|p-Dicyanobenzene: Photoamination Catalyst....||Bookmark|
Awhile back, I myself, among others past, had wondered if over the counter p-dichlorobenzene, found in mothballs, could be used to synthesize p-dicyanobenzene, a noted photoamination catalyst, as presented long ago by Drone 342.
The answer was not favorable. The dichloride is very inert to many reagents, and the truth of that matter is that these particular variety of bastard halogens just won't let go of that ring, greedy fucks as they are.
So, it seems that my old thought of using the traditional sodium cyanide halogen swap used for aliphatic chlorides, won't work here. Well, that appeared to be the end of it for some time.
Look what I saw today:
Well, it appears that although sodium cyanide will not swap with aromatic chlorine, but perhaps cuprous cyanide might. I don't know hoew hard it is to prepare this compound (cuprous chloride and sodium cyanide???? extremely doubtful) but maybe CuCN will add on the -CN groups to those positions occupied by the chlorine atoms. 'twoud be neato if it did.
p-Dichlorobenzene is dirt cheap and available. I am still pushing the incentive to look hard into this, this catalyst is used to go directly from safrole --> MDMA with zero intermediates! This is but one application! Styrene --> PEA with ammonia's use. The list goes on forever.
Vivent Longtemps La Ruche!
Terephtaldehyde treated with hydroxylamine to form the dioxime, followed by dehydration with acetic anhydride or microwave heating should produce p-dicyanobenzene.
CuCN will not substitue aromatic Chlorines. To do that, you would need a homogenous Palladium catalyst or the like. I have talked before about using Zn(CN)2 with Pd(dppf)Cl2 in MeCN/THF or DMF. You can also use KCN, Pd(OAc)2, PPh3and TMEDA in DMF; CuCN and a phase transfer catalyst in MeCN; KCN, NiCl2, PPh3, and Zn powder in THF; CuCN in sulpholane at >200°C.
I am still pushing the incentive to look hard into this, this catalyst is used to go directly from safrole --> MDMA with zero intermediates! This is but one application! Styrene --> PEA with ammonia's use. The list goes on forever.
Not quite. I have looked into the matter, and Drone was(like always) full of shit. The yields are not good, and the only reference on the photoamination used 1,1-Diphenylethylene, to give 1,1-Diphenylethylamine, a far cry from our beloved secondary amine. The yields were not good either. There is no compelling reason (yet) to believe that you could go from safrole -hv-> MDMA.
But please, I emplore you to keep trying. Dig up some references, find some good stuff for us, I know you can.
(Ubiquitous Precursor Medal Winner)
I looked up some old-Hive threads appertaining thereunto, earliest available being a thread Post 102375 (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:
and Rev. Drone backed up this assertion, in Post 102391 (rev drone: "Re: Photo-amination. A shortcut please!", Chemistry Discourse)
and in Post 102399 (rev drone: "Re: Photo-amination. A shortcut please!", Chemistry Discourse)
a half a pints a half a pound a half a world a half a round
Sidearm n. Flask neck tube.
(Official Hive Translator)
Excellent, Half-A-Pint, was very interesting to read.
Personally i believe there must bee some hidden diamond in one of these routes....someday....
(Stoni's sexual toy)
|> p-dicyanobenzene : start with this compound, ...||Bookmark|
> p-dicyanobenzene : start with this compound,
> 2HNCH2-C6H4-CH2NH2 + P2O5 ==dehydration===>>
> NC-C6H4-CN or C6H4(CN)2
There's a typo, it should be:
2HNCO-C6H4-CONH2 + P2O5 ==dehydration===>>
P2O5 is a very common chemical. This reaction is a dehydration, not a dehydrogenation!
I'm not fat just horizontally disproportionate.