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Elementary
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Joined: 18 Apr 2005 |
Posts: 100 |
Location: UK |
3449.86 Points
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Willgerodt Reaction (phenylacetic acid route)
Wed Apr 20, 2005 3:49 pm |
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I believe the reaction was originally carried out with ammonium polysulphide rather than morpholine and sulphur.
Has anybody got an english translation of C. Willgerodt, Ber. 20, 2467 (1887); 21, 534 (1888) ?
I would also be interested in knowing if styrene can be used as well as acetophenone in the original reaction using ammonium polysulphide.
This reaction would be a nice OTC way of making phenyacetic acid as styrene monomer is easily acquired. Acetophenone would not be too much of a hardship to make either.
ADD ON:-
http://www.orgsyn.org/orgsyn/orgsyn/prepcontent.asp?print=1&showprint=1&prep=CV4P0760
See discussion (phenylacetamide made from acetophenone and ammonium polysulfide)
! Phenylacetamine can be hydrolysed easily to phenylacetic acid)
Would love to have a look at this ref :- Houben, Ber., 59, 2878 (1926). |
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IndoleAmine
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Thu Apr 21, 2005 3:44 am |
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"nice OTC way" involving ammonium disulfide???
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Monograph Number: 501
Title: Ammonium Bisulfide
CAS Registry Number: 12124-99-1
Additional Names: Ammonium hydrogen sulfide; ammonium hydrosulfide; ammonium sulfhydrate
Molecular Formula: H5NS
Molecular Weight: 51.11.
Percent Composition: H 9.86%, N 27.41%, S 62.74%
Line Formula: NH4HS
Literature References: Prepd by mixing stoichiometric amts of NH3 and H2S gases at 0°: Thomas, Riding, J. Chem. Soc. 123, 1181 (1923).
Properties: White, tetragonal or orthorhombic crystals. d 1.17. Sublimes in vacuo. Decomposes into H2S and NH3 rather easily at room temp when in crystal form. The commercial product is furnished in porcelain-like lumps which are more stable and can be stored in a closed bottle at a cool place. Dissociation press. at room temp about 350 mm Hg. Freely sol in water or alcohol giving colorless solns which turn yellow rapidly. Decomposed by boiling water. Soly (0°): 128.1 g/100 g H2O. Slightly sol in acetone; almost insol in ether, benzene.
Density: d 1.17
CAUTION: Very irritating to skin; penetrates more rapidly than hydrogen sulfide and may be fatal.
Use: In lubricants.
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Polverone
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Joined: 12 Feb 2005 |
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Thu Apr 21, 2005 9:30 am |
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Ammonium polysulfide can be used with styrene, but it's effective only if you have an autoclave handy. I've tried the variation based on a Chinese patent, posted on the Hive some time back, and didn't get much of anything because I couldn't run it under pressure.
The way I attempted it, after the failure of the first straightforward attempt, was by mixing ethanol, sulfur, and styrene monomer in a jar and adding sufficient Na2S and NH4NO3 to form ammonium polysulfide in situ. This was then capped and left to the attention of the sun's warmth (sealed in garbage bag) for several months. If stinkiness is the measure of success, this worked much better than simply trying to reflux aqueous ammonia, ethanol, sulfur, and styrene like the patent seemed to suggest, but I don't think it worked that well and I don't think it ever will work well without heating under pressure. I did just well enough to make a horrendous stench. The stink clings. I could taste it for a day after working with the crude reaction mixture. I can still smell it faintly on the shirt I was wearing that day and the shirts that were next to it in the laundry basket, though they've been washed 2-3 times now. It smells too bad for me to be eager to attempt other refinements.
I attempted to make a pressure vessel out of water pipe, but preliminary runs with colored alcohol showed that I couldn't get the endcaps to seal tightly enough, even with liberal teflon tape application. Maybe someday, with finely threaded stainless steel pipe... |
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IndoleAmine
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Thu Apr 21, 2005 12:31 pm |
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Quote: |
I did just well enough to make a horrendous stench. The stink clings. I could taste it for a day after working with the crude reaction mixture. I can still smell it faintly on the shirt I was wearing that day and the shirts that were next to it in the laundry basket, though they've been washed 2-3 times now. It smells too bad for me to be eager to attempt other refinements.
