benzylchloride1
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Sulfanilic Acid
I am currently working on the synthesis of sulfanilic acid, which I plan to use for the synthesis of o-nitroaniline. I started with aniline sulfate
and dissolved it in concentrated sulfuric acid. I heated it with a heating mantle at around 190 celsius for 8 hours. The temperature exceeded 208
degrees for about 20 minutes. The mixture turned to a purple black colored and gave off fumes of sulfur dioxide near the end of the heating period.
The mixture was poured into water and a solid precipitated and the solution was a distanctive purple in color. The procedure I used mentioned some
discoloring, but the color seems excessive. I think that the temperature caused the sulfuric acid to oxidize the aniline to aniline black, producing
sulfur dioxide in small quantity. I doubled the scale of the procedure in Laboratory Experiments in Organic Chemistry by Adams, Johnson and Wilcox.
This procedure mentions a yield of around 50% after heating for five hours. I am afraid that my attempt at increasing the yield by heating for a
longer peroid may have decreased my yield substantially. I will post the yield as soon as the product is isolated and dried.
[Edited on 10-2-2009 by benzylchloride1]
Amateur NMR spectroscopist
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benzylchloride1
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I then poured the reaction mixture into water and then filtered the crude sulfanilic acid. The crude acid was then washed with water and was a greyish
purple color. The sulfanilic acid was then suspended in water and sodium hydroxide solution added until the solution was neutral. Powdered
decolorizing charcoal was added and the mixture was heated to boiling. The mixture was than filtered and the slightly discolored solution acidified
with hydrochloric acid. Crystals of sulfanilic acid formed and the solution was cooled in an ice bath. The crystals were than filtered off and dried
in a 80 celsius oven. The mother liquer from the crystallization was then concentrated to half of its volume and crystals formed after seeding and
cooling.
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Axt
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Here a section of a writeup that I'm yet to, if ever complete. I dont recommend using your mums kitchen microwave like I did (it stinks) but it sure
beats heating it conventionaly for 8 hours. I dont seem to have recorded the yield though it was quite good. I added concentrated H2SO4 to the
water-aniline here but it would be better to add aniline to the diluted acid instead.
<b>Sulphanilic Acid</b>
Sulphanilic acid a clear, crystalline compound that is typically prepared by heating aniline with concentrated sulphuric acid. It decomposes below its
melting point at 280-300°C and is slowly soluble in about 90 parts water, 15 parts boiling water; though almost insoluble in alcohol, benzene and
ether. The typical preparation by heating aniline in concentrated sulphuric acid is undesirable, due to the high temperatures and long reaction time
that is necessary to complete the sulphonation[1].
The sulphonation is reportedly 75 times faster under microwave irradiation, reducing the reaction time from 5 hours to just 4 minutes[3]. This rapid
reaction rate is attributed to the selective absorption of microwave energy by polar molecules. Being strongly polar the sulphate salts rapidly reach
a high temperature and undergo dehydration and rearrangement forming the sulphonated product.
<i>Preparation</i>: 20g aniline (215mmol) is added to 38ml water in a 400ml beaker. 25g (255mmol) sulphuric acid is added slowly; forming
a thick slurry of aniline sulphate (figure?). The slurry was then irradiated in a kitchen microwave oven for 4 minutes.
After the irradiation the product remained as a hard, purple, pumice like solid in the bottom of the beaker (figure ?) which was broken up with a
knife.
30g sodium carbonate in 200ml water was added, with heating, to dissolve the product as its sodium salt. The dark purple solution was filtered
removing some of the purple by-product, and then 35ml of 32% hydrochloric acid was added to precipitate the sulphanilic acid as glistening light
purple crystals with a pearly lustre (figure ?). The precipitate was filtered and washed on the filter paper with 100ml ethanol, which removed much of
the purple by-product but the crystals retained a faint lilac colour.
[Edited on 13-2-2009 by Axt]
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benzylchloride1
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That is impressive! Thank you for sharing this on Sciencemadness. Im planning on getting a cheap used microwave for my home lab for my experiments. I
purchased a kilogram of aniline sulfate off of Ebay for around $25.00. Did you prepare your aniline from benzene or purchase it? My sulfanilic acid is
currently drying in a drying oven to remove the water of crystallization. It is currently a gray color. Your reaction mixture looks similar to what I
obtained. The crystals look just like the crystals that I obtained. Axt do you have a reference for your procedure, I would like to read more about
this method as it seems excellent. The yield from my experiment seems to be way lower than 50%.
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Axt
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In this case the aniline was purchased, old and near black by now. This was investigated on route to OTC benzotrifuroxan, which is a 10 step
procedure, thus the reason my interest in completing it fizzled 
Sorry I cant find the bloody article though I know I had it at some stage, the citation is “A Study on the sulfonation of Aromatic Amines with
Sulfuric acid Under Microwave Irradiation”, Journal of Chemical Research, 493-494 (2003).
