[Soval]

I am interested in the following esterification reaction:

C₂H₅OH + ClCH₂COOH <-> ClCH₂COOC₂H₅ + H₂O

(ethanol + chloroacetic acid <-> ethyl chloroacetate + water)

I have been reading about the synthesis of ethyl bromoacetate in Vogel and in several other sources and I assume the synthesis of ethyl chloroacetate would be similar. However, most of the preparation methods that I encountered, require some way of water removal from the reaction, in order to shift the equilibrium in favor of the product. In case one didn't have the necessary equipment to facilitate the removal of water, would simply adding a surplus of ethanol be enough to achieve a reasonable yield?

Also, after the reaction solution has been refluxed for some time in order to achieve equilibrium, could the ester simply be obtained by dumping the mixture in cold water? Chloroacetic acid and ethanol are miscible/soluble in water. However, ethyl chloroacetate doesn't dissolve in water, so it would thereby separate and could be collected and dried?

Sorry if this seems banal, but I just wanted to check if I understand things correctly.

[Doc Oc]

Yes, if you use ethanol as the solvent it should promote esterification.  I'd recommend using an acid catalyst with that.

However, in the case of simple acids like this, I've been able to esterify using a mild base (eg; triethylamine) and ethyl iodide.

[discodermolide]

I am interested in the following esterification reaction:

C₂H₅OH + ClCH₂COOH <-> ClCH₂COOC₂H₅ + H₂O

(ethanol + chloroacetic acid <-> ethyl chloroacetate + water)

I have been reading about the synthesis of ethyl bromoacetate in Vogel and in several other sources and I assume the synthesis of ethyl chloroacetate would be similar. However, most of the preparation methods that I encountered, require some way of water removal from the reaction, in order to shift the equilibrium in favor of the product. In case one didn't have the necessary equipment to facilitate the removal of water, would simply adding a surplus of ethanol be enough to achieve a reasonable yield?

Also, after the reaction solution has been refluxed for some time in order to achieve equilibrium, could the ester simply be obtained by dumping the mixture in cold water? Chloroacetic acid and ethanol are miscible/soluble in water. However, ethyl chloroacetate doesn't dissolve in water, so it would thereby separate and could be collected and dried?

Sorry if this seems banal, but I just wanted to check if I understand things correctly.

Look up the Fischer esterification.
Or suspend the acid and ethanol in hexane or heptane, heat to reflux and add conc H2SO4. When the reaction is finished (monitor tlc or GC) cool separate the layers collect the heptane phase wash with bicarbonate (CO2 evolution) and remove the solvent by distillation.
If necessary distill the product
 

[Soval]

Look up the Fischer esterification.
Or suspend the acid and ethanol in hexane or heptane, heat to reflux and add conc H2SO4. When the reaction is finished (monitor tlc or GC) cool separate the layers collect the heptane phase wash with bicarbonate (CO2 evolution) and remove the solvent by distillation.
If necessary distill the product

So if I understand correctly - during the reaction, the produced ethyl chloroacetate is dissolved in the non-polar solvent (I assume benzene could also be used), while the water stays away from the ethyl chloroacetate as it isn't miscible with the non-polar solvent. Since this shifts the equilibrium greatly in favor of the product, the second layer should mostly be composed of water and excess of ethanol.

After the reaction is finished, the reaction mixture is cooled down, the layer composed of the non-polar solvent and ethyl chloroacetate is removed, neutralized and distilled, whereby benzene is the compound being removed from ethyl chloroacetate as it has a much lower boiling point.

Is this correct?

Also, I noticed that this is similar to the method described in Vogel's Textbook of Practical Organic Chemistry for the synthesis of ethyl bromoacetate (also similar to the one found here). So why exactly is Dean-Stark apparatus preferred in these sources? Does it help to obtain an even higher yield, or is the reason something else?

Unfortunately, along with the relatively basic knowledge of theory related to esterifications, I don't have much personal experience with this type of reactions, so I would appreciate any additional insight and advices.

[discodermolide]

Look up the Fischer esterification.
Or suspend the acid and ethanol in hexane or heptane, heat to reflux and add conc H2SO4. When the reaction is finished (monitor tlc or GC) cool separate the layers collect the heptane phase wash with bicarbonate (CO2 evolution) and remove the solvent by distillation.
If necessary distill the product

That's correct. You can use a Dean-Stark. You just azeotrope out the water. Don't use benzene it is carcinogenic, use toluene.

So if I understand correctly - during the reaction, the produced ethyl chloroacetate is dissolved in the non-polar solvent (I assume benzene could also be used), while the water stays away from the ethyl chloroacetate as it isn't miscible with the non-polar solvent. Since this shifts the equilibrium greatly in favor of the product, the second layer should mostly be composed of water and excess of ethanol.

After the reaction is finished, the reaction mixture is cooled down, the layer composed of the non-polar solvent and ethyl chloroacetate is removed, neutralized and distilled, whereby benzene is the compound being removed from ethyl chloroacetate as it has a much lower boiling point.

Is this correct?

Also, I noticed that this is similar to the method described in Vogel's Textbook of Practical Organic Chemistry for the synthesis of ethyl bromoacetate (also similar to the one found here). So why exactly is Dean-Stark apparatus preferred in these sources? Does it help to obtain an even higher yield, or is the reason something else?

Unfortunately, along with the relatively basic knowledge of theory related to esterifications, I don't have much personal experience with this type of reactions, so I would appreciate any additional insight and advices.

[Orthocelsus]

The acid-catalyzed esterification of an alcohol with a carboxylic acid is an equilibrium reaction, which means it can never go to 100% completion unless you mess with it some way. At a certain point,the rate of ester formation will be equal to the rate of acid-catalyzed ester hydrolysis and there it will stay. Sometimes--if the workup is easy and the reagents are cheap--