Sciencemadness Discussion Board - Naphthaleneacetic acid Synthesis

Naphthaleneacetic acid Synthesis

Waffles SS - 28-4-2013 at 06:54

Quote:

1-Naphthaleneacetic acid (NAA) is an organic compound with the formula C10H7CH2CO2H. This colorless solid is soluble in organic solvents. It features a carboxylmethyl group (CH2CO2H) linked to the "1-position" of naphthalene.
http://en.wikipedia.org/wiki/1-Naphthaleneacetic_acid

Does Friedel Crafts of MCA(Mono Chloro Acetic Acid)and Naphthalene Lead to NAA?There are any simpler way?

[Edited on 28-4-2013 by Waffles SS]

ScienceSquirrel - 28-4-2013 at 11:40

See here;

http://pubs.acs.org/doi/abs/10.1021/ja01165a533

Waffles SS - 9-5-2013 at 00:55

It seems cheaper and more dangerous way will be

First Chloro Methylation of Naphthalene
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv3...

and then Making Naphthalene acetonitrile and finally hydrolysis by acid to form 1-Naphthalene acetic acid.

Making Naphthaleneacetonitrile is possible by reacting of Sodium/Potassium Cyanide to chloromethylnaphthalene (same as Benzyl cyanide from benzyl chloride).I want to know this reaction happen fast or slow?how can i improve yield?

[Edited on 9-5-2013 by Waffles SS]

ScienceSquirrel - 9-5-2013 at 12:21

That may be the best approach.
I suspect that a quick literature review will pull up well tested preparations that should be easy to repeat.
I would not describe chloromethylation or reaction with cyanide as dangerous if you have a good fume hood and reasonable technique.

DraconicAcid - 9-5-2013 at 12:36

Quote: Originally posted by ScienceSquirrel

That may be the best approach.
I suspect that a quick literature review will pull up well tested preparations that should be easy to repeat.
I would not describe chloromethylation or reaction with cyanide as dangerous if you have a good fume hood and reasonable technique.

If you're paranoid about cyanide, you can probably make a Grignard reagent with the chloromethylnaphthalene and react it with carbon dioxide.

Waffles SS - 9-5-2013 at 22:31

Another possible route will be reacting 1-Naphthylmagnesium bromide(Grigniard reagent) with Chloroacetic acid
US2290401(But not certain detail about yield)

Somebody has experience on making 1-Bromo Naphthalene ?

Vogel 5TH Page863

Attachment: US2290401A.pdf (86kB)
This file has been downloaded 568 times

[Edited on 10-5-2013 by Waffles SS]

ScienceSquirrel - 10-5-2013 at 05:56

1-Naphthylmagnesium bromide will react with chloroacetic acetic acid to give you you napthalene.

Waffles SS - 10-5-2013 at 06:29

This mean US2290401 is Bullshit?

ScienceSquirrel - 10-5-2013 at 07:11

I would be a little dubious about that patent.
If you have a look at it the maximum yield you can achieve is 50%.
The first reaction is to form napthalene and magnesium bromide chloroacetate, as I said above.
So half of your Grignard reagent is consumed doing this.
The magnesium bromide chloroacetate then reacts with the remaining Grignard to form napthylacetic acid.
Worth a try if you have the reagents to hand and want to make a few grams but it is not the cheapest or the best way.

Waffles SS - 10-5-2013 at 08:45

What is your suggestion?what method you prefer?

ScienceSquirrel - 10-5-2013 at 12:07

If I wanted a few grams and I had a source available I would buy it.
It is moderately available from all sorts of places, put a watch on it on eBay for example and it will turn up in a few months.
If you can access a research chemical supplier or someone who acts as reseller then you can just order it.
I suspect that professional nursery and hydroponics suppliers can supply it also.
If I had to make a few grams, I would go for either the Friedel Crafts or the Grignard reaction.
If I wanted kilos and I had the time I would go for bromomethylation on a research scale or chloromethylation on an industrial scale, reaction with cyanide and hydrolysis.
It is a three step process but optimised I reckon you could do better than 90% on each stage, it is highly atom efficient with cheap reagents and will produce very little 'glop'.

