8
$\begingroup$

Usually, to produce ketones from secondary alcohols (e.g. propanone from 2-propanol), people use a solution of potassium or sodium dichromate with a small amount of sulfuric acid. Can other oxidizers like hydrogen peroxide be used, and will the use of hydrogen peroxide produce organic peroxides?

$$\ce{C3H8O + H2O2 -> C3H6O + 2 H2O}$$

This is not for any particular purpose.

| improve this question | |
$\endgroup$
  • $\begingroup$ You can use acidified potassium dichromate. $\endgroup$ – Kenny Lau Aug 17 '16 at 13:19
  • $\begingroup$ @KennyLau The question is "can I use other oxidizers", since potassium dichromate is quite toxic and I don't have access to it. $\endgroup$ – sadljkfhalskdjfh Aug 17 '16 at 13:28
  • $\begingroup$ Oh, sorry, I thought oxidizers other than hydrogen peroxide. $\endgroup$ – Kenny Lau Aug 17 '16 at 13:30
  • 3
    $\begingroup$ H2O2 oxidation of secondary alcohols has been reported in many articles but I suspect you won't have any luck with just H2O2 - most have some other stuff added in e.g. transition metal catalyst $\endgroup$ – orthocresol♦ Aug 17 '16 at 14:34
  • 1
    $\begingroup$ Bleach, aka sodium hypochlorite. The one you can get from a corner store will work just fine. And is, probably, the greenest way you could find. Benzylic alcohols can also be oxydized with oxygen from air in an ultrasonic bath (although, that's not the most "home friendly" experiment, since, well, ultrasonic baths aren't easily available from a corner store :) ) $\endgroup$ – ChemistryHelpCenter Aug 17 '16 at 17:54
9
$\begingroup$

I think it is possible to use hydrogen peroxide. This paper discusses it: http://greenchem.uoregon.edu/PDFs/ResourceID88.pdf

Other alternatives:

  1. Pyridinium Chlorochromate (or PCC for short)

  2. Dess-Martin Reagent

  3. Swern Oxidation: oxalyl chloride in DMSO with triethyl amine enter image description here

  4. Fétizon Oxidation: silver(I) carbonate absorbed onto the surface of celite (Fétizon's reagent). This can be prepared by adding silver nitrate to aqueous sodium carbonate, in the presence of purified celite.

enter image description here

  1. Oppeneaur Oxidation: excess ketone reagent (such as acetone) and an aluminium triisopropoxide catalyst enter image description here

  2. Pfitzner–Moffatt oxidation: dimethyl sulfoxide (DMSO) activated with a carbodiimide, such as dicyclohexylcarbodiimide (DCC) enter image description here

  3. Corey-Kim Oxidation: Dimethyl sulfide is treated with N-chlorosuccinimide (NCS), and then addition of triethylamine enter image description here

| improve this answer | |
$\endgroup$
-2
$\begingroup$

There are several moments:

(1) Chemists are mostly interested in routes yielding products that are otherwise difficult to obtain. Oxidation of alcohols to ketones is a generic operation. There must be zillions of undiscovered methods to produce ketones, but there is no motivation to discover those, because the traditional methods work just as well. (2) Peroxides are reactive/corrosive/hard to work with compounds. There are copious synthetic methods that use peroxides, but this is done only if milder methods are not known. For the same reason you don't put sodium perchlorate in your soup to enhance taste, since table salt has very similar effect on taste. (3) You definitely can turn alcohol to a ketone using a peroxide (based on delta G), but the yield might be low, other reaction groups (such as double bond) might not survive and there is zero incentive to come up with yet another way to turn an alcohol to a ketone.

http://www.organic-chemistry.org/synthesis/C2O/ketones/oxidationsalcohols.shtm This page has 40+ common oxidation reactions to prepare a ketone from an alcohol. Choose less toxic alternative if you want.

Bottom line: you will not make a Nature paper with yet another oxidation of alcohol to a ketone. Thus, academia doesn't care. H2O2 is more dangerous (especially considering explosion hazard) than CrO3. Industry doesn't care.

| improve this answer | |
$\endgroup$
  • 1
    $\begingroup$ The motivation is to be able to use a less toxic and more easily accessible reagent. $\endgroup$ – f'' Aug 17 '16 at 20:07
  • $\begingroup$ @f'' CrO3 is much easier to work with than H2O2. Similar toxicity, while H2O2 is more corrosive and explosive. There is no demand on the market for a new oxidation of alcohols to ketones on the market. $\endgroup$ – sixtytrees Aug 18 '16 at 16:13
  • 4
    $\begingroup$ The OP is not trying to make a Nature paper. They are trying to oxidize an alcohol using reagents that they can access at home. Hydrogen peroxide solutions are easily obtained in stores, while chromium trioxide is not. Chromium trioxide is quite dangerous in its own right and can ignite alcohols on contact. Dilute solutions of hydrogen peroxide, which are widely available, are much safer. $\endgroup$ – f'' Aug 18 '16 at 17:01
  • 1
    $\begingroup$ If you look at the work done by Shannon Stahl and others, it looks like industrially at least there is huge demand for new and environmentally benign oxidations (eg using oxygen from the atmosphere). I'd also echo f" with the comments about chromium and related oxidations. $\endgroup$ – NotEvans. Aug 18 '16 at 17:22
  • $\begingroup$ Nature paper? I think it's a valid topic $\endgroup$ – Technetium Aug 18 '16 at 22:46

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.