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As said already:
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CAUTION: Very irritating to skin; penetrates more rapidly than hydrogen sulfide and may be fatal.
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Nice you're still with us!
..and
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Maybe someday, with finely threaded stainless steel pipe...
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...and lots of teflon sealing tape on the threads insides, as well as plumber's seal on the outside, and done outdoors please.... |
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Elementary
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Thanks
Thu Apr 21, 2005 3:17 pm |
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Thanks Polverone Another dream that seemed so simple
Ammonium Polysulphide OTC you ask :-
Here would be your starting chemicals
Iron wool or filings heated with sulphur (garden centre) = Iron sulphide
Iron sulphide + Acid = Hydrogen sulphide
Household ammonia + hydrogen sulphide = ammonium polysulphide
BTW : Hydrogen sulphide is really poisonous |
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Nicodem
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Joined: 22 Feb 2005 |
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Thu Apr 21, 2005 7:33 pm |
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Ammonium polysulphide, (NH4)2Sx, is not ammonium bisulfide, NH4HS.
These are different compounds. And you get ammonium bisulfide by absorbtion of H2S in ammonia. You need also elementary sulphur to make polysulphides from sulphides. You can disolve elementary sulphur in aquoeus sulphide solutions.
example:
Na2S + S => Na2S2
Na2S2 + S => Na2S3
...and so on to higher sodium polysulphides
or you can make it by partial oxidation of the sulphides like Polverone did. |
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Polverone
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Joined: 12 Feb 2005 |
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Fri Apr 22, 2005 9:08 am |
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You misunderstand a bit. The stench is not that of hydrogen sulfide from dissociating ammonium polysulfide (though there is some of that too, and of course you must take care not to be poisoned by the sulfides) but of products formed with the styrene. It is a smell unlike anything else I have experienced, and it lasts/clings far longer than inorganic sulfides or polysulfides. I wish I had a pure reference sample of phenylacetamide to figure out if that's what the smell was. |
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nubee
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Fri Apr 22, 2005 9:23 am |
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im not pretending to have any opinion or know anything about what this thread is trying to work out, but i did a quick look around and found this info:
Quote: |
ORGLIST: Summary: oxidation of ethylbenzene
Thank you for all contributions to the problem: oxidation of substituted
ethylbenzene to substituted phenylacetic acid.
Allmost all contributions say, that the direct oxidation of ethylbenzene
to phenylacetic acid is not possible, since benzoic acid is formed.
One possible way is the oxidation of (substituted) acetophenone using
elementar sulphur and morpholine. This reaction is called
Willgerodt-Kindler-reaction. Unfortunately H2S is formed after
hydrolysis, which can be a great disadvantage of this reaction.
Another proposal was to start with a substituted styrene derivative,
which can be oxidized by hydroboration. However, hydroborations are not
very regioselective, or styrene itself gives a rather large percentage
of benzylic alcohol. Selectivity can be increased by using some
dialkylborane.
Another possibility is the Grignard reaction of alpha-bromotoluene using
Mg and carbon dioxide or of bromobenzene using Mg and ethylene oxide
with following oxidation.
An usual way is the chloromethylation of benzene to obtain
benzylchloride, followed by cyanuration to get the benzylnitrile, which
can be hydrolysed to the desired acid.
Now, I will think, which way I will try at first. Another possibility
could be also the Reformatsky reaction from substituted phenylbromide
and alpha-bromo ethyl acetate with activated zinc and Ni(PPh3)4
catalyst.
