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Author: Subject: benzyl alcohol oxidation
kmno4
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"The acid is the solvent for the alcohol and is in great excess. Everything should be stirred well for several hours (that is probably too long). The dense lower layer is collected and separated with a funnel to remove any of the acid solution. It is then dried with a suitable drying agent and is ready to use for many purposes."

At this conditions - dense lower layer is HCl(aq). I do not know what are "many purposes" but making benzyl cyanide from this crude product was very unsuccessful. Besides, I always wanted to do some quantitative measurements of reaction: benzyl alcohol+ HCl(aq)... And now I am going to do that (If I have time ).
Sorry for starting offtopic.

By Nicodem:

Assuming x = 0.5 as a realistic value we get:
k1/k2 ≈ e^(6.05) ≈ 423

(...)Yet, taking those approximations, the calculation indicates the oxidation of BnOH might even be a few hundred times faster than the oxidation of PhCHO (assuming the same order of reaction).

I agree with it. But look at Table 1 in ACS paper:
BDE(C-H) for ØCH2OH is 79 (or ~84) kcal/mol
BDE(C-H) for ØCHO is 86 kcal/mol

and
"Normalized Second-Order Rate Constant of H-Abstraction from H-Donor Substrates by BTNO" in MeCN:
k<sub>H</sub> for ØCH2OH is 0,94 (1/Ms)
k<sub>H</sub> for ØCHO is 0,8 (1/Ms)

so k<sub>1</sub>/k<sub>2</sub> &#8776 1
Besides there is large acceleration of rate in protic, H-bonding solvent (AcOH) and order is this time reverted: hydrogen is abstracted from aldehyde faster than from alcohole.

[Edited on 27-4-2008 by kmno4]
Nicodem
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Indeed I agree. Assuming the Evans-Polanyi relation for the two reactions to be of a similar value (calculated as equal) is the weakest assumption in my calculations. This factor depends highly on the one electron oxidant used and other conditions and I have no idea how the persulfate influences it. Therefore x=y was the only assumption I could take without using too much imagination.
With some transition metal one electron oxidants even the oxidation of toluene to benzaldehyde most commonly completely stops at PhCHO stage (talking about the numerous and well studied Co/Cu/Mn/etc catalyzed oxidations of toluene with oxygen). Often no PhCOOH can be detected. Considering that the BDE of Bn-H is 89 kcal/mol, thus even more than for PhCO-H, I can't think of anything else but that the E<sub>a</sub> for radical oxidations of PhCHO is commonly quite higher (but obviously not always as demonstrated by the kinetic measurement you cite).
Anyway, those calculations were plain exercise since they can not give a reliable number given the bold assumptions used. It was more about showing the difference in the BDE values of the two substrates and showing how small absolute differences can give rise to huge differences in the kinetics.
Anyway, if anybody has another explanation for the reaction stopping at the PhCHO stage, I would be glad to hear it. Radical oxidations are not something I'm familiar with.

Done.

Attachment: BDE_values_for_BnOH_and_BzH_references.rar (1.2MB)

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Ephoton
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Mood: trying to figure out why I need a dark room retreat when I live in a forest of wattle.

I found a good source of otc benzyl alcohol the other day I would like to share.
concrete floor stripper. usualy around 20 + %

hehe (I am now a hazard to others look out world)

[Edited on 29-4-2008 by Ephoton]

bash-2.05#

evil_lurker
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Take your BzOH, place in diethyl ether with an equivalent of sodium hydroxide and molecular sieves to form sodium benzylate.

React with BnCl ala Williamson ether synthesis to dibenzyl ether (DBE).

Oxidize the DBE with dilute nitric acid catalized with sodium nitrite.

Reported yields as high as 80% based on DBE with the reaction sucessfully scaled up to 1 mole with similar results.

