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Author: Subject: Martius Yellow - fun with dyes
aga
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[*] posted on 6-1-2017 at 14:37


It'd be very nice to see them enshrined here as well, as and when you get the time.

They are Great photos of an amateur chemist doing amateur chemistry ...




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PHILOU Zrealone
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[*] posted on 7-1-2017 at 13:20


I wonder if 1,5-dihydroxynaphtalene and 1,8-dihydroxynaphtalene can be sulfonated and nitrated with the same method as for Martius Yellow synthesis to yield 1,5-dihydroxy-2,4,6,8-tetranitronaphtalene and 1,8-dihydroxy-2,4,5,7-tetranitronaphtalene...both being related to 2,4,6-trinitrophenol (TNP) what is also a yellow dye; they must also be interesting dyes...with the same field of applications.

I also like their possible application as dense High Energy Explosive probably more powerful than TNP (because denser and with a similar OB) and also forming shock and heat sensitive metallic salts.




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Boffis
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[*] posted on 12-1-2017 at 10:13


Hi Philou, the answer is yes.

Attachment: Nitration of 1,5-dihydroxynaphthalene, 1,5-diacetoxy and 1,5-dimethoxyN JCS Thomson et al 1947.pdf (156kB)
This file has been downloaded 44 times

Attachment: Nitration of 1,8-dihydroxynaphthlene JCS Calvert & Canero 1936.pdf (149kB)
This file has been downloaded 42 times

It sound like they are sensitive to oxidation and so need special conditions. By the way in one of the papers it refers to an interesting nitrating mixture; copper nitrate and acetic anhydride. The question is are they taking about anhydrous copper nitrate or the normal trihydrate and the acetic anhydride is basically to take up the water as well as the acetyl nitrate? Its not clear from the article.
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PHILOU Zrealone
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[*] posted on 13-1-2017 at 14:05


@Boffis,

Thank you for those papers.

Cu(NO3)2 is sometimes used anhydrous for special aromatic nitrations, but such anhydrous nitrate tends to be very oxydant/reactive...so maybe here they used it as hydrate with Ac2O to temper the reaction a bit vs the sensitive dihydroxynaphtalen.




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[*] posted on 13-1-2017 at 14:50


Probably off topic but I didn't think anhydrous copper (II) nitrate was even possible.
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[*] posted on 13-1-2017 at 22:48


Anhydrous copric nitrate is possible. Many years ago when I was at university its preparation was one of the final year undergrad practicals. While I didn't study chemistry several of my friends did and somewhere at home I have some copies of their lab sheets which came from a practical chemistry book by Rocket and Marr. I always though these were very appropriate names for authors of a chemistry book. I can't remember whether it is made by dissolving copper metal or black copper oxide in liquid NO2 and allowing the excess NO2 to evaporate.
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[*] posted on 14-1-2017 at 11:35


Quote: Originally posted by j_sum1  
Probably off topic but I didn't think anhydrous copper (II) nitrate was even possible.

Possible as explained by Boffis.
copper (II) nitrate from wikipedia
The link also gives the name of the aromatic nitration by anhydrous Cu(NO3)2 and Ac2O --> Menke conditions

Refering to link 14)
Menke J.B. (1925). "Nitration with nitrates".
Recueil des Travaux Chimiques des Pays-Bas. 44: 141. doi:10.1002/recl.19250440209.

Edit:

Menke nitration papers kindly provided by gdflp into the requested document section.

