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Author: Subject: Martius Yellow - fun with dyes
Magpie
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[*] posted on 14-3-2013 at 13:36
Martius Yellow - fun with dyes


Using 5g of the homemade 1-naphthol that I reported on yesterday, I made Martius Yellow, a dye. I used the procedure found in Louis Fieser's book Experiments in Organic Chemistry, 3rd ed, rev., (1957), pp. 234-236. My yield was 4.6g compared to Fieser's 7.7g, 88.5% yield.

The procedure was to sulfonate the 1-naphthol at the 2, 4 positions, then convert this disulfonate to 2,4 dinitro. This is then converted to a 2,4 diammonium chloride salt. This is shown below in dried form:

Martius Yellow.JPG - 123kB
Martius Yellow

This salt will be used to make the remaining several dyes in Fieser's series.

In the past I have also made methyl orange, malachite green, and fluorescein dyes. They are fun to make, providing pleasing colors, and some can be useful as pH indicators for titrations. It is also quite educational to see how easily contamination is spread during one's lab work. The evidence is everywhere.





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[*] posted on 14-3-2013 at 17:45


Quote: Originally posted by Magpie  
It is also quite educational to see how easily contamination is spread during one's lab work. The evidence is everywhere.

Ain't that the truth. Of all chemicals, intense fluorescent dyes are high on my list of nasty things I don't enjoy working with. They get under gloves, contaminate your glass and other work for weeks, and if you let a solution of it bump in a rotavap... oh boy.

Alright... they're not that bad, but it certainly is eyeopening to find out just how present chemical residues really are in the lab and on your person. :o
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[*] posted on 15-3-2013 at 01:54


What you mean is that you don't like being able to see the contamination. The same level of contamination exists whether or not you can see it.
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[*] posted on 15-3-2013 at 07:19


To some extent even something as common as KMNO4 is like that when rinsing off glasswear. The tiniest flecks produce deep purple traces when water touches them. And while certainly not good to breathe, just grinding some in a mortar and pestle you can detect some contamination in the air, a slightly sweet smell. When I would wash the mortar and pestle with the garden hose, there was an explosion of purple from the smallest remains.
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Magpie
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[*] posted on 15-3-2013 at 14:44


Here's a couple more pictures from today's efforts. I'm sure glad I don't have to do this series in 2 ea 3-4hr lab periods as did Fieser's students!

just another day at the dye lab.JPG - 117kB

just another day at the dye lab

Attachment: phpsq28xN (95kB)
This file has been downloaded 217 times

II and IV of Fieser's Marius Yellow dye series

II is 2-amino-1,4-naphthoquinonimine hydrochloride. IV is 2,4-diacetylamino-1-naphthol. These will be converted to still yet other dyes.

BTW sodium hydrosulfite is available OTC from DanielSmith, Inc.





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[*] posted on 17-3-2013 at 19:31


Today I made dyes III and VII from dye II:

II. 2-amino-1,4-naphthoquinonimine HCl.JPG - 106kB

II. 2-amino-1,4-naphthoquinonimine HCl

III. 2-amino-1,4-naphthoquinonimine diacetate.JPG - 91kB

III. 2-amino-1,4-naphthoquinonimine diacetate

VII.  4-amino-1,2-naphthoquinone.JPG - 91kB

VII. 4-amino-1,2-naphthoquinone


There are just two more dyes to make: V and VI from IV. II is my favorite so far. Here's another picture of VII, recrystallized into needles from hot water:


VII. 4-amino-1,2-naphthoquinone, crystallizing.JPG - 105kB




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[*] posted on 17-3-2013 at 20:29


Quote: Originally posted by Magpie  
The procedure was to sulfonate the 1-naphthol at the 2, 4 positions, then convert this disulfonate to 2,4 dinitro.

How is the sulfonate converted to nitro ?
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[*] posted on 18-3-2013 at 07:46


Quote: Originally posted by AndersHoveland  
Quote: Originally posted by Magpie  
The procedure was to sulfonate the 1-naphthol at the 2, 4 positions, then convert this disulfonate to 2,4 dinitro.

How is the sulfonate converted to nitro ?


Actually, I misspoke there. It was a disulfonic acid that was converted to a dinitro. It's a two step process. First the 1-napthol is treated with con sulfuric to make 2,4 disulfonic acid-1-naphthol. In the second step that product is treated with con nitric acid to form 2,4 dinitro-1-naphthol (Martius Yellow).

This 2-step process has me a little confused. I've never seen it before. My education and experience is that of using nitrating acid, ie, mixed H2SO4 and HNO3, to install nitro groups on an aromatic compound.





[Edited on 18-3-2013 by Magpie]




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[*] posted on 18-3-2013 at 07:51


Quote: Originally posted by Magpie  

This 2-step process has me a little confused. I've never seen it before. My education and experience is that of using nitrating acid, ie, mixed H2SO4 and HNO3, to install nitro groups on an aromatic compound.

IIRC the same technique is used for installing the final nitro group in TNT (trinitrotoluene), but oleum is used instead. I think the idea is that the ring is so deactivated by the two nitro groups that using mixed acids is useless, while sulfonation with oleum occurs more readily. The resulting sulfonic acid is then subjected to nitric acid, replacing the -OSO2OH moiety with a nitro.


[Edited on 18-3-2013 by Lambda-Eyde]




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[*] posted on 19-3-2013 at 08:40


Here's photos of the last 2 dyes, V and VI. V was made from IV and VI was made from V.