Waffles SS - 15-6-2013 at 08:53

Quote:

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv2...

Ethyl α-Naphthoate prepare by reaction of α-naphthylmagnesium bromide with Diethyl carbonate.I think this should be possible for 1-Naphthaleneacetic acid, methyl ester by reaction of 1-(Magnesium Chloromethyl) Naphthalene with Dimethyl Carbonate.am i wrong?

Waffles SS - 20-6-2013 at 22:26

Naphthyl Acetic Acid by Willgerodt reaction

Vogel 5th

Naphthyl Methyl Ketone

Vogel 5th

Quote:

Naphthyl Methyl Ketone

(1) Acetic anhydride (20.4 g.; 1 mol.) was gradually added to a well stirred mixture of aluminium
chloride (56 g. ; 2 mols.) in ethylene chloride (100 c.c.). After 3 hours stirring, a solution of naphthalene
(25.6 g.) in ethylene chloride (50 c.c.) was gradually added. The temperature was kept at 35c during
the addition, but was subsequently raised to 50c to complete the reaction. After decomposition with
dilute hydrochloric acid the product provided a fraction (20 g.; b. p. 163c/15 mm.; m. p. 9.0 and
mixed m. p. 9.5 with pure a-naphthyl methyl ketone) which was almost pure a-naphthyl methyl
ketone. Picrate analysis indicated 97.5% of a-ketone.
(2) A solution of acetyl chloride (8 g. ; 1 mol.) and aluminium chloride (14 g. ; 1 mol.) in ethylene
chloride (30 c.c.) was gradually added to a solution of naphthalene (13 g.) in ethylene chloride (30 c.c.)
at 35c. A ready reaction occurred, and a solid separated. The mixture was decomposed with dilute
hydrochloric acid, and the product provided a fraction (16 g. ; b. p. 163c/15 mm. ; m. p. 9.0c and mixed
m. p. 9.5 with pure a-naphthyl methyl ketone) which was almost pure a-naphthyl methyl ketone.
Picrate analysis indicated 98% of a-ketone. A similar result was obtained when the solution of naphthalene
was gradually added to the solution of acetyl and aluminium chlorides.

The acylation of naphthalene by the friedel–crafts reactionG. BaddeleyJ.
Chem. Soc.1949, S99-S103
DOI: 10.1039/JR9490000S99

It seems this is possible to make 1-Naphthyl Acetic Acid by Willgerodt reaction,and also Naphthyl Methyl Ketone by FC.
Unfortunately i dont have access to anhydrous AlCl3 and i dont want to work with CCl4.I know FeCl3 is another possible catalyst for FC but i dont know this is effective in this reaction or not?.I want to acylation of Naphthalene by F3Cl3 as catalyst and Methylene Chloridei(CH2Cl2) as solvent(like above reaction).Somebody has experience on these reactions?

[Edited on 21-6-2013 by Waffles SS]

Furboffle - 21-6-2013 at 09:54

Idk if you just really wanna make it. But check out Caisson Labs. They focus on stuff for cell cultures but sell naphthalene acetic acid as a culture nutrient. Pretty cheap 100g for 25$.
I ordered indole acetic acid from them and they sent me a goody back with 5g indole butyric acid, 5g naphthalene acetic acid and a bunch of murshige and skoog as if I'm trying trying to do some cell culture project. Cheap and great customer service.

[Edited on 21-6-2013 by Furboffle]

Zephyr - 8-4-2015 at 15:47

I've recently attempted a synthesis of NAA using the procedure waffles linked.
Here are some photos:

The above pictured crystals are just a small test portion of the total batch.

The total 8g of dirty brown goop was recrystallized twice, total yield 4.5g, about 35%.