[Edited on 15-1-2017 by PHILOU Zrealone]




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Boffis
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[*] posted on 15-1-2017 at 07:48


Hi Philou, I haven't read the Menke paper from Recueil des Travaux Chimiques des Pays-Bas in detail but from the brief look I gave it it is quite clear that he is referring to the copper II nitrate trihydrate (he states this catagorically). This is interesting because hydrated copper nitrate is easy to obtain and it appears that it tends to be preferentially o- orientating. One of the paper you requested specifically the nitration of aniline to give 2-nitroaniline and only traces of the 4- isomer; I wonder if they nitrated aniline itself or acetanilide?
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[*] posted on 15-1-2017 at 11:28


Quote: Originally posted by Boffis  
Hi Philou, I haven't read the Menke paper from Recueil des Travaux Chimiques des Pays-Bas in detail but from the brief look I gave it it is quite clear that he is referring to the copper II nitrate trihydrate (he states this catagorically). This is interesting because hydrated copper nitrate is easy to obtain and it appears that it tends to be preferentially o- orientating. One of the paper you requested specifically the nitration of aniline to give 2-nitroaniline and only traces of the 4- isomer; I wonder if they nitrated aniline itself or acetanilide?

Yes I requested two documents (edited into previous post); it seems that the copper nitrate hydrate and acetic anhydride or that copper nitrate hydrate and acetic acid are used when the substrate is strongly activated to ensure mono-nitration.

As I explained anhydrous Cu(NO3)2 is too strong: allows formation of trinitrophenol from phenol or dinitrotoluen from toluen; while when water is present via acetic acid instead of anhydride or via Cu(NO3)2 hydrate, only mono-nitro compounds are formed.

I think they used the anilin straight without acyl protection.
Seems a good way to o-nitroanilin...precursor of your interesting benzotriazen and triazole chemistry ;)

I'm trying to read the German text...but will take me more time.

Edit:
I did a quick translation screening of the german text and found out that Menke used Cu(NO3)2.3H2O with acetic anhydride...and got directly o-nitro-acetanilid...what seems logical because of the acetic anhydride.

[Edited on 15-1-2017 by PHILOU Zrealone]




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[*] posted on 28-1-2017 at 12:13


Today I took a stab at making 2,4-diaminonaphthol from Martius yellow. It's a very important compound because while not a dye itself, it is the intermediate needed to make the rest of the dyes in Fieser's series. The procedure is pretty straightforward- reduce the Martius yellow with sodium dithionite, collect the beige precipitate, and then dissolve it in HCl to yield a colorless solution of the hydrochloride which can then be used to prepare the other dyes.

It appears that my sodium dithionite is no longer active though, as the reduction didn't work. It clearly did something, but the color never faded, and the precipitate remained orange.

IMG_2994.JPG - 1.2MB
Once again it's turning my pictures sideways. This, aga, is why I prefer to post on my blog.

Full post: https://texium.wordpress.com/2017/01/28/attempt-at-making-24...




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[*] posted on 28-1-2017 at 13:47


Awww. The horizontal gravity is quaint. Must be a Texas thing.
I can't help with the dodgy dithionate or mystery orange compound.
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[*] posted on 28-1-2017 at 18:02


Maybe use iron powder (or whool) and HCl instead of dithionite?



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[*] posted on 28-1-2017 at 19:33


Rit White-Wash is sodium hydrosulfite (sodium dithionite) plus a little sodium carbonate, available at your supermarket or Wally Mart:

https://www.walmart.com/ip/Rit-White-Wash-Laundry-Treatment-...

Also Dharma Trading:

http://www.dharmatrading.com/chemicals/jacquard_sodium_hydro...

[Edited on 29-1-2017 by Magpie]

[Edited on 29-1-2017 by Magpie]




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[*] posted on 28-1-2017 at 21:24


Thanks Magpie! I'll probably order some of that from Dharma Trading.



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[*] posted on 29-1-2017 at 12:13


Quote: Originally posted by j_sum1  
The horizontal gravity is quaint.

This only happens in Texas within the bio-generated gravity-radius of a fully-occupied McDonalds' ;)

Quote: Originally posted by zts16  
This, aga, is why I prefer to post on my blog

There's an old photographer's trick called 'rotate the camera' ...

Beautifully clear photo.

Thanks for posting it here as well as your blog.





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