V.  2-acetylamino-1,4-naphthoquinone.JPG - 87kB

V. 2-acetylamino-1,4-naphthoquinone

VI. 2-amino-1,4-naphthoquinone.JPG - 76kB

VI. 2-amino-1,4-naphthoquinone

VI.  2-amino-1,4-naphthoquinone (from water).JPG - 80kB

VI. in water

My son, who is an artist, was impressed with the intensity of some of these dyes. He asked if any of them could be used as pigments and were light fast. I couldn't answer him but suspect that since, with the exception of Martius Yellow, they don't have commercial names (that I am aware of) they probably aren't useful for oil painting. Anyone know about this?




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[*] posted on 19-3-2013 at 08:45


Have him try them. Make a simple painting with them, stick it in the sun for a month or two, see if there is any degradation.



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[*] posted on 9-9-2014 at 23:47


magpie
i have finished making the 2,4 dinitro naphtol.but i am having problems with recrystallization(tried with ethanol,but the dye wont dissolve completely) and after the ethanol has evaporated away, all that is left a dry yellow powder,far from fieser's yellow needles.also for the reduction to the diamino,could you use a reagent other than Na2S2O4 (according to fieser,we could use tin/hcl but the purification will be difficult and i wont have much product left(i started with 2g 1-napthol).could we use hypo(Na2S2O3).the mechanism of the reduction is a free radicle SO2 i think,i will try to get the article
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[*] posted on 10-9-2014 at 13:07


Quote: Originally posted by CuReUS  
magpie
i have finished making the 2,4 dinitro naphtol.but i am having problems with recrystallization(tried with ethanol,but the dye wont dissolve completely) and after the ethanol has evaporated away, all that is left a dry yellow powder,far from fieser's yellow needles.


Looking back in my notes it looks like I did not convert any of the ammonium salt of Martius Yellow into Martius Yellow. So I can't help you there.


Quote: Originally posted by CuReUS  

also for the reduction to the diamino,could you use a reagent other than Na2S2O4 (according to fieser,we could use tin/hcl but the purification will be difficult and i wont have much product left(i started with 2g 1-napthol).could we use hypo(Na2S2O3).the mechanism of the reduction is a free radicle SO2 i think,i will try to get the article


Na2S2O4, sodium dithionite (aka sodium hydrosulfite), is available from DanielSmith Co. It should also be available locally as a Rit dye (Rit Color Remover). Try your grocery store. IIRC it is sodium dithionite with a few per cent sodium carbonate added as stabilizer. See:

https://www.ritstudio.com/techniques/the-basics/rit-color-re...

https://www.ritstudio.com/wp-content/uploads/2014/05/MSDS_RI...

I wouldn't know from experience about the suitability of other reducers - sorry.




[Edited on 10-9-2014 by Magpie]

[Edited on 10-9-2014 by Magpie]




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[*] posted on 25-12-2016 at 16:28


Magpie, I was thinking of trying the synthesis of these dyes myself. I read the procedure in the 2nd edition of Fieser's book, and for the initial sulfonation, he writes "Pour 10 cc. of c.p. concentrated sulfuric acid sulfuric acid onto 5 g. of powdered 1-naphthol" but I was not sure what concentration "c.p." concentrated sulfuric acid is. I assume it stands for contact process, since a lot of times in the old days they referred to sulfuric acid by how it was produced, but I wanted to verify that and see what concentration you used.



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[*] posted on 25-12-2016 at 17:11


I believe c.p. just means "chemically pure."

I made no notes about this acid so assume I just used Rooto con H2SO4. This is ≥93wt% I believe.




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[*] posted on 25-12-2016 at 17:42


C.P. means chemically pure in this context.



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[*] posted on 25-12-2016 at 20:22


Oh ok, thanks. I will use my good 95% stuff then rather than my contaminated and cheap 91% in that case.



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[*] posted on 27-12-2016 at 18:26


I tried the Martius yellow synthesis tonight, and despite following the procedure to the letter I got some strange results. The sulfonation yielded a dark green (almost black) product which was readily water soluble, and upon addition to nitric acid this turned dark red, and no yellow precipitate formed when it was heated. I think maybe I just overheated it during the sulfonation, since I used a hot plate rather than a steam bath, although I did try to keep the temperature fairly low.

I made a post on my new blog with all of the details: https://texium.wordpress.com/2016/12/27/failed-synthesis-of-...

@Magpie, did yours get so dark during the sulfonation?




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[*] posted on 28-12-2016 at 09:44


More cool OC stuff to do !

Nice one Magpie.

I definitely need to summon the courage to get on with the Congo Red thing, then try these puppies.




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[*] posted on 28-12-2016 at 10:03


Quote: Originally posted by zts16  


@Magpie, did yours get so dark during the sulfonation?


I made no comment on this so can't say.




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[*] posted on 28-12-2016 at 11:06


Hmm, I guess I'll try it again today then but with less strong heating during the sulfonation. My gut feeling is that that's the part that went wrong. Too bad I don't have a steam bath as recommended by Fieser. That would make things easier.



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[*] posted on 28-12-2016 at 11:40


Would a metal bowl of water on a hotplate with Al foil wrapped around so it comes up to the RBF not be more-or-less a steam bath ?



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[*] posted on 6-1-2017 at 08:17


I tried the reaction again yesterday using an improvised steam bath (made out of a large Erlenmeyer and a funnel) and it worked very well!

https://texium.wordpress.com/2017/01/06/synthesis-of-martius...




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[*] posted on 6-1-2017 at 12:17


Very nice work zts !

It would be nice to see those photos here as well as on your blog.

SM is a bit lacking in photographic evidence of people's own work, and it certainly brightens the place up, especially with dyes !




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[*] posted on 6-1-2017 at 14:00


Well I would post them here, however, to do so would require resizing each one of them, as my phone takes pictures that are just barely over the maximum size allowed by the forum. Much easier to simply post a link to my blog.



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