I'm very interested in synthesizing and comparing the effects of IAA. Does anyone know if The same synthesis can be used by just switching the naphthalene with indole? Or possibly of source of indole more affordable than elemental scientific?

Ps. sorry to dredge up this old thread.

Waffles SS - 8-4-2015 at 21:37

Which method you used?

For IAA try first :

Synthesis Indole-3-acetonitrile by Cyanomethylation of Indole with Diethylaminoacetonitrile
(https://erowid.org/archive/rhodium/chemistry/diethylaminoace...)

Then hydrolysis Indole-3-acetonitrile by 20% KOH soultion

[Edited on 9-4-2015 by Waffles SS]

Zephyr - 9-4-2015 at 07:52

I used the chloroacetic acid and naphthalene with iron oxide and potassium bromide as catalysts.

I could do that synthesis, but I would prefer to try an easier one first.

Waffles SS - 9-4-2015 at 09:31

Please let us know the deatils.

I attached Reaxys search of IAA and NAA.you can find another interesting method for synthesis IAA and NAA.

I have experience on synthesis of Auxins(IAA , NAA ,IBA,PAA) and will share with you.

I think my suggest method is one of the easier method for synthesis IAA.

(also you can follow Inole synthesis in below topic:
http://www.sciencemadness.org/talk/viewthread.php?tid=13152)

Attachment: IAA reaxys search.pdf (357kB)
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Attachment: NAA reaxys search.pdf (336kB)
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[Edited on 9-4-2015 by Waffles SS]

Zephyr - 10-4-2015 at 22:58

I vaguely followed this procedure for both of my syntheses:
http://pubs.acs.org/doi/abs/10.1021/ja01165a533
*just realized this was sciencesquirrels not waffles

For my first synthesis I messed with the catalysts a little, using iron oxide and sodium bromide instead of potassium bromide.
For this synthesis I used a 3g of chloroacetic acid and 12g of naphthalene. I refluxed this for four hours at 190C, but when I washed the resulting black glob I used a vast over excess of NaOH solution (amount was not specified in the procedure). As a result I need a lot of hydrochloric acid to neutralize the solution, and at this point I had ~500ml of neutralized solution with very little precipitate. I filter and got a tiny amount, not nearly enough to recrystallize.

My second try was much more successful, and it is where the photos are from. The procedure remained essentially the same, except I used the recommended catalysts, refluxed for eight hours and at 210C, and only washed with 3 50ml portions of 1/2 molar NaOH solution, after neutralization ending up with ~200ml of solution. These improvements allowed a much better yield.

I plan on doing a larger version of this in order to receive enough NAA to use it for experimenting on plants.

Ps. is it just me or are superscripts not working???

Waffles SS - 11-4-2015 at 10:05

I tried this method X100 your scale but i was unsuccessful.I got 10-15gr grey powder that dont seems to be NAA

I was successful in synthesis of NAA by Willgerodt reaction(according to my above procedure) but this methos has several step and make NAA more expensive.

I want to try MCA + Naphthalene method again.

[Edited on 11-4-2015 by Waffles SS]

Attachment: The Role of Chloroacetylpolyglycolic Acids.pdf (564kB)
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Attachment: US1951686A.pdf (150kB)
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Attachment: US2617822A.pdf (707kB)
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Zephyr - 11-4-2015 at 11:35

I hope you tried recrystallizing the grey powder? Prior to recrystallization I had brown mud.

Waffles SS - 12-4-2015 at 08:22

Yes i did it.

I am not sure about my Iron(III)Oxide,that was industrial grade and i am looking for lab grade sample

Do you have pic from your brown mass?

[Edited on 12-4-2015 by Waffles SS]

woelen - 14-4-2015 at 23:46

Moved thread after request. This thread is beyond beginner-level and organic chemistry seems to be a proper place for it.

Zephyr - 18-4-2015 at 20:08

Yes, here is a picture of the brown gunk prior to recrystallization: