Here I will share some literature references for the preparation of simple chemicals.
I will begin with the preparation of H2S.
Fresenius (1887) prepares it by thermally reducing CaSO4 to CaS using charcoal and rye flour, then adding HCl(aq). The article is in German. An
English abstract is provided.
Prothiere (1902) prepares it by heating vaseline and sulfur. The article is in French. An English abstract is provided.
The articles are identified by a clickable yellow note once you open the files.
Webster (1839) prepares it by burning sulfur in air with a little potassium nitrate over a cup that stands above a dish of water under a bell-shaped
receiver.
The reactions are those of the lead chamber process. The burning produces sulfur dioxide, which combines catalitically with oxygen from the air, the
cataliser being the nitrogen oxides formed from the potassium nitrate, forming sulfur trioxide. Water then gives sulfuric acid.
The text is actually about potassium nitrate, go straight to the second paragraph of the second page to see the preparation of sulfuric acid.
Thompson (1849) prepares it by the digesting calcium sulfate and oxalic acid in water. The insolubility of calcium oxalate drives the equilibrium to
the right.
Both texts are in English now. Please warn me if there is a digital problem with any files from any message.
Phelps (1907) prepares acetamide in excellent yield and purity by mixing cold ethyl acetate and cold aqueous ammonia and waiting many days to complete
the reaction. The product is isolated by distillation. The ethyl acetate used was store-bought.
Phellps (1907) prepares formamide in excellent yield and purity by mixing cold ethyl formate and cold aqueous ammonia and waiting many hours to
complete the reaction. The product is isolated by distillation. The ethyl formate used was prepared from absolute alcohol, sodium formate, and
sulfuric acid, as described in the paper.
Both papers are in English. By the way, if you have trouble with French or German, try to use Google Translator.
There are no clickable yellow notes to identify these two papers because they have identification printed on them.
The Thompson 1849 paper about sulfuric acid also describes the analogous preparation of phosphoric acid from oxalic acid and calcium phosphate.
The Webster 1839 book extract also sketches a little the extraction of potassium nitrate from natural sources.
Some preparations related to the amides above.
Pabst (1880) prepares ethyl acetate in good yield continuously from glacial acetic acid, alcohol, and concentrated sulfuric acid. The article is in
French.
Montgomery (1931) prepares formic acid from cellulose in good yield. The reactions are analogous to the glycerol method. Concentration of formic acid
via its lead salt is sketched. Cotton is used as a cellulose source.
You can also prepare Hydrogen Sulphide with Sulphur and wax (I believe)pedrovecchio - 11-4-2012 at 00:44
dann2, you are probably right: there is a book, whose title I forgot, which shows a preparation of hydrogen sulfide by heating sulfur and candle wax.
But vaseline has the advantage of being a fluid, thus easier to mix with the other reactant (sulfur), giving a smooth process. You don't want trouble
when generating hydrogen sulfide since it is as toxic as hydrogen cyanide (death chamber gas).
Of course, the standard method uses iron sulfide and hydrochloric acid.
I forgot to say: the Montgomery paper about formic acid is in English.
Here are some references for oxalic acid.
Thompson (1848) prepares it from nitric acid and sugar.
Othmer (1942) prepares it from sawdust, sodium hydroxide, calcium oxide, and sulfuric acid.
Both processes are well know. Both papers are in English.
In this message is also attached an English abstract to the Pabst French paper about ethyl acetate.
Now some references on the preparation of phosphorus.
Webster (1839) describes the preparation and properties of phosphorus, its oxides, and its oxyacids. He prepares a tiny amount of phosphorus (probably
around half a gram) by greatly heating for a long time charcoal with either phosphoric acid or superphosphate of lime. The apparatus employed is
minutely described, and so is the preparation of phosphoric acid or superphosphate of lime from sulfuric acid and calcined bones.
