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Hexavalent
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[*] posted on 9-4-2012 at 04:15
Anthranilic Acid Synthesis


Target compound;



Is there a way to selectively nitrate benzoic acid on the meta position and then reduce it to an amine in the same fashion that NurdRage uses at the end of his luminol synthesis video, at http://www.youtube.com/watch?v=58Ve69s0qD0 ??

I plan to use the anthranilic acid following Ozonelab's procedure to make 2-Iodobenzoic acid, and have reviewed alternative methods to make the anthranilic, yet unfortunately do not have the required reagents. Just considering alternative methods here.

[Edited on 9-4-2012 by Hexavalent]




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mnick12
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[*] posted on 9-4-2012 at 06:51


Yes nitration of benzoic acid or its esters will yield the 3-nitro compound. However if you are interested in anthranilic acid then you want the 2-nitro compound. There are a number of ways to synthesize aminobenzoic acid, and a few have already been discussed. You may consider the Hofmann rearrangement of phthalimide, or nitration of benzyl acetate. Or if you want something a little more OTC toluene can be nitrated, and its isomers easily separated by vacuum distillation (from my own experience it works quite well). From there 2-aminobenzoic acid is only a few steps away. Also look to see if anthraniliamide is available to you, it is easily hydrolyzed to anthranilic acid.
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Hexavalent
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[*] posted on 9-4-2012 at 07:03


I do not have access to phthalimide, benzoic acid, toluene or anthraniliamide, that is why I was looking for alternative synthesis routes.



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barley81
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[*] posted on 9-4-2012 at 07:32


Phthalimide can be made from phthalic anhydride and either aqueous ammonia or ammonium carbonate. One might also be able to use urea, since it is possible to make amides with urea. Here is the link:

http://orgsyn.org/orgsyn/default.asp?formgroup=basenpe_form_...

Since you made luminol, I think you have some phthalic anhydride. Ammonium carbonate is used for baking and should be easy to get, if you don't already have concentrated ammonia.


Benzyl acetate is made from benzyl alcohol and acetic acid, not benzoic acid. Benzyl alcohol should be easy to get on eBay or from a chemical supplier, and acetic acid is sold at photography stores (for darkroom stuff).
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peach
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[*] posted on 9-4-2012 at 08:26


Phthalic anhydride can be made by extracting a box of disposable vinyl gloves, if need be.

I will be making some Anthranilic at some point soon, as I want to go to IBX. Thankfully, I have a small amount of Phthalic anhydride already floating around.

You could buy some sodium benzoate food preservative and make the benzoic from that.

This video demonstrates the glove idea. He has the rest of the videos in his profile:

<iframe sandbox width="560" height="315" src="//www.youtube-nocookie.com/embed/cooRCFa3J3s?rel=0" frameborder="0" allowfullscreen></iframe>

[Edited on 9-4-2012 by peach]

<!-- bfesser_edit_tag -->[<a href="u2u.php?action=send&username=bfesser">bfesser</a>: fixed broken embed]

[Edited on 23.12.13 by bfesser]
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[*] posted on 9-4-2012 at 11:14


Sounds grape.

Have you considered purifying methyl anthranilate from goose repellent concentrate, then trivially hydrolyzing the ester?

Goose repellent is usually at least 50% pure with a dose of clove oil (or similar) and alcohol.

For example:
Liquid Fence Goose Repellent MSDS

[Edited on 9-4-2012 by arsphenamine]
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barley81
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[*] posted on 9-4-2012 at 14:37


Esters of anthranilic acid are DEA List 1 chemicals in the US. Red phosphorus is also on the list. It's funny/strange that red phosphorus is near impossible to buy (for individuals) but methyl anthranilate is sold in bulk quantities over the counter.
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[*] posted on 9-4-2012 at 18:03


DEA List 1 sounds a lot more dire than it is. It seems to be a catch list for whenever a prosecution for conspiracy is desired. It also amounts to price support for the (dying) US Chemical industry. DEA has no license requirements for researchers. It does have restricted lists but those are different. E.g. I can buy anthranillic acid and red P all day but I can't buy ergotamine,



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[*] posted on 10-4-2012 at 18:50


Quote: Originally posted by Hexavalent  
I do not have access to phthalimide, benzoic acid, toluene or anthraniliamide, that is why I was looking for alternative synthesis routes.


Mind telling us which reagents which are available to you? If you cant get phthalimide, benzoic acid, or toluene then how do plan on achieving the aromatic nucleus of anthranilic acid? Sure there are other options, but they would surely be much more complicated. I would recommend you stick to tried and true methods, I am all for ingenuity but there is no need to over complicate things. Toluene can be purchased in most hardware stores across the world, and can easily be mono-nitrated with excellent yields. This compound provides a basis for the cheap and relatively simple synthesis of 4- and 2- aminobenzoic acids.

