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Author: Subject: Acetaldehyde synthesis
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[*] posted on 27-3-2019 at 06:11


Quote: Originally posted by draculic acid69  
Calcium formate and calcium acetate destructively distilled seems to be the best easiest way to go if you need some for a rxn.can easily be scaled up to create larger amounts quickly.

destructive distillation of calcium acetate gives acetone right? not acetaldehyde





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[*] posted on 31-3-2019 at 07:33


Calcium acetate intimately mixed with calcium formate apparently yeilds acetyldehyde and if the mixing is inadequate probably some acetone as well.further back in the thread someone claims to have made 200 mls of acetyldehyde by this method. Also apparently acetylene bubbled through a hgso4 solution yeilds acetyldehyde. Formates + other carboxylic acid salts yeilds the corresponding aldehyde is a well known thing.

[Edited on 31-3-2019 by draculic acid69]
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[*] posted on 10-4-2019 at 21:20
VLE Data


Would anyone by chance have access to vapor-liquid-equilibrium data for Acetaldehyde, Ethanol, and Water or any combination thereof?

I am looking for a boiling point chart for varying concentrations.

I do not currently have access to Dortmund data bank, and am unable to find this data on sciencedirect or similar papers.

Thanks kindly.
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[*] posted on 3-6-2019 at 09:01


Quote: Originally posted by S.C. Wack  
Page 4686 of JCS (1956) claims a 50% yield by reflux of EtOH with excess MnO2 for 20 min. No explicit experimental is given in this case. A number of aldehydes and a few ketones are prepared, but my copy (from microfilm) is of poor quality.


Barakat et al. - Oxidation of Organic Compounds by Solid Manganese Dioxide - Notes, Journal of the Chemical Society (1956) Pages 4685-4687


CJ

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[*] posted on 30-6-2019 at 16:07


Machine translation, with tweaks from another member

Quote:


L. Rosenthaler:

Notes on the Behavior of Monohydric Alcohols towards Ferrous Sulfate and Hydrogen Peroxide.

(Communication from the Pharmaceutical Institute of the University of Bern.)

Received on September 10, 1929.


The English chemist Fenton is known to have fundamental valuable studies on the reactions of organic substances with hydrogen peroxide in the presence of ferrous salts ausr guided. These studies also have a biochemical interest, since we know through the examinations of Warburgs, which role iron plays in the oxidation processes of the organism.
Now also monohydric alcohols oxidized in the animal organism become an indication of Fenton and Jackson [Ref.1], methyl, ethyl, propyl, isopropyl and amyl alcohol behave indifferent against Hydrogen peroxide both in the presence and in the absence of Iron and showed completely indifferent behavior, this requires further research.

The investigation was generally carried out with a fifth of mol. of Alcohol in at least 200g of water (less soluble alcohols in as much water as is required for complete solution) dissolved, after dissolution of 6 g of ferrous sulfate, 20 g of hydrogen peroxide (30%) were added.
After 24 hours, the reaction was distilled. The distillate was added to calcium carbonate and re-distilled.
With the distillate the reactions of aldehydes employed and the p-Nitrophenylhydrazone was prepared, and from the distillation residues the calcium and silver salt were produced.

The results were the following:

Methanol: Formaldehyde and formic acid were formed, as evidenced by the usual qualitative reactions.

Ethanol: Acetaldehyde and Acetic acid were detected.

p-Nitrophenylhydrazone, Fp. 128°.
0.0639 g Sbst.: 13.9 ccm N (17°, 711 mm).
Ber.: N 23.47.
Gef.: N 23.48.

Silver salts.
0.2340 g Sbst.: 0.1514 g Ag.
Ber.: Ag 64.64.
Gef.: Ag 64.14.


n-Propanol: n-Propylaldehyde and Propionic acid were detected.

p-Nitrophenylhydrazone.
0.0582 g Sbst.: 12 ccm N (20°, 716 mm).
Ber.: N 21.77.
Gef.: N 22.08.

Silver salts.
Ber.: Ag 59.63.
Gef.: Ag 60.3.