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Magpie
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Quote: Originally posted by entropy51  | | Quote: Originally posted by Magpie |
BTW entropy, you will be glad to know that I'm now tending a little batch of sulfanilic acid per Brewster. |
Yes! I finally ran a Brewster prep before Magpie.
I'm sure you will get a higher yield, however.
Did you distill your aniline first? If not, your product may be a tad off-color. |
I'm not so sure about that yield. I got lazy and am just using antifreeze straight out of the jug as heat transfer fluid. The stuff bumps! Next
time I will use purified ethylene glycol.
Lazy on the second count also - did not distill my amber aniline. I just want enough good product to make some methyl orange. I'll post a picture on
edit.
Edit: The thermometer is reading 160-162C.
[Edited on 19-10-2010 by Magpie]
The single most important condition for a successful synthesis is good mixing - Nicodem
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entropy51
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| Quote: Originally posted by Magpie | | I'm not so sure about that yield. I got lazy and am just using antifreeze straight out of the jug as heat transfer fluid. The stuff bumps! Next
time I will use purified ethylene glycol. |
It will bump less if you put a little stir bar it, or at least
that's true when distilling antifreeze.
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MagicJigPipe
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Wouldn't there be some ortho-sulfanilic acid created as well? I suppose it would be much less than 50% due to the bulky sulfonate group, but surely
it's not all the para, right?
I'm referring to Axt's picture.
I've been trying to apply what I've been learning in organic to interpreting things on the forum so some input would be really helpful and
appreciated.
"There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any
question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and
that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think,
free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer
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entropy51
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Heating the aniline sulfate to about 180 C yields only the para isomer. Milder conditions are said to yield some ortho as well.
I'm sure Nicodem knows why this is so. I do not.
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Sandmeyer
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Great work Axt, though your mum would probably disagree!
| Quote: Originally posted by entropy51 | Heating the aniline sulfate to about 180 C yields only the para isomer. Milder conditions are said to yield some ortho as well.
I'm sure Nicodem knows why this is so. I do not. |
So, at lower temp the reaction gives some ortho prod while at higher temp it gives exclusively para prod with no ortho - what's the reference? It can
be argued that the ortho-product should be less stable due to the unfavourable steric interactions, the para product is free from this steric effect
hence the para product should be a more stable system. Sulfonation is a reversible process and at 180*C the major product should be that which is the
most stable one (i.e para), or if you like fancy words - the reaction will be under thermodynamic control.
[Edited on 20-10-2010 by Sandmeyer]
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Magpie
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Here's some preliminary results on the sulfanilic acid synthesis I began earlier this week. As I indicated I used antifreeze straight out of the jug
as heat transfer fluid for the heating period. This boils at 166C so I did not get the high soak temperature of ~195C that I would have if I had used
pure ethylene glycol. I tried to make up for this by using a long (8 hour) soak time.
At the end of the soak the product was poured into a beaker of crushed ice as shown below. This resulted in the precipitation of a somewhat gummy
suspension. This was then placed on a 7cm Buchner and pumped dry, saving the filtrate. The solids were then redissolved in hot water and some
activated charcoal added to remove some slight discoloration. This could be described as a very light red or purple. Suspecting that a lot of
product was in the filtrate from before I added this to the hot water solution followed by a little more charcoal. This was then heated to boiling
and filtered to remove the charcoal.
The filtrate flask was then cooled in an ice bath and the gummy product recovered on the Buchner funnel. It was washed with 5mL denatured alcohol.
Then it was placed on a dinner plate to dry at 55C. Then I turned up the oven to 80C. After several hours it was still gummy. It was then placed in
a desiccator over CaCl2 (per Vogel). After several hours I weighed it at 15.4g (see 2nd picture).
Tentatively assuming this is sulfanilic acid dihydrate, the yield would be 68%. I'm suspecting that I didn't get it washed well, especially in regard
to residual sulfuric acid. Monday I will recrystallize it and try to isolate a more pure sulfanilic acid product.
 
The single most important condition for a successful synthesis is good mixing - Nicodem
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Magpie
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The 15.4g of preliminary product sulfanilic acid was washed on a 7cm Buchner funnel as follows:
1. mix with 10mL ice cold water, stir, pump dry
2. mix with 5mL of 95% ethanol, stir, pump dry
3. wash with 10mL of ether and pump dry.
The washed product looked a lot better, ie, whiter and dryer, not gummy. It was placed on a piece of paper and dried at room temperature for 6 hours.
The chunks were chopped up using a razor blade. It looked quite dry. See picture below.
A lot of weight was lost during this washing, especially during the water wash. The final product weighed 5.6g. Assuming it is anhydrous sulfanilic
acid, the yield is 29.8%.
As a check on purity, 0.173g of the product was titrated to a phenolphthalein endpoint using 0.11N NaOH. This indicated a MW of 134 vs a book value
of 173. Although not as pure as hoped for it is a good improvement over the MW of 90 calculated for the unwashed preliminary product.
The single most important condition for a successful synthesis is good mixing - Nicodem
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