[Edited on 29-4-2008 by evil_lurker]

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
kmno4
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Offtopically about reaction of benzyl alcohol(=BA) and HCl(aq)(=AC).
On the picture: 5 test-tubes with with mixtures BA and AC, shaken
many times to reach equilibrium or close to it (at least I think so).
Test tube 1: 2g BA/2g AC [ 75 minutes]
Test tube 2: 2g BA/3g AC [ 50 minutes]
Test tube 3: 2g BA/4g AC [ 30 minutes]
Test tube 4: 2g BA/5g AC [ less than 30 minutes]
Test tube 5: 2g BA/6g AC [ less than 30 minutes]
I also made 2g BA/1g AC but this mixture did not split into separate layers ( I waited 8 hours). For the rest of mixtures, time of separating given in [ ].
To estimate degree of conversion BA into benzyl chloride I titrated (twice) remaining water-acid layer.
Results:
Test tube 1: 2g BA/2g AC -------------
Test tube 2: 2g BA/3g AC 44%
Test tube 3: 2g BA/4g AC 52%
Test tube 4: 2g BA/5g AC 67%
Test tube 5: 2g BA/6g AC 73%
Layer from test tube 1 was not investigated, because water+acid was not separated completly from organic layer and it would cause too big errors.
(from 2g BA/1g AC mixture it did not separete at all)
In no case density of organic layer is larger than water layer, as can be seen. To convert alcohol into chloride quantitatively, large excess of acid is needed. Use of CaCl2, ZnCl2 etc..., would be more convenient.

All values given by me are approximations. It would be good if someone could repeat these measurements.
End of offtopic
I have found interesting article about oxidation of benzyl alcohol with persulfate.
Aqueous Media Oxidation of Alcohols with Ammonium Persulfate
Chinese Journal of Chemistry, 2007, 25, 836—838
If someone is interested, link to article: http://mihd.net/egpdyq2

[Edited on 3-5-2008 by kmno4]

Magpie
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Thanks, kmno4, for posting that journal article. I will be trying their method for making n-butyraldehyde soon.
evil_lurker
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Well I think I have me a project for this summer.

1. Partially convert BnOH to BzCl as close to 1:1 ratio within reason. Start by adding the appropriate amount of 37% HCl to the alchol, heat and agitate to 80íC till it reaches equilibrium.

2. Drain water/acd, add in small quantity of NaOH (enough to remove HCl from previous reaction) then add in concentrated NaOH solution with either a tiny bit of triethylamine or tri-n-butylamine to form the ether.

3 Drain NaOH solution, rinse with a little nitric acid to remove alkali, drain again, then add in dilute HN03/NaNO2 catalyst solution and stirr for several hours.

If one used a reaction flask with bottom drain it could damn near be "one pot" with no solvents, use fairly cheap and easy to get reagents, and be completed in 5-6 hours with no need for isolation of intermediate products.

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
Nicodem
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Kmno4, that was some nice looking and strict scientific experimentation of which I wish we had posted more and more often.

Thanks also for the paper. It is interesting to see that no overoxidation products are detected. But what is most confusing to me is that butanol reacts efficiently already at 30°C, while for the benzylic, allylic and secondary alcohols they used 75-85°C. Looks like a reversed reactivity order of what is expected for a radical oxidation (and the authors don't even bother giving any hypothesis to account for the differences).

Magpie, you better don't use this method as is on a larger scale since it was developed on a 1 mmol scale. Scaling it up by multiplication could get you in troubles of the type you encountered in your latest butanol oxidation trial. In my experience similar mmol reactions (of which Tetrahedron letter and Synthesis abounds) scaled up usually end up in runaways.

Evil_lurker, you might want to first try out that Bn2O oxidation with HNO3/NaNO2 on BnOH itself before wasting time with its etherification.

[Edited on 3/5/2008 by Nicodem]

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evil_lurker
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 Quote: Originally posted by Nicodem Evil_lurker, you might want to first try out that Bn2O oxidation with HNO3/NaNO2 on BnOH itself before wasting time with its etherification.

I had considered that... did I miss something in the paper amongst all the tecnical info?

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
Nicodem
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You forgot that in 15% HNO3 the media is acidic enough to cleave Bn2O to BnOH. You also forgot the context of the article – the authors were looking for an economical use of Bn2O which is a worthless side product in the industrial preparation of BnOH. Cited from the paper:

 Quote: During the oxidation of DBE, BnOH is formed and oxidised to BzH.[ref 7] Benzoic acid is formed by oxidation of benzaldehyde. Therefore, with the progress of the reaction the yield of BnOH decreases and that of BzOH increases. Presence of BnOH in the final product may not be a serious problem as it can be recovered from the reaction mixture by fractional distillation and is a value-added product.

In short, the treatment of BnOH with refluxing HNO3 gives BzOH just like when starting with toluene (BnH), but at milder conditions (90°C) you can actually get viable yields of BzH with BzOH being the major side product. The presence of nitrite works in your favor, assumingly as a source of NO2 to start the radical chain reaction.
garage chemist
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KMnO4, the mixtures of benzyl alcohol and conc HCl have to be heated to effect the reaction! Try it again, and this time heat the test tubes in a boiling water bath.