Isopropanol: Acetone (by the reactions of Legal and Deniges, the iodine ammonia reaction u. a.) and acetic acid were detected.
The latter is made of acetone, which, like was found experimentally in the oxidation with hydrogen peroxide and ferrous sulfate, except formic acid, formaldehyde (indicated by the qualitative reactions) and supplied acetic acid.
For the proof of the acetic acid the calcium salts of the Formic acid and acetic acid-containing solution (see above) with silver nitrate heated until the acid was completely decomposed to the end. The silver which crystallized from the filtrate became silver and was analyzed.

0.1940 g Sbst .: 0.1255g Ag.
Ber.: Ag 64.64.
Gef.: Ag 64.4.

It may then be considered safe, that also in the oxidation of isopropyl alcohol with hydrogen peroxide and ferrous sulphate, acetic acid is formed.


n-Butyl, iso-Butyl and iso-amyl alcohol can be oxidized by hydrogen peroxide and ferrous sulfate also to aldehydes and acids, as the reductions of them, and the preparation of p-nitrophenylhydrazones and silver salts, have confirmed.
The analysis did not gave the values normally expected.
It is undoubtedly related to this that the acidic acids present were further oxidized by hydrogen peroxide and ferrous sulfate.
In fact, we know from earlier experiments, from Dakin, that certain fatty acids are already attacked by hydrogen peroxide alone.
The addition of ferrosulphate could only increase the oxidizing strengths at most.
An experiment showed that when butyric acid was oxidised with hydrogen peroxide and ferrous sulfate, a p-Nitrophenylhydrazone compound was obtained from the distillate.

Conclusion: The monovalent alcohols of methyl to Amyl alcohol are contrary to the data of Fenton and Jackson oxidized by hydrogen peroxide and ferrous sulfate.




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[*] posted on 30-6-2019 at 17:51


Sugimoto, H., & Sawyer, D. T. (1984).
Iron(II)-induced activation of hydrogen peroxide to ferryl ion (FeO2+) and singlet oxygen (1O2) in acetonitrile: monoxygenations, dehydrogenations, and dioxygenations of organic substrates.

Journal of the American Chemical Society, 106(15), 4283–4285.


/CJ

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[*] posted on 2-7-2019 at 17:38


"We have oxidised a wide variety of organic substances with manganese dioxide.
Hydroxy-compounds were oxidised to carbonyl compounds, and aromatic aldehydes gave the corresponding
carboxylic acids. Polybasic hydroxy-acids (eg., tartaric) in ice-cold solution gave carbon dioxide and acetaldehyde"

Leoncini, Chemisches Zentralblatt, nb. I; (1910); p. 1655


Request.....


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[*] posted on 5-7-2019 at 15:59


The above post is pretty redundant and it's too late to edit -

Some Ethanol to Acetaldehyde references without chromates or a hot copper tube......... The first 4 are posted above.


Barakat et al. - Oxidation of Organic Compounds by Solid Manganese Dioxide
Notes, Journal of the Chemical Society (1956) Pages 4685-4687
With MnO2, no solvent.
Polybasic hydroxy-acids (eg., tartaric) and MnO2 gave carbon dioxide and acetaldehyde.

Rosenthaler; Archiv der Pharmazie (Weinheim, Germany); (1929); p. 600
With dihydrogen peroxide, iron(II) sulfate in water.


With dihydrogen peroxide, iron(II) in acetonitrile, Yield given. Yields of byproduct given
Sugimoto, Hiroshi; Sawyer, Donald T.; Journal of the American Chemical Society; vol. 106; nb. 15; (1984); p.
4283 - 4285






Leoncini, Chemisches Zentralblatt, nb. I; (1910); p. 1655
Tartaric acid and MnO2 gave carbon dioxide and acetaldehyde


Gelissen; Hermans; Chemische Berichte; vol. 58; (1925); p. 768
With dibenzoyl peroxide


Courtot; Chemisches Zentralblatt; vol. 81; nb. I; (1910); p. 1847
With iodine


Mathieu; Chemisches Zentralblatt; vol. 76; nb. II; (1905); p. 782
With air, ethanol, for simple contact, dilute fluids; the education is promoted if the solution is oxydable
Bodies such as SO2, FeSO4, FeO, MnO, etc .; Sunlight increases the oxidation.