This is just one of many possible routes, but at some point you are going to need a simple aromatic molecule to modify. The compounds mentioned earlier are by no means the only ones that will work, but are certainly among the most convenient.

Even if these reagents are not currently available, many of them are OTC and can be found locally with little effort. Its all about what you have available, and if you are willing to put in the effort.
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[*] posted on 11-4-2012 at 11:21


could salysilic acid not be refluxed in ammonia and then acidified to form Anthranilic acid and water as the by product, as this could be easily done as salysilic acid is easily available from aspirin tables as the aspirin would only need to be extracted and then saponified to get salycilic acid.
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[*] posted on 12-4-2012 at 04:36


Refluxing in ammonia won't yank off that hydroxyl group and replace it with an amine. You probably can't make anthranilic acid from salicylic acid.

Do you have a reference for that?
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[*] posted on 12-4-2012 at 04:48


That's a shame TBH, as I have plentiful access to ammonia and salicylic acid. If absolutely necessary, though, I guess I could get some toluene off eBay for the synthesis.



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[*] posted on 12-4-2012 at 06:11


Preparation from toluene is a fairly long affair. Nitration and separation of the isomers, oxidation to the 2-nitrobenzoic acid, reduction to the anthranilic acid, diazotization and iodination gets you to 2-iodobenzoic acid, in 5 steps. Even assuming an optimistic/unrealistic 80% yield for each step, overall yield for this linear synthesis is 33% overall.
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[*] posted on 12-4-2012 at 08:41


just realised my salycilic acid method won't work as i was thinking of replacing a halogen with and amine oops.
should probably read through my reference before posting and not just try and remember it.
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[*] posted on 9-8-2012 at 09:29
Sythesised anthranilic acid today


Hello people,

Today as a part of my syllabi, I synthesized anthranilic acid. Three sets were used first being NaOH and water kept in subzero conditions, second being NaOH and water at normal r.t., third was pthalamide wetted to pourable consistency.

To first cold mixture bromine was added to get sod.hypobromite, pthalamide was added and third mixture (water and NaOH at rt) this was then heated on water bath for approx two minutes.

The above heated mixture was again placed in ice bath slowly and gradually with strong stirring and swirling conc. HCl was added to neutralize, after neutralizing of mixture the crude yeild was precipatated out by adding glacial acetic acid temprature still maintained low.

The crude is recrystallized by hot water with charcoal treatment. I didnt write quantities as its std procedure in Vogels book. All being said I could'nt get white crystals, I Screwed up in recrystallization process. Final crystals were very light brownish and yield was ok.




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[*] posted on 3-12-2012 at 07:04


Hi, I synthesized anthranilic acid from phtalimide via chlorine water oxidation, it workfine , the trick is to precipitate the anthranilic acid with galcial acetic acid then recryst from water with a lot of charcoal like 1 tsp. I got the same light brownish crystals and when i checked the crystals under uv-light the crystals glowing green-bluish meaning that there are few impurities left, then I re- recryst from water again and i got some nice white crystals.



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[*] posted on 11-6-2013 at 08:50


Quote:

Anthranilic Acid

Dissolve 8.0g of sodium hydroxide in 30ml of distilled water in a 100ml erlenmeyer flask containing a magnetic stirrer bar and cool the solution with stirring in an ice bath. Add the bromine [2.1ml, 6.5g, 41mmol] (CARE!) in one portion and stir the mixture vigorously until all of the bromine has reacted [look for the disappearance of the brown colouration] and the mixture has cooled to ca. 0*C. Continue vigorous stirring and add all of the finely powdered phthalimide [5.9g, 40mmol] to the solution, followed by a solution of a further 5.5g of sodium hydroxide in 20ml of water. Remove the ice bath, allow the temperature of the mixture to rise spontaneously to ca. 70*C and continue stirring for a further 10 min. Cool the clear solution in an ice bath with stirring (if the mixture is cloudy, filter under gravity before cooling), and add concentrated hydrochloric acid dropwise with a pipette until the solution is just neutral when a drop is spotted onto universal indicator paper (ca. 15ml should be necessary). If too much acid is added, the mixture may be brought back to neutrality by adding further quantities of sodium hydroxide solution, but it is better to avoid this by careful addition of acid in the first instance. Transfer the mixture to a 500ml beaker (foaming occurs in the next stage) and precipitate the 2-aminobenzoic acid by addition of glacial acetic acid (ca. 5ml). Filter off the precipitate with suction, wash the residue with 10ml of cold water and dissolve it in the minimum quantity of boiling water containing a little activated charcoal. Filter the hot solution to remove the charcoal and cool the filtrate with ice. Filter off the pure acid with suction, dry the residue with suction on the filter for 5 min and complete the drying to constant weight in an oven at 100-120*C

Vogel 5th

I like to try this method but i want to replace Sodium HypoBromite with Calcium HypoChlorite(H.T.H).Bromine is nasty and toxic and i dont want to work with that.
Somebody has experience of it?Can i replace H.T.H with NaOBr?
How much should i use?


