Keras
International Hazard
Posts: 1134
Registered: 20-8-2018
Location: (48, 2)
Member Is Offline
|
|
Binaphthyl and perylene
Folks,
I know several (old) threads have been dedicated to the synthesis of perylene, but none of them seems to have ended up with a practical recipe.
Perylene apparently can be made either directly from naphthalene using AlCl₃ at 180 °C but with a yield < 1%. A better alternative is to use
dinaphthyl, in which case the needed temperature is only 120 °C and the yield is rather like 10 to 20%. But the question is: how to produce
binaphthyl from naphthalene?
Alternatively, is there a way to synthesise perylene by another (more high yielding) process?
|
|
|
Fery
International Hazard
Posts: 1102
Registered: 27-8-2019
Location: Czechoslovakia
Member Is Offline
|
|
biphenyl is a sideproduct of grignard from brombenzene, so binaphthyl the same from bromonaphthalene
the side reaction is minimized by slow addition of bromo..., but you need to maximize the side reaction, so add extra bromo... after all Mg is
consumed
1-bromonaphthalene is made by bromination of naphthalene with Br2 in solvent - cheapest and most available seems to be acetic acid
| Quote: | Perylene from 1,1'-Dinaphthyl
10 g of 1,1'-Dinaphthyl and 40 g of aluminum chloride are thoroughly ground together, and the mixture is heated in a flask fitted with a calcium
chloride tube for 1 hour at 140°C. It is carefully decomposed with water, and the brown, powdery mass is boiled several times with dilute
hydrochloric acid. After drying at 110°C, the residue is sublimed from a small vessel in a carbon dioxide stream in a combustion chamber using a
small air drying box, whereby the perylene dissolves into shiny yellow flakes at approximately 350-400°C. A dark, brittle residue remains in the
vessel, from which nothing usable could be obtained.
The sublimate is dissolved in hot benzene; upon cooling, the perylene crystallizes from the solution in beautiful bronze-lustrous flakes, which are
recrystallized for further purification from glacial acetic acid, which is difficult to dissolve at boiling temperatures. Yield 1.5 g.
|
https://annas-archive.se/scidb/10.1002/cber.191004302175/
Attachment: cber_191004302175.pdf (355kB)
This file has been downloaded 12 times
[Edited on 4-1-2026 by Fery]
|
|
|
Keras
International Hazard
Posts: 1134
Registered: 20-8-2018
Location: (48, 2)
Member Is Offline
|
|
Thanks for the pointer! As usual, you’re such a reliable adviser! 
The Wikipedia™ page for biphenyl also states that it can be made from phenyl magnesium bromide and copper II salts. Maybe such a process would also
give a higher yield of binaphthyl? Mixing naphthyl magnesium bromide with copper sulphate.
Another process involves the diazotisation of the amine, but the prospect of working with 1-naphthylamine seems scary.
Also [EDIT] the procedure to make bromonaphthalene requires of course an inert solvent. The Organic Synthesis mentions carbon tetrachloride, which is
unavailable. Dichloromethane wouldn't probably work, nor chloroform. Toluene neither. What could work?
[Edited on 5-1-2026 by Keras]
|
|
|
bnull
National Hazard
Posts: 933
Registered: 15-1-2024
Location: East Woods
Member Is Offline
Mood: Happy New Year!
|
|
Just a comment. Always check the sources in a Wikipedia article. Saccharine has a faulty reaction scheme and the source given, Ullmann's, uses the
wrong patent.
|
|
|
Keras
International Hazard
Posts: 1134
Registered: 20-8-2018
Location: (48, 2)
Member Is Offline
|
|
That’s a good idea, yes. I tend (probably like others) to take Wikipedia™ as gospel.
In any case, I wonder if in my case starting from acenaphthene is not more sensible. The pigments are all derived from perylenetetracarboxylic acid,
which apparently can be made starting with acenaphthene.
