Intergalactic_Captain - 21-3-2005 at 18:55
Well, I have a habit of obtaining things that "don't exist" - IE, I own a celphone and once owned a laptop to which the manufacturers
refused to acknowledge the existance of, among other things. Now, this little quirk tends to get into my chemical adventures...To say it short, I
enjoy making things that I can find absolutely no information whatsoever on.
My last experiment involved an attempet to make phenethylamine out of p-dichlorobenzene. In a slip of mind, I accidentally made 4-ehtoxyphenol,
instead of the 4-ethylphenol alcohol that I was after...Realizing this, I decided to look into phenoxyethylamines and their relationship to
phenethylamines. Needless to say, I didn't find much.
So, the other day I got bored and decided to nitrate it. The idea came from COPAE, where I was reading about Trinitrophenoxyethyl nitrate. I got to
thinking - If the hydroxyl group on picric acid allows it to form explosive metal salts, what would a hydroxyl group substituted for the 4-nitro group
in this explosive allow me to do?
I looked through my notebooks and found my standard H2SO4/NH4NO3 nitrating mix, and tailored it to suit what I had to work with. I ended up with a
reaction mix of 100ml H2SO4, 60g NH4NO3, and 40g of 4-ethoxyphenol (1/3 mol, assuming nitration in 3 spots). The mix was prepared on the assumption
that the end product would be 2,6-dinitro phenoxyethyl nitrate.I prepared the acid mix, added the 4-ethoxyphenol, and placed it on my hotplate with a
niggerrigged condenser atop it...Nitric fumes are not my friend.
Now, this is where it gets tricky - After being on for four hours, the organic phase took a yellow hue. Assuming the reaction was over, I turned off
the hotplate. As it cooled and solidiifed, I noticed that not all of it had reacted. The next day, I gave it another four hours - When it cooled
this time, half the organic phase was resolved as a red-orrange oil, while the other half was seen to be the same yellow mass as the night before. I
fired it up again today, and now, as it is cooling, nothing appears to be solidifying out - I am looking at an organic phase in the form of a
yellow-orange oil. Tomorrow, I plan on an icewater crash and a few boilings to clean it up.
This oil has me completely dumbfounded - The compound I'm trying to emulate has a mp of ~100C. This oil is a liquid at room temperature.
Cross-checking everything I know about nitrated hydrocarbons (which is still not that much), I see no reason that this should be a liquid, leaving me
with the nagging suspicion that what I made is nowhere near what I am after.
Now, assuming that my starting material was indeed 4-ethoxyphenol (I haven't been able to verify it) does anyone have any idea what I have made?
I'm assuming that it would nitrate at the 2,6 and alpha spots, but realize that it could be at the 3,5 spots as well. Also, is it even possible
to nitrate the ethyl radical without a hydroxyl group on it (maybe it might go to a nitro group instead?)? I would also appreciate it if anyone could
tell me in what order these nitrations would take place? Any help would be greatly appreciated...This thing has me completely dumbfounded.
EDIT - Realized that 4-hydroxy, 2,6-dinitro phenoxyethyl nitrate is redundant...should just be 2,6-dinitrophenoxyethyl nitrate...or something along
those lines...I need to get some sleep...
[Edited on 3-22-05 by Intergalactic_Captain]
chemoleo - 22-3-2005 at 04:43
Could you just describe first how exactly you made 4-ethoxy phenol from 1,4 paradichlorobenzene?
Maybe the answer to your question lies in there.
Intergalactic_Captain - 22-3-2005 at 08:23
The 4-ethoxyphenol was made in a two step reaction. First, p-dcb and a 2x molar amount of aqueous NaOH were reacted for ~24 hours at ~120C and 2x
atmospheric pressure. On reaction completion, the organic phase looked different than p-dcb, and had a different melting temp...I'd post the
data, but I don't think I doccumented it.
The (supposed) 4-chlorophenol was then reacted with a slight molar excess of sodium ethoxide(aq) in the same conditions as above, but only for ~6
hours. The result was definitely not p-dcb or 4-chlorophenol, so I'm assuming some success was had. Unfortunately, I have found no information
on 4-ehtoxy chlorobenzene or 4-ethoxy phenol to cross-check my results with.
PainKilla - 22-3-2005 at 09:03
Ok Basically here is what I think happened:
Cl-Bz-Cl ----NaOH> OH-Bz-Cl ------NaOEt> OH-Bz-OEt ---HNO3> either : NO2-Bz-OEt or OH-Bz< NO2/OEt (latter is more likely ) I am
curious though whether this is possible: OH-Bz-OEt-NO2 ???
The second (of the three final) seems like the most likely route. Although the NO2 could have landed on some other position but unlikely.
Could you please PM on how you got NaOEt and your results on making PEA please ?
Much thanks 
.
Oh Crap I forgot to save the name of that compound fuck hold on..... here we go:
p-chlorophenetole;
p-ethoxychlorobenzene;
p-chlorophenyl ethyl ether;
phenetole, p-chloro-;
benzene, 1-chloro-4-ethoxy-;
1-chloro-4-ethoxy-benzene;
1-Ethoxy-chlorobenzene
Good luck!
OMG i keep misreading (my contact fell out)
[Edited on 22-3-2005 by PainKilla]