Boyl (1693) prepares it by greatly heating for a long time boiled down urine and sand. The sand probably serves some physical purpose, such as
countering bumping, or maybe the silicon dioxide in the sand forms some silicate thus also helping chemically? Urine contains reducing agents (organic
substances) and phosphorus in an oxidized state (phosphate salts), which explains the production of phosphorus.
Divers (1899) prepares sodium or potassium nitrite from nitric acid and sodium or potassium carbonate.
The nitric acid is heated with starch or arsenious oxide, producing nitrous gas, which is absorbed in the hydroxide or carbonate solution until the
latter is almost only slightly alkaline. Special directions are necessary in the case of sodium carbonate and the author gives them.
Nitrous gas is a mixture of NO and NO2. In equimolar amounts, they react as if they were nitrous acid anhydride, thus forming nitrite in alkaline
solution. NO2 can be regarded as the mixed anhydride of nitric and nitrous acid, thus any excess of it will produce nitrite and nitrate (not wanted).
Any excess of NO will escape unabsorbed without reacting (inert). The author regulates the generation of nitrous gas so as to have always a slight
excess of NO, which can be observed in a bubbler as gas that is not absorbed. This gives the best nitrite yield with the least nitrate contamination.
Divers' paper about alkali nitrites, posted above, is in English.
Another reference on the preparation of formic acid:
Lengfeld (1892) prepares it from oxalic acid and glycerin. He heats the mixture some degrees above water's boiling point using an oil bath, and gets
better results in comparison with the use of a water bath. The paper is in English.
"Here is a paper that shows simple methods of making oxygen and chlorine from bleaching powder. The latter is catalytically decomposed to oxygen by
cobalt oxide, and also oxidizes hydrochloric acid to chlorine. Clear instructions are given and simple equipment is used."
The paper is also attached to this message, since some people may not be reading the messages here and may be just clicking in the PDF download links.
The paper is in English.
Back to formic acid now.
Maquenne (1888) concentrates aqueous formic acid by distilling it with sulfuric acid at reduced pressure. Control of temperature and amount of
sulfuric acid used keeps decomposition of formic acid negligible. Repeating the procedure a few times gives formic acid as concentrated as one wishes
for.
The paper is in French. An English abstract is provided.
Formic acid has a boiling point very close to that of water so it is impossible to concentrate it by distillation. Heating it too much also causes
decomposition into carbon monoxide and water. Sulfuric acid, a powerful drying agent, speeds up this process, unless the author's directions are
followed.
Something about Maquenne's paper: formic acid is obtained dilute when made by procedures such as Lengfeld's or Montgomery's. If it is to be used to
generate carbon monoxide or to make methyl formate (substrate for trichloromethyl chloroformate), to give a few examples, it must be very
concentrated. Hence the importante of a method to concentre formic acid.
Something about Pabst's paper: the paper is old but not outdated; this is the procedure all modern textbooks use.
Time for more references: Hitch (1913) prepares acetamide by heating ammonium acetate and acetic acid (catalyser). The process is well documented (see
Org Synth).
Yield and purity is a little smaller in comparison with the ethyl acetate method (Phelps), but the process is faster. The paper is in English.
Zincke (1869) prepares phenylacetic acid by heating to 180-200 degrees (Celsius?) the ethyl ester of chloroacetic acid with bromobenzene and copper
powder. The yield is not stated. Chlorobenzene can probably be used instead. The paper is in German.
This is an unusual kind of the Ullmann's coupling reaction.
For the preparation of chlorobenzene and chloroacetic acid, see Cumming's book at S. C. Wack's 4shared folder.
In most cases the chlorobenzene might work, but usually it will be at about 1/10th the rate of the bromobenzene for coupling reactions, so that might
take very harsh conditions and/or a very long time. In Ullman's the iodo is almost always the best yield, but that is harder to get.
Thompson (1849) prepares it by the digesting calcium sulfate and oxalic acid in water. The insolubility of calcium oxalate drives the equilibrium to
the right.
I've gotten this to work with copper sulfate, see this thread. Copper sulfate is much more soluble in water than calcium sulfate so would require a lot less water. Copper oxalate is also more
insoluble than calcium oxalate, which makes copper sulfate also the better choice to use. Though copper residues in acid could have a more catalytic
effect than calcium.
