dH2O, followed by acetone).

The dry and pure Zinc was slowly added to the nitropropene solution, while stirring at 700rpm. When ~2/3 of the
Zinc had been added the solution turned ”rust-red”. When all the Zinc had been added the temperature was 80C.

The solution was still stirred at 700rpm, the goal was to heat it to 100C, but it became 106C, at which point it boiled(?!). The solution was no longer “rust-red”, the Zinc was again gray and the solution appeared to be light-pink/red (observed by stopping the stirring for a while).

The stirrer speed was increased to 1100rpm and the solution was held like this for another 30min (total time ~45min). The solution is now light yellow, with some colorless foam.

”Perhaps I have made P2P instead the chemist thought.” (I think I’ve read in March that it can be made with

60ml 37% ACS hydrochloric acid is put into the additionfunnel and added over perhaps 20min, no spectacular
reaction at all. 1-2 hour later another 20ml hydrochloric acid is added, can’t hurt I mean.

The solution is now near colorless, its decantated from unreacted Zinc, the solution dumped into 1000ml cool dH2O, the Zinc washed with 100ml dH2O.

The solution was washed with 3*60+50ml DCM (500ml sep. funnel ;). Then basified with NaOH solution until pH 10-11, then extracted with 3*70+50ml DCM.

The solvent was removed by destillation, leaving VERY LITTLE of ”something”, 15ml anhydrous acetone was added and 2-3 small drops of 98% sulfuric acid, crystals percipitated. But we are talking about a yield in the 100mg range… The chemist dumped it all out, being more of a curios chemist then a desperate speedhead.

The washings was also stripped from solvent by destillation and then dumped into a satured bisulfitesolution, but no crystals formed.

Hmm, IF this reaction can give an acceptable yield this is at least NOT the way to get it, there is really not much to do then but to try with lower temperature, but I am not motivated."


(Stonium's / Changer)
10-23-00 00:03
No 62479
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

Amalgamated Zn should work much better.
10-24-00 00:28
No 62719
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

Os. --
           I agree, the only one I know of is the ZN-Hg reduction of nitrostyrenes....the author was reducing our favorite,,,a 3,4-methylenedioxy nitrostyrene, but one that he had used nitromethane instead of the ethane,,therefore, converting to the phenethylamine, my memory of the write-up was, that he wrote  an exhaustive  hypothesis of all the 7 stages involved in the creation of the styrene itself,,(I think) -- the experimental portion was very easy, dissolve styrene into MeOH ( I think,,or else EtOH),,add to Zn amalgamated with a set amount of mercuric chloride,, add HCL till yellow color of styrene is replaced by the brown color of impure amine (the conversion really happens that fast..) - let stir for another half hour,,and that's it.
...I'm going crazy trying to find it in the short time I have to do research,,the ref, is in Psychedelic Chemistry by Michael Valentine Smith,,,in the Amphetamines and friends chapter (obviously)..if anyone has it,,I would GREATLY appreciate it if they could e-mail me the ref. (I think it's American Journal of Chemistry,,but not sure)...it's kinda hidden,,hard to find..but it's definitely there..I remember the yield in the write-up being more than 70%...which is one reason we tried it..however..he had (M.V.Smith) had summarized it wrong, had written - add HCL till colorless,,,the original said till yellow color of styrene was  gone - changed to brown. I was tired,,left,,,it to my dumb-ass-assistant..who did not take it all the way..never got to find out how well it worked,,,but I know the author was one who was very reliable, a frequent contributor in the field...
but it looked totally good...am surprised that more people have not dreamed this one....so please!!! somebody send me the ref. to Chinacat88@hushmail.com - and Thanx!!!!
10-25-00 01:03
No 63038
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

How does this sound:

Synthesis of dl-cepharanthine
Source:Tetrahedron Lett. no. 13 (1967): 1201-6

Methylenation of 5-bromoprotocatechualdehyde with CH2Br2 in HCONMe2 in the presence of CuO yielded 42% 5-bromopiperonal. Condensation with MeNO2 in AcOH contg. NH4OAc gave 73% of the nitrostyrene, reduced according to Clemmensen to the corresponding phenethylamine in 68% yield!

Clemmensen of course refers to using zing/Hg
(Hive Bee / Eraser)
12-03-00 14:20
No 72169
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

I tried different Hg/Zn approaches several times and it was not easy, the yields where very low. Also the environmental concerns should be considered. Perhaps if someone could fine a good method and a procedure for reusing the amalgam. Something along the line of just adding more Zn to what is left.

(Hive Bee)
12-04-00 07:38
No 72315
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

You can also use Al instead of Zn, yields are not good either (50%). See

E.Spaeth, Riedl and Kubiczek, Monatshefte Chemie, Bd 79, 1948, page 72

They reduce the 2,3 dimethoxyphenylnitroethen with Al in GAA/EtOH/H2O
with a tiny bit HgCl2 to initiate the rxn only.

Cave Canem! Latin.
12-06-00 12:44
No 72992
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

2,3-Diethoxy-PEA from 2,3-Diethoxynitrostyrene with Zn-Hg :

G.Tsatsas, Bl.[5] 16, 884 (1949)

66,5% yield
(Chief Bee)
12-06-00 13:26
No 73002
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

What journal does the abbreviation "Bl." stand for?

12-06-00 14:57
No 73031
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

Bulletin de la Société Chimique de France smile

You might also look at:

Houben-Weyl, (1957) Bd. 11/1
Reduktion von Nitroverbindungen zu Aminen:
- mit Zink p.463
- mit Aluminium p.469
(Hive Bee)
03-24-01 16:52
No 180336
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

I don't have the ref. chinacat is refering to but I do have that book by M. Valentine Smith. The ref he's refering to is JOC 37,1861 (1972) but he says that for another catalytic reduction you should also see this ref.


Vae victis meretrix est et mors venit.
(Hive Addict)
09-13-01 15:34
No 213060
      Re: Anyone tried zinc/hcl reduction of nitrostyrene?  Bookmark   

2,3-Diethoxy-PEA from 2,3-Diethoxynitrostyrene with Zn-Hg :

G.Tsatsas, Bl.[5] 16, 884 (1949)

66,5% yield

Has anyone found this ref?  Can someone post the text here or give to Rhod for publication on ../rhodium???

"And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"