Spoehr; Biochemische Zeitschrift; vol. 57; (1913); p. 107
With air, Irradiation.im ultravioletten Licht


Sykora, Jan; Jakubcova, Maria; Cvengrosova, Zuzana; Collection of Czechoslovak Chemical Communications;
vol. 47; nb. 8; (1982); p. 2061 - 2068
With copper dichloride in acetonitrile, Time= 0.75h, T= 20 °C , Irradiation, other concentrations of CuCl2, Quantum
yield


Stepuro, I. I.; Ignatenko, V. A.; Oparin, D. A.; Russian Journal of Physical Chemistry; vol. 64; nb. 7; (1990); p. 951
- 956; Zhurnal Fizicheskoi Khimii; vol. 64; (1990); p. 1774 - 1782
With dihydrogen peroxide, iron(III) chloride in water, other catalysts, variation of conditions, Product distribution, Kinetics


With borax, sodium perchlorate, iodine, potassium iodide in water, Time= 1h, T= 35 °C , the effect of pH, other solvents,
other temp., neutral salts, stoicheiometry; Kinetics, Mechanism, Thermodynamic data
Sharma, Satish Kumar; Manglik, Anita; Gazzetta Chimica Italiana; vol. 112; nb. 5/6; (1982); p. 239 - 242

With zinc(II) oxide in tetrahydrofuran, toluene, UV-irradiation
Carroll, Gerard M.; Schimpf, Alina M.; Tsui, Emily Y.; Gamelin, Daniel R.; Journal of the American Chemical Society;
vol. 137; nb. 34; (2015); p. 11163 - 11169


1.1 : First, the preparation of acetaldehyde
Copper acetate solid weighed one kilogram of ethanol, fully milled 500 g (the copper acetate powder 20-40 mesh),
after the dehydrogenation reaction of acetaldehyde.
With copper acetate, Large scale
Patent; Kureha Chemicals Shanghai Co. Ltd.; Ding, Hui; (5 pag.); CN105367542; (2016); (A) Chinese


With potassium ferrate(VI), sodium hydroxide in aq. phosphate buffer, T= 25 °C , pH= 9.5, Kinetics
Xie, Jianhui; Lo, Po-Kam; Lam, Chow-Shing; Lau, Kai-Chung; Lau, Tai-Chu; Dalton Transactions; vol. 47; nb. 1;
(2018); p. 240 - 245


With sodium hypochlorite, iron(III) chloride hexahydrate in water, Time= 4h, T= 20 °C , p= 760.051Torr , UV-irradiation,
Catalytic behavior, Reagent/catalyst
Makhmutov; Russian Journal of General Chemistry; vol. 88; nb. 5; (2018); p. 892 - 897; Zh. Obshch. Khim.; vol. 88;
nb. 5; (2018); p. 747 - 753,7


With dihydrogen peroxide in aq. buffer, pH= 5, Irradiation
Wang, Chen; Shi, Yi; Dan, Yuan-Yuan; Nie, Xing-Guo; Li, Jian; Xia, Xing-Hua; Chemistry - A European Journal;
vol. 23; nb. 28; (2017); p. 6717 - 6723


With sodium hypochlorite, iron(III) chloride hexahydrate in water, T= 100 °C
Makhmutov; Russian Journal of General Chemistry; vol. 88; nb. 5; (2018); p. 892 - 897; Zh. Obshch. Khim.; vol. 88;
nb. 5; (2018); p. 747 - 753,7


With nitric acid, Time= 8h, T= 79.84 °C
Jasinska, Jadwiga; Krzyzynska, Beata; Kozlowski, Mieczyslaw; Central European Journal of Chemistry; vol. 9;
nb. 5; (2011); p. 925 - 931


With hydrogenchloride in water, Time= 12h, T= 24.84 °C , UV-irradiation, Inert atmosphere, Catalytic behavior, Reagent/
catalyst
Weng, Bo; Quan, Quan; Xu, Yi-Jun; Journal of Materials Chemistry A; vol. 4; nb. 47; (2016); p. 18366 - 18377


