Sciencemadness Discussion Board

Martius Yellow - fun with dyes

Magpie - 14-3-2013 at 13:36

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.


Sublimatus - 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

Paddywhacker - 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.

Morgan - 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.

Magpie - 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)
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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.


Magpie - 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

AndersHoveland - 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 ?

Magpie - 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]

Lambda-Eyde - 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 -OSO<sub>2</sub>OH moiety with a nitro.


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

Magpie - 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?

DraconicAcid - 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.

CuReUS - 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

Magpie - 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]

Texium - 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.

Magpie - 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.

Metacelsus - 25-12-2016 at 17:42

C.P. means chemically pure in this context.

Texium - 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.

Texium - 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?

aga - 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.

Magpie - 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.

Texium - 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.

aga - 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 ?

Texium - 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...

aga - 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 !

Texium - 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.

aga - 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 ...

PHILOU Zrealone - 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.

Boffis - 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 360 times

Attachment: Nitration of 1,8-dihydroxynaphthlene JCS Calvert & Canero 1936.pdf (149kB)
This file has been downloaded 396 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.

PHILOU Zrealone - 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.

j_sum1 - 13-1-2017 at 14:50

Probably off topic but I didn't think anhydrous copper (II) nitrate was even possible.

Boffis - 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.

PHILOU Zrealone - 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]

Boffis - 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?

PHILOU Zrealone - 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]

Texium - 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...

j_sum1 - 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.

PHILOU Zrealone - 28-1-2017 at 18:02

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

Magpie - 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]

Texium - 28-1-2017 at 21:24

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

aga - 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.