Cornelia
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ORGLIST - Organic Chemistry Mailing List
Website and Archive: http://www.orglist.net/
List coordinator: Joao Aires de Sousa (jas@mail.fct.unl.pt)
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http://www.dq.fct.unl.pt/orglist/archive/orgl1999/00000148.htm
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- N-METHYLTYRAMINE AND N,O-DIMETHYLTYRAMINE
SYNTHESIS VIA INTERMEDIATE
4-METHOXYPHENYL-N-METHYLTHIOACETAMIDE
Keywords: galanthamine synthesis half-products, N-methyltyramine, N-methyltyramine ethers, N,O-dimethyltyramine, arylthioacetamide, Willgerodt-Kindler reaction
N-Methyltyramine and its alkyl or benzyl ethers are common intermediate products in the syntheses of narwedine, and galanthamine alkaloids [1-8]. They are usually produced from the corresponding arylacetamides by lithium aluminium hydride reduction. In order to avoid application of inflammable lithium aluminium hydride bulgarian scientists have transformed arylacetamide to arylthioacetamide with phosphorus (V) sulfide with following reduction of arylthioacetamide with complex sodium borohydride - nickel or cobalt chloride agents [7, 8].
Here we present a new short way route to N-methyltyramine and its ethers via the corresponding aryl-N-methylthioacetamides, shown at the scheme 1 at the example of N-methyltyramine and N,O-dimethyltyramine synthesis.
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http://pages.unibas.ch/mdpi/ecsoc-3/a0020/a0020.html
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IndoleAmine
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Fri Apr 22, 2005 7:28 pm |
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Quote: |
The stench is not that of hydrogen sulfide
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Oh, then of course... sorry.
Anyway, are you guys sure that (NH4)2S2 etc. are not poisonous? All other simpler sulfides are... |
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worker
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styrene product odors
Sat Apr 23, 2005 8:39 am |
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Working around styrene reactions in industrial fiberglass/epoxy plants had the side effect of not being able to shower enough to not offend the sensitive noses of the men working out in the below ground gyms .Those days of sweat,mold, no ventalation....and they were really agrivated by my aroma |
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bio
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Mon Apr 25, 2005 5:35 pm |
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Polverone wrote: |
It is a smell unlike anything else I have experienced, and it lasts/clings far longer than inorganic sulfides or polysulfides. I wish I had a pure reference sample of phenylacetamide to figure out if that's what the smell was.
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I'm pretty sure it was Vogel in edition 3 that characterized the smell as "like mice". And probably they were unwashed mice at that. ![Mad](images/smiles/icon_mad.gif) |
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Polverone
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Tue Apr 26, 2005 10:26 am |
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Stick some unwashed mice in the soxhlet, extract for 12 hours with ethanol, and post me a mL. I will try to confirm or deny the mouselike aroma of my reaction products. Say, isn't acetamide described as smelling like mice? This didn't exactly smell like acetamide. |
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bio
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Tue Apr 26, 2005 12:51 pm |
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Yes Polverone, you are correct but, no ain't gonna reflux no mice.
However, I did find this little tidbit from Vogel that should also work with the phenyl derivative. Have been wanting to try this method if ever the time is available and saw a procedure recently that uses a sealed appararus at around 200 deg or so with managable pressures (glass was used). Advantage here is no Morpholine needed and NO SMELL at least until it's opened anyway. Time to break out the stainless steel reactor!
Good old Mr. Vogel had this to say...
.....The acetamide often contains a minute amount of.impurity having an odour resembling mice excrement;.............
this can be removed by washing with a small volume of a 10 per cent, solution of ethyl alcohol in ether or by recrystallisation. Dissolve 5 g. of impure acetamide in a mixture of 5 ml. of benzene and 1 • 5 ml. of dry ethyl acetate ; warm on a water bath until all is dissolved and cool rapidly in ice or cold water. Filter off the
crystals, press between filter paper and dry in a desiccator. The unpleasant
odour is absent and the pure acetamide melts at 81°. Beautiful
large crystals may be obtained by dissolving the acetamide (5 g.) in warm
methyl alcohol (4 ml.), adding ether (40 ml.) and allowing to stand....................
I wonder if the awfull smell you described is also an impurity? Would bet that it is, especially since phenyl compounds usually smell better than their aliphatic counterparts. |
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