With nickel iron copper catalyst, T= 200 °C , Kinetics, Mechanism, Reagent/catalyst
Kumar; Miller; Mukasyan; Wolf; Applied Catalysis A: General; vol. 467; (2013); p. 593 - 603


With sodium hydroxide in water, Time= 1.5h, T= 20 °C , Irradiation, Inert atmosphere, Kinetics, Catalytic behavior,
Concentration
Markovskaya; Kozlova; Kinetics and Catalysis; vol. 59; nb. 6; (2018); p. 727 - 734; Kinet. Katal.; vol. 59; nb. 6;
(2018); p. 685 - 693,9


There's more, but that'll do for now.


/CJ




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[*] posted on 5-7-2019 at 16:36


More........ And related literature.


/CJ

Attachment: The Oxidation of Ethanol by H2O2 Part I. Catalysis by Ferric Ion.pdf (577kB)
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Attachment: Efficient solvent-free iron(III) catalyzed oxidation of alcohols by H2O2 - Martin and Garrone (2002).pdf (258kB)
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Attachment: Copper Catalysts For Alcohol Oxidation - J. Ahmad (Helsinki) (2012).pdf (1.4MB)
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Attachment: Epoxidation of Alkenes with Bicarbonate-Activated H202.pdf (110kB)
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Attachment: The Oxidation of Cinnamaldehyde with Alkaline H2O2 to Benzaldehyde.pdf (553kB)
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Attachment: Autocatalytic oxidation of nitrobenzene using H2O2 and Fe(III) - Nichela (2008).pdf (596kB)
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[*] posted on 9-7-2019 at 14:46



Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja; ACS Catalysis; vol. 5; nb. 3; (2015); p. 1629 - 1637


100% yields using ethanol, oxygen, iron(III) perchlorate, ozone,
Kinetics, Reagent/catalyst, Concentration Parameters Experimental data



/CJ



Attachment: Iron(II) Catalysis in Oxidation of Hydrocarbons with Ozone in Acetonitrile.pdf (672kB)
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[*] posted on 13-8-2019 at 10:22


Thanks to S.C. Wack for finding these.........Machine translations, with tweaks from another member.


Quote:


Leoncini, Chemisches Zentralblatt, nb. I; (1910); p. 1655


Effect of manganese peroxide in winemaking on tartaric acid.


If you treat aq. solution of tartaric acid with MnO2 in the heat, at 35 °C CO2-evolution begins. At the same time acetaldehyde forms:

C4H6O6 + MnO2 = 2CO2 + CH3COH + H2O + MnO + O.

The reaction is at approx. 80 °C complete and can be used for aldehyde synthesis. If MnO2 is in excess, all tartaric acid decomposes; if this is not the case, additionally a white, insoluble powder of manganese tartrate C2H2(OH)2(COO)2Mn is formed.
If this salt remains in the tartaric acid solution, it turns into a crystalline, reddish powder in C2H2 (OH)2(COO)2Mn + 2H2O, which loses its water at 100 °C. A decomposition of tartaric acid also takes place when no more MnO2 is present, but only the soluble manganese tartrate.
Also, MnO2 acts in the same way on soluble acidic tartrates and on acids containing the group - CH(OH), such as malic and citric acid.

Wines, whose must ( https://en.wikipedia.org/wiki/Must ) has been treated with MnO2, will contain more aldehyde compounds, except for the aldehyde that arised due to direct incorporation of MnO2 on alcohol.
Furthermore composites of ethers, acetals and volatile acids will be present and such a wine would have the characteristics of an old wine.
The disadvantage would be the reduction of tartaric acid and hence the shelf life and the content of Mn salts.
A vinegar made with MnO2 and containing much Mn salts showed a normal taste.
When using the MnO2 for winemaking a presumably harmful action of Mn should be noted.

(Stasi Sperm Agrarian, Italian, 43. 33-45 [November 1909. Pisa, Laboratory for Agricultural Chemistry, K. Univ.)




Quote:


C. Courtot - Chemisches Zentralblatt; vol. 81; nb. I; (1910); p. 1847


change in tincture of iodine.