[Edited on 11-6-2013 by Waffles SS]
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[*] posted on 11-6-2013 at 11:31


Quote: Originally posted by barley81  
Esters of anthranilic acid are DEA List 1 chemicals in the US. Red phosphorus is also on the list. It's funny/strange that red phosphorus is near impossible to buy (for individuals) but methyl anthranilate is sold in bulk quantities over the counter.

Methyl anthranilate is an extremely common flavouring agent. Red phosphorus isn't.




Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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plante1999
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[*] posted on 11-6-2013 at 13:11


Quote: Originally posted by DraconicAcid  
Quote: Originally posted by barley81  
Esters of anthranilic acid are DEA List 1 chemicals in the US. Red phosphorus is also on the list. It's funny/strange that red phosphorus is near impossible to buy (for individuals) but methyl anthranilate is sold in bulk quantities over the counter.

Methyl anthranilate is an extremely common flavouring agent. Red phosphorus isn't.


never saw any on the shelf's, or on the internet.




I never asked for this.
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[*] posted on 11-6-2013 at 14:08


I should have said "industrial flavouring agent". Anything grape flavoured will contain it- my college can easily buy it, even though we can't buy anthranilic acid any more.



Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
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[*] posted on 1-4-2015 at 03:25


Okay, I've managed to get some amount of phthalimide, but...
I followed rhodium's procedure for anthranilic acid preparation: cool NaOCl, add NaOH to it (dr dream says to add more NaOH later, but I don't know why and it works neither way for me), cool, add phthalimide with good stirring, mixture turns pale yellow-brown, heat to 80 C, cool, add HCl until 7 ph, filter precipitate (i always get like 0.5-1 g of it), add acetic acid -> a lot of bubbles come out -> mixture turns brown and nothing precipitates. Just a nice clear brown solution.
First i thought it's some wrong phthalimide. Tried m.p. check - got approx. 226 C. Looks like a mixture of something. Thought it's a phthalamide, so to conver it into phthalimide i boiled it - m.p. of the liquid-solid became like 233 C, but the liquid was strongly colored in dark brown. I was not able to smell any ammonia, so probably it was not a phthalic diamide.
Next I sublimated it trying to get a purified phthalimide, got a cracked flask and completely clogged outlet with some nice white soid, because I suck at sublimation.
Attempt to use sublimated white solid in reaction and got absolutely the same result: pale yellow NaOCl+phthalimide solution, brown after acidification without precipitate.
The brown liquid colors a light blue solution of CuSO4 in 10% acetic acid into bright green, but no precipitate comes out (anthranilic acid is used in gravimetric analysis of metals like zinc, lead, copper, etc precipitating the complex with metal), so I don't even know if there is some anthranilic acid in the solution or not.
Probably the question that bothers me the most is: wtf is my main precursor? So, let's take some of those shiny crystals, put in the flask with resorcinol (x:resorcinol = 1:1.5, standard procedure for phthalic anhydride) and add the same amount of conc H2SO4 in it, then boil for a few minutes, dillute and basify (red clear solution turns opaque green). Few drops of it into a glass of water give us the picture.
Similar reaction with phenol gives in the dillute basic solution gives a pink color (the flask to the right)
Fluorescience and phthaleine.JPG - 193kB
It looks like something o-phthalic, but how can i use it for anthranilic acid preparation? Maybe it's some really dirty phthalimide, and maybe the content of phthalimide is less then 50%, or i'm just stupid enough to take the wrong part of the solid after sublimation (m.b. should use the one that is left in the source flask).
And i was unable to find any qualitative tests to distunguish between phthalimide, phthalic anhydride for chromatography - I would probably get the same phthalein and phluorescien reactions for any o-phthalic derivative.
Also i'd like to mention that my "phthalimide" smells like a jasmine.
upd: forgot to link the rhodium page https://www.erowid.org/archive/rhodium/chemistry/anthranilic...

[Edited on 1-4-2015 by byko3y]
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morganbw
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[*] posted on 1-4-2015 at 14:54


Quote: Originally posted by byko3y  
https://www.erowid.org/archive/rhodium/chemistry/anthranilic...

[Edited on 1-4-2015 by byko3y]


Only now do I understand. :(
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