Sciencemadness Discussion Board - Binaphthyl and perylene

Binaphthyl and perylene

Keras - 4-1-2026 at 00:05

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 - 4-1-2026 at 11:46

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 15 times

[Edited on 4-1-2026 by Fery]

Keras - 4-1-2026 at 23:14

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 - 5-1-2026 at 02:45

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 - 5-1-2026 at 03:07

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 - 5-1-2026 at 07:06

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 - 5-1-2026 at 08:06

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 - 5-1-2026 at 15:02

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 - 6-1-2026 at 23:09

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 - 7-1-2026 at 09:36

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 3 times

bnull - 7-1-2026 at 16:58

Fieser & Fieser's Organic Chemistry (2nd ed.), chapter 34 "Polynuclear Hydrocarbons", pp. 830-831:

and chapter 28 "Phenols", p. 678:

and the end-of-chapter references for chapter 34:

My apologies for the quality of the images. The book won't fit the scanner, so it is either transcribe the text or take these crappy shots. Crappy shots won this time.

Chapter 34 gives several preparative methods for other polynuclear hydrocarbons. They may give you some ideas to try.

Edit: In the 3rd edition (https://archive.org/details/organicchemistry0000unse_k1l1/pa...) the pages are 779-780 and 637-638.

[Edited on 8-1-2026 by bnull]