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Author: Subject: Synthesis of diisobutyl 3,9 perylenedicarboxylate
mackolol
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[*] posted on 5-11-2017 at 13:16
Synthesis of diisobutyl 3,9 perylenedicarboxylate


Im interested in making compound named diisobutyl 3,9 perylenedicarboxylate. And i have an idea but i dont know will it work. I want to make dicarboxy perylene by scholl reaction with 1 naphthoic acid and lewis acid but i dont know how to make naphthoic acid. Maybe better way is to make dicarboxy perylene from perylene itself. Then i want to esterificate it with isobuthanol.
There is picture of this compounds structure. It seems easy to make.

68474.png - 6kB

[Edited on 5-11-2017 by mackolol]

[Edited on 6-11-2017 by mackolol]
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mackolol
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[*] posted on 7-11-2017 at 00:53


All i want to know is if it work and how can i make 1-naphthoic acid. Can somebody help me?
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The Volatile Chemist
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[*] posted on 7-11-2017 at 18:40


It looks like it might be a colorful compound - but why do you want to make it?




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mackolol
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[*] posted on 7-11-2017 at 23:20


Green chemiluminescent dye and i think it could be easiest green dye to synthesise. Other two i know is coumarin 7 there is topic about it and 9,10bis phenylethynyl anthracene
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Boffis
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[*] posted on 8-11-2017 at 01:07


@ Mackolol, I have done a bit of research and it looks like there are two routes to the basic acid. The first is from 3,9-dibromo or dichloroperylene, halogen displacement to the dinitrile using cuprous cyanide (easily prepared from ferrocyanide see SM thread) and then hydrolysis of the cyano group to and acid. Or alternatively from perylene via a double Freidel-Craft acylation with acetyl chloride to 3,9-diacetylperylene and then alkaline oxidation to the required diacid.

The problem in the first case is the source of 3,9-dihaloperylenes, however, although I haven't found a definite procedure yet it appears that direct bromination in a fashion similar to the procedures for naphthalene (eg in Vogel) yields mainly the 3,9 disubstituted product. I have found a reference to the preparation of perylene from bis-(2-naphthol) which is prepapred by oxidising 2-naphthol with ferric chloride etc. The yield is low however but there may be better methods (maybe ask nicely of someone on the references thread and they will run a reaxys search for you :) ).

Here are a few refs about perylene to keep you busy:
Scholl et al.; Berichte C.; 1910, v43, p2203
Hansging & Zinke; Monatsh.. ; 1919; v40 p404
Zinke et al; Monatsh.. ; 1932; v61 p1
Clar; Berchte C.; 1932; v65, p846
Morgan & Mitchell; JCS; 1934; p534. (this last refs contains a reference to a simple prep for perylene but the yield is low)

For Perylene-3,9-dicarboxylic acid check out:
Pongratz; Monatsch, 1927; v 48 p585 & 1929: v52, p9
Pongratz et al.; 1933; v62 p71

Another possible route is via the degradation and reduction of perylenequinone vat dyes or perylene 3,4,9,10 tetracarboxylic acid which may partly decarboxylate at high termperatures. There are lots of patents on these two groups, most of the ones I have found so far are in German. Can you read German?

For the preparation of the tetracarboxylic acid try:
German Patents: 394794; 408513 and 412122

I have a book about the synthesis of VAT dyes and there may also be something in there. The significance of a route via perylene vat dyes is that inorder to be commercially useful it had to be easy to prepare in 1900s via a simple mix-n-bake type procedure.
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[*] posted on 8-11-2017 at 06:18


1.Napthalene to perylene using scholl reaction -http://onlinelibrary.wiley.com/doi/10.1002/cber.191004302175...
2.perylene to 3,9-dibromoperylene - http://onlinelibrary.wiley.com/doi/10.1002/jlac.199719970218...
3.Convert DBP to a double grignard reagent and react with dry ice to get dicarboxylic acid
4.esterification with isobutanol -http://www.tandfonline.com/doi/full/10.1080/00397911.2013.83...
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mackolol
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[*] posted on 8-11-2017 at 13:28


Thank you and how would it look like if i will use acetyl chloride and if potassium permanganate is enough to ozidise it to acid?
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[*] posted on 8-11-2017 at 14:30


If you are going to go via FC acylation then acetyl chloride and AlCl3 looks good. The usual method of oxidation of acetophenone to benzoic acid is with sodium hypochlorite and this reaction ought to be analogous though I think KOH/NaOH and KMnO4 would work too but is more expensive.
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[*] posted on 8-11-2017 at 22:47


Quote: Originally posted by mackolol  
how can i make 1-naphthoic acid. Can somebody help me?

1-napthoic acid might not undergo the scholl reaction since COOH is a deactivating group
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mackolol
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[*] posted on 12-11-2017 at 04:57


Quote: Originally posted by CuReUS  
1.Napthalene to perylene using scholl reaction -http://onlinelibrary.wiley.com/doi/10.1002/cber.191004302175...
2.perylene to 3,9-dibromoperylene - http://onlinelibrary.wiley.com/doi/10.1002/jlac.199719970218...
3.Convert DBP to a double grignard reagent and react with dry ice to get dicarboxylic acid
4.esterification with isobutanol -http://www.tandfonline.com/doi/full/10.1080/00397911.2013.83...

Do you have any other source than onlinelibrary? Because i dont have access to this and dont wont to pay.
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[*] posted on 12-11-2017 at 12:34




Attachment: scholl1910.pdf (355kB)
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Attachment: schlichting1997.pdf (1.4MB)
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