Though it was more complicated than mixing, filtering precipitate and simply boiling down. I had all of the acid eject upon boiling near the end and
not now why (this was very dangerous!). My thought is sulfuric acid might not act on oxalate residues until it is concentrated, at which point hot
acid acts vigorously to decompose oxalate forming CO and CO2 which expand quickly, ejecting the mixture.
My suggestion there is to do at least one crystallization after filtering and boiling before proceeding to boil down more, and then heat more gently
when nearing the end. This should allow the reaction to proceed more smoothly than what I've seen once before.pedrovecchio - 24-5-2012 at 01:03
Dr. Bob, if iodobenzene works too well it may end up coupling with itself instead of with the ethyl ester of chloroacetic acid (X), giving biphenyl.
If chlorobenzene works too bad X may end up coupling with itself, giving the diethyl ester of succinic acid. Maybe that is why the author used
bromobenzene.
Formatik, thanks for the link provided and experience shared.
More references: Rossel (1894) prepares phosphorus by distilling a mixture of a phosphate of an alkali or alkaline earth metal, sand, and aluminum, in
a current of hydrogen. Aluminum and hydrogen are much better reducing agents than charcoal, making this process more feasible than the ones that
employ the latter.
The paper is in German and an English abstract is provided.
Formatik, I just recalled that there is a paper by the same Lewis Thompson where he prepares sulfuric acid from oxalic acid and copper or iron
sulfate. Unfortunately, I lost the reference many years ago. It could be found via Google Books for some time but then, could not be found anymore.pedrovecchio - 26-5-2012 at 08:43
Haworth (1896) prepares ethylene glycol directly from 1,2-dibromoethane and aqueous K2CO3. This is more straightforward than the glycol diacetate
process employed in Gattermann's book (see Science Madness' Library).
The authors claim a yield of 50-60%, and that it is practicable to make 1 kg of product in 10-14 days. The process probably works with
1,2-dichloroethane instead of the bromo-compound.
Formatik, I just recalled that there is a paper by the same Lewis Thompson where he prepares sulfuric acid from oxalic acid and copper or iron
sulfate. Unfortunately, I lost the reference many years ago. It could be found via Google Books for some time but then, could not be found anymore.
Found it. Its French but an English abstract is provided.
Also provided is a German paper with English abstract on the preparation of hydrobromic acid from H2SO4 and KBr plus the preparation of dry hydrogen
bromide from hydrobromic acid and anhydrous CaBr2. The authors avoid the oxidation to bromine by the use of dilute sulfuric acid. Another author
studies this process a bit, see the last paper. For more information see Inorg. Synth. 1 and an ACS paper by author Heisig.
References:
Journal de pharmacie et des sciences accessoires, 1836, 22, 204
Philosophical Magazine, Series 3, 1836, 9, 52, 155
Chemiker-Zeitung, 1891, 15, 444
J. Chem. Soc., Abstr., 1891, 60, 1320
J. Chem. Soc., Trans., 1892, 61, 94
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Thanks for reviving this thread. I can see that I will have to study it closely and pick out some procedures that are useful to me.byko3y - 5-1-2016 at 09:16
Zincke (1869) prepares phenylacetic acid by heating to 180-200 degrees (Celsius?) the ethyl ester of chloroacetic acid with bromobenzene and copper
powder. The yield is not stated. Chlorobenzene can probably be used instead. The paper is in German.
This is an unusual kind of the Ullmann's coupling reaction.
I know i'm really late with answer, but this reaction drew my attention. Ullmann coupling couples aryl halide with NUCLEOPHILE. Chloroacetate is a
definite electropile on its alpha position.
What I want to say - the author of the article did not analyze the products well enoguh to find that the phenylacetic acid is not a real product of
the reaction.
[Edited on 5-1-2016 by byko3y]stillhere - 25-1-2016 at 09:18
