I looked up some old-Hive threads appertaining thereunto, earliest available being a thread
Post 102375 (missing)
(CHEM GUY: "Photo-amination. A shortcut please!", Chemistry Discourse) marked by discussion of the syntheses of the poisons cyanide, fentanyl, and 3 different nerve gases. Excerpts:
Torch
(Member)
06-25-99 15:28
No 102379
Re: Photo-amination. A shortcut please! Reply
I have no clue about photo-amination but, p-dichlorobenzene is what those toilet mints you aim for in the urinal are mainly comprised of... OTC 'Outta The Commode'
yellium
(Member)
07-24-99 15:52
No 102397
Re: Photo-amination. A shortcut please! Reply
Chemguy: If you would have taken the time to actually go to the library and *READ* the fscking article that's mentioned, you would have noticed that para-dicyanobenzene does catalyze the rx, but also forms unwanted adducts, thus reducing yields & making xtalization more troublesome. m-DCB doesn't have this disadvantage.
and Rev. Drone backed up this assertion, in Post 102391 (missing)
(rev drone: "Re: Photo-amination. A shortcut please!", Chemistry Discourse)
What can be used instead of meta-dicyanobenzene (not para, as people continually insist)?
and in Post 102399 (missing)
(rev drone: "Re: Photo-amination. A shortcut please!", Chemistry Discourse)
Re: Photo-amination. A shortcut please! Reply
Yellium,
Its true enough that p-dicyanobenzene promotes some side reactions (as I've said repeatedly after I wrote that article on Rhodium's page)
...
Also, it doesn't mention anything about Pyrex killing the reaction for a very specific reason: the reaction was performed in a Pyrex vessel, and, to quote a phrase "If you would have taken the time to actually go to the library and *READ* the fscking article that's mentioned", I believe the abstract specifically mentions that the light used was borosilicate (Pyrex) filtered.
In another later thread:
CHEM GUY
(Member)
10-30-99 19:11
No 104616
Re: Isomerizing dicyanobenzene (phthalodinitrile) from 1,2 to 1,3 Reply
Forget the DiCynoBenzene route. Read the patent # 4483757.
I listed all the parts I thought important in the thread called:- Homogeneous catalyzed amination of olefins - in the novel discourse forum.
The advantages for this patent are :
NO DCB
The catalyst is NH4I or NH4Br, or if used in stochimetric amounts, NH4Cl or NH4F
Uses UV light, with a wavelength about 160 nm.
Takes about 4 hours
Uses only the catalyst, olefin, and aminating agent.
Aminating agent is just about anything with minor restrictions that are listed.
MOST OF ALL, IT'S SIMPLE!
Read it, understand it, love it,...
Right rev drone,
rev drone
(Member)
10-31-99 05:50
No 104618
Re: Isomerizing dicyanobenzene (phthalodinitrile) from 1,2 to 1,3 Reply
CHEM GUY,
Likewise, I have to say, it sounds just too good to be true. There's got to be a reason M. Yasuda and company chose to use DCB as the catalyst for their reactions, and I'm pretty sure its not because it was on sale.
Slappy
(Moderator)
11-01-99 22:11
No 104621
Re: Isomerizing dicyanobenzene (phthalodinitrile) from 1,2 to 1,3 Reply
Yes. m-DCB is your best bet. Just like Drone said, "meta, meta, meta!".
The only real synthetic contribution for the catalyst is for the debunked para isomer:
Wizard X
(Moderator)
07-07-99 00:23
No 102382
Re: Photo-amination. A shortcut please! Reply
p-dicyanobenzene : start with this compound,
2HNCH2-C6H4-CH2NH2 + P2O5 ==dehydration===>>
NC-C6H4-CN or C6H4(CN)2
and though I don't believe in the existence of P2O5, never having seen any, there may bee some agency which could perform such a dehydrogenation. If so, I can contribute that m-xylene is the predominant isomer in the can of solvent at the hardware. Dichlorination, by tacking a single chlorine on each of m-xylene's methyl groups, gives m-dichlorodimethyl benzene, or dichloro-m-xylene. These chloromethyl groups could both bee aminated, giving you the preferred meta isomer of WizardX's starting compound above.
Now Slappy sounds discouraging. I was hoping this photocatalyst would prove the magic bullet. I got unsatisfactory results using ammonium bromide catalyst, though my test rxn conditions were not very rigorous, and the mercury-catalyzed photoamination isn't very appealing. It's still up in the air, far as I'm concerned.
a half a pints a half a pound a half a world a half a round
Sidearm
n. Flask neck tube.