I have very successfully made benzyl chloride many times from conc aqueous HCl and benzyl alcohol. At a certain temperature, the reaction spntaneously takes place and is over in a few minutes, with complete separation of phases. HCl is used in at least threefold excess. No other reagents are added.
Look at Rhodiums methods for benzyl chloride from -alcohol.

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detritus
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Hi,

Really interesting stuff here. But I am not old enough to buy the pure alcohol from any distributors, can anyone help with any info on OTC source of BzOH in the US?
MagicJigPipe
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There's probably no useful OTC source of BnOH (it's Bn not Bz) in the US. You can get it from pharmacies but when I did that it cost me like $18 for 100mL (I think a couple of other places quoted$40 a quart). Definitely not a practical source unless you work with VERY small amounts like Woelen.

"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
evil_lurker
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www.lemelange.com $45 gallon USP grade (repacked under non USP conditions so it can't be labelled as such due to FDA regs). [Edited on 3-5-2008 by evil_lurker] [Edited on 3-5-2008 by evil_lurker] Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer. MagicJigPipe International Hazard Posts: 1553 Registered: 19-9-2007 Location: USA Member Is Offline Mood: Suspicious Hey! They used to be$35 a gallon! Or are you including shipping?

"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
evil_lurker
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They went up on it I reckon. Need to order a gallon or so.

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
azo
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pitty you don't live in australia i could of given you a gallon i use it for work as a addative solvent.
MagicJigPipe
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Just mail it. Even with shipping it might be cheaper and it's certainly not HAZMAT.

"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
kmno4
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 Quote: Originally posted by garage chemist KMnO4, the mixtures of benzyl alcohol and conc HCl have to be heated to effect the reaction! Try it again, and this time heat the test tubes in a boiling water bath. (...)

I do not say no. My experiments were conducted at room temperature, concentration of HCl(aq) is 35.4%, only to prove
that Fleaker's post says untruth.
Besides, heating of concentrated HCl somehow scares me....
I do not like gaseous HCl
kmno4
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 Quote: Originally posted by Nicodem In short, the treatment of BnOH with refluxing HNO3 gives BzOH just like when starting with toluene (BnH), but at milder conditions (90°C) you can actually get viable yields of BzH with BzOH being the major side product. The presence of nitrite works in your favor, assumingly as a source of NO2 to start the radical chain reaction.

Kinetics of Oxidation of Benzyl Alcohol with Dilute Nitric Acid
Ind. Eng. Chem. Res. 2005, 44, 325-333

Attachment: ie0303911.pdf (176kB)

evil_lurker
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Dude, the information that paper contains is sweeet.

If it is indeed true, we may now finally have a viable method for the home manufacture of BnH from BnOH.

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
MagicJigPipe
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Why would you want to make toluene out of BnOH? What a waste!

"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
evil_lurker
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 Quote: Originally posted by MagicJigPipe Why would you want to make toluene out of BnOH? What a waste!

Ummm did you miss something here?

BnH is benzaldehyde, BnOH is benzyl alcohol.

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
Nicodem
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I just knew this would happen as it always happens every time abbreviations and acronyms are used on this forum (like the TCCA vs. TCT confusion coming up all the time).

BnH is toluene since Bn stands for benzyl. Benzaldehyde would be BzH since Bz stands for benzoyl. Therefore it would be preferable to simply use PhCHO for benzaldehyde to avoid further confusion among those who are unfamiliar with such organic shorthand conventions as Bz which are rarely used anyway.
MagicJigPipe
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Yes, evil lurker. Abbv. like that are based on a certain structure/moeity and not just an abbv. of a certain word.

Bn = Ph-CH2 Therefore, like Nicodem pointed out, a benzyl group with a hydrogen is toluene. Another example: Ph is C6H5 so benzene would be PhH (I've also seen benzene represented as "Ph" but that is technically incorrect) and phenol is PhOH. I can understand BzH. If that was used I would have realized he was speaking of benzaldehyde.

I just find BzH easier than typing PhCHO.

[Edited on 5-7-2008 by MagicJigPipe]

"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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 Sciencemadness Discussion Board » Fundamentals » Organic Chemistry » benzyl alcohol oxidation Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues   » Detritus   » Test Forum