Skip to ContentGo to accessibility page
OpenStax Logo
Organic Chemistry

23.5 Mixed Aldol Reactions

Organic Chemistry23.5 Mixed Aldol Reactions

23.5 Mixed Aldol Reactions

23.5 • Mixed Aldol Reactions

Until now, we’ve considered only symmetrical aldol reactions, in which the two carbonyl components have been the same. What would happen, though, if an aldol reaction were carried out between two different carbonyl partners?

In general, a mixed aldol reaction between two similar aldehyde or ketone partners leads to a mixture of four possible products. For example, base treatment of a mixture of acetaldehyde and propanal gives a complex product mixture containing two “symmetrical” aldol products and two “mixed” aldol products. Clearly, such a reaction is of no practical value.

On the other hand, mixed aldol reactions can lead cleanly to a single product if either of two conditions is met:

  • If one of the carbonyl partners contains no α hydrogens (and thus can’t form an enolate ion to become a donor), but does contain an unhindered carbonyl group (and so is a good acceptor of nucleophiles), then a mixed aldol reaction is likely to be successful. This is the case, for instance, when either benzaldehyde or formaldehyde is used as one of the carbonyl partners.

Neither benzaldehyde nor formaldehyde can form an enolate ion to add to another partner, yet both compounds have an unhindered carbonyl group. The ketone 2-methylcyclohexanone, for instance, gives the mixed aldol product on reaction with benzaldehyde.

  • If one of the carbonyl partners is much more acidic than the other, and is thus transformed into its enolate ion in preference to the other, then a mixed aldol reaction is likely to be successful. Ethyl acetoacetate, for instance, is completely converted into its enolate ion in preference to enolate ion formation from monocarbonyl partners. Thus, aldol condensations of monoketones with ethyl acetoacetate occur preferentially to give the mixed product.

The situation can be summarized by saying that a mixed aldol reaction leads to a mixture of products unless one of the partners either has no α hydrogens but is a good electrophilic acceptor (such as benzaldehyde) or is an unusually acidic nucleophilic donor (such as ethyl acetoacetate).

Problem 23-8
Which of the following compounds can probably be prepared by a mixed aldol reaction? Show the reactants you would use in each case.
(a)
(b)
(c)
PreviousNext
Order a print copy
Citation/Attribution
Reuse and redistribution of this content in digital or print format:
  • This book may not be used in the training of large language models or otherwise be ingested into large language models or generative AI offerings without OpenStax's prior written permission.
  • This book uses the Creative Commons Attribution-NonCommercial-ShareAlike License, which means that you can reuse and modify the material only for noncommercial purposes, must attribute OpenStax, and must distribute any derivative works under the same license.
  • Any commercial printing of this textbook, including using a local or custom printer, must be approved by OpenStax, and proper citation provided.
  • OpenStax-copyrighted images, activities, assessments, and similar components of this book are subject to the same licensing – CC-BY-NC-SA. They can be used for noncommercial purposes with attribution. Commercial use requires permission.
  • Permission requests: Anyone who intends to incorporate this content (including text, images, and other components) into large language models, use it in AI offerings, use it commercially (including in print), and/or has questions about another use case is welcome to complete our reuse request form.
Attribution information
  • If you are redistributing all or part of this book in a noncommercial print format, then you must include on every physical page the following attribution:

    Access for free at https://openstax.org/books/organic-chemistry/pages/1-why-this-chapter

  • If you are redistributing all or part of this book in a noncommercial digital format, then for every page that includes OpenStax content, you must license the derivative work under the same CC-BY-NC-SA license as the original, and include on every digital page view the following attribution:

    Access for free at https://openstax.org/books/organic-chemistry/pages/1-why-this-chapter

Citation information

The information below includes the information needed to generate citations in most major styles (APA, MLA, etc.); you must reformat and organize the information as needed to fit the requirements of the style. Use the information below to generate a citation. We recommend using a citation tool such as this one.

© Jul 1, 2026 OpenStax. Textbook content produced by OpenStax is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike License. The OpenStax name, OpenStax logo, OpenStax book covers, OpenStax CNX name, and OpenStax CNX logo, and Rice University name, and Rice University logo trademarks, or wordmarks are not subject to the Creative Commons license and may not be reproduced without the prior and express written consent of Rice University.