Wikipedia™ (once more) says that acenaphthene can be made by mixing acetylene and naphthalene vapours, but I’m not a big fan of using acetylene at
250 °C. Any other – safer – way?
|
|
|
bnull
National Hazard
Posts: 933
Registered: 15-1-2024
Location: East Woods
Member Is Offline
Mood: Happy New Year!
|
|
Something like this: E. D. Bergmann, Jacob Szmuszkovicz, A New Synthesis of Acenaphthene, https://doi.org/10.1021/ja01107a501
March's Advanced Organic Chemistry (5th ed.) has a small section on extrusion of SO2 from cyclic sulfones (pp. 1354-1355). You may want to
take a look at the references given there:
Gould, I.R.; Tung, C; Turro, N.J.; Givens, R.S.; Matuszewski, B. J. Am. Chem. Soc, 1984, 106, 1789;
Vögtle, R; Rossa, L. Angew. Chem. Int. Ed. Engl., 1979,18, 515;
Stark, B.P.; Duke, A.J. Extrusion Reactions; Pergamon: Elmsford, NY, 1967, p. 72;
The Chemistry of Organic Sulfur Compounds, vol. 2; Pergamon: Elmsford, NY, 1966, p. 115.
|
|
|
Keras
International Hazard
Posts: 1134
Registered: 20-8-2018
Location: (48, 2)
Member Is Offline
|
|
Well, I also found this article but it is uses a lot of weird reactants: LiAH, diazomethane, benzyl lithium and so on, so definitely no-go (although
one could probably try with milder reagents, like sodium borohydride and dimethyl carbonate or dimethyl oxalate).
I’m going to take a look at the other references, thanks for posting them.
[EDIT] Even the Merck Index doesn’t seem to quote anything usable besides the original procedure. Most of the other reactions cited seem to start
from a substituted acenaphthene, so nothing much interesting.
[Edited on 5-1-2026 by Keras]
|
|
|
bnull
National Hazard
Posts: 933
Registered: 15-1-2024
Location: East Woods
Member Is Offline
Mood: Happy New Year!
|
|
I'll take a look at other books and see if I can find a friendlier method that doesn't involve diazomethane or heating acetylene.
|
|
|
Keras
International Hazard
Posts: 1134
Registered: 20-8-2018
Location: (48, 2)
Member Is Offline
|
|
Thanks a lot! I’m pretty limited when it comes to book searching.
Of course, I could also simply buy Naphthalenetetracarboxylic dianhydride.
It seems it can be also made starting from pyrene, which is not cheap but not that dear either. Can pyrene be made from naphthalene by aromatic
fusion?
|
|
|
RU_KLO
Hazard to Others
Posts: 315
Registered: 12-10-2022
Location: Argentina
Member Is Offline
|
|
Found some papers that could help you, but as org. chem is way out of my league, don't know the possibility of making it:
Perylene Synthesis by the Parallel Cycloaromatization of Adjacent Enediynes
Siew-Yin Chow, Grant J. Palmer, Daniel M. Bowles, and John E. Anthony*
Department of Chemistry, UniVersity of Kentucky, Lexington, Kentucky 40506-0055
Received February 2, 2000
"Biphenyl 7 was desilylated by treatment with sodium methoxide in methanol-THF, yielding tetrayne 8 in quantitative yield. Cycloaromatization of 8,
which required heating a 0.01 M solution of the tetrayne in 10:1 (v/v) benzene/1,4-cyclohexadiene to 180 °C in a sealed steel bomb 9 for 2 h, led to
the desired perylene 9 as the major product (66% yield), along with a small amount (10%) of the binaphthyl 10"
(attached)
Synthesis of Perylene
Satoshi IWASHIMA and Junji AOKI
1) Zinc Dust fusion of beta-dynaphtylene oxide (from internet: it the same as 2-naphthol (β-naphthol)) - dont know how hard is to make/get this
reagent, but seems the most amateur procedure to follows
6.6% yield
2) reduction of 2-naphthol by Martins method
7.7% yield
3) decarboxtlation of Perylene Tetracarboxylic Anhydride (PTCDA)
80% yield
(attached)
Hope it helps.
Attachment: ol005615f.pdf (47kB)
This file has been downloaded 2 times
Attachment: bcsj.41.2789.pdf (2.4MB)
This file has been downloaded 2 times
Go SAFE, because stupidity and bad Luck exist.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