In order to be able to follow the changes over time in the tincture of iodine, which, as it turned out, existed in the formation of HI, aldehyde and ethyl acetate.
Author prepared a solution of 67.5 g Iodine in 1000ml of 90% ethanol, a second of 67.5 g of iodine and 0.3 g of acetaldehyde in 1000ml of 90% ethanol and a third of 67.5 g of iodine and 0.3 g of acetaldehyde in 1000ml of absolute alcohol.
And in this solution at monthly intervals determined the content of free iodine, HI, aldehyde, and ethyl acetate.

This determination gave the following.
In the tincture of iodine (Lg. 1) forms HI, acetaldehyde and ethyl acetate. After the reaction, Iodine acts on the alcohol with the formation of HI and aldehyde.



C2H5OH + 2I = 2HI + CH3CHO.

The aldehyde is then oxidized to H 2 and acetic acid by the iodine and the water contained in the tincture:

H2O + 2I + CH3CHO = CH3COOH + 2HI

The acetic acid is esterified to the extent of its formation by the ethanol. In the first two months after the preparation of the tincture (Lg. 1) these reactions are very effective, but then weaken constantly and progressively, since they are affected by the hydrogenating properties of the HI.
Their quantity by the first two reaction is enlarged, paralyzed. After 7-8 months the working of this reaction is equal to zero, and the composition -
The tincture (Lsg. 1) has become a constant - 54.610 g of iodine, 12.799 g of HI, 0.195 g of aldehyde, 1.936 g of ethyl acetate.
The iodine-rich tincture of the new codex undergoes the same changes.

(Journ Pharm-et Chim. 1. [7] 297-301 .16 / 3. 354-59. 1/4.)




Quote:


L. Mathieu - Chemisches Zentralblatt; vol. 76; nb. II; (1905); p. 782


On the spontaneous oxidation of ethyl alcohol.


Author reports on a number of attempts that followed the formation of aldehyde in ethanol containing flakes. In this case, the following results were found:

1. In wines and ethanol of the same strength, aldehyde forms in simple contact of the alcohol with the air at ordinary temperature and without co-weight of porous bodies or microorganisms. -

2. This process is considerably accelerated if the solution contains oxidizable bodies such as SO2, FeSO4, FeO, MnO, etc. -

3. The sunlight increases the oxidation. -

4. Green glass vessels favor oxidation less than colorless.

The acceleration of the exothermic formation of the aldehyde by reducing agent is one of the phenomena that Berthelot (C.R. d. L'Acad. Of science 124 June) by the exothermic reaction. In the case of these oxidation processes, Bertrand (C. de l'Acadé of Science, 124 June) has put forward a very satisfactory theory.

The present observations have special significance for the legal definition of the limit numbers for aldehyde and SO2, in wines and the like. Spirits, for the analysis and the storage of alcoholic samples.
(Forts, follows.) (Bull, de l'Assoc. Of Chim. De Sucr. And Dist., 22nd, 1283-93, June, Beaune, Oenological Stat.)




Quote:


Spoehr - Biochemische Zeitschrift; vol. 57; (1913); p. 107


Ethyl alcohol is easily oxidized under the action of ultraviolet rays in the presence of atmospheric oxygen. There is plenty of carbon dioxide, also formic acid, acetic acid and traces of oxalic acid, and of course a lot of acetaldehyde.




/CJ


[Edited on 14-8-2019 by Corrosive Joeseph]




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[*] posted on 23-8-2019 at 19:31


With zinc(II) oxide in tetrahydrofuran, toluene, UV-irradiation

Redox Potentials of Colloidal n-Type ZnO Nanocrystals: Effects of Confinement, Electron Density, and Fermi-Level Pinning by Aldehyde Hydrogenation
Gerard M. CarrollAlina M. SchimpfEmily Y. TsuiDaniel R. Gamelin

J. Am. Chem. Soc. 2015, 137 34 11163-11169


/CJ

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[*] posted on 23-8-2019 at 23:31


^^^^^^^^^

https://www.sciencemadness.org/talk/viewthread.php?tid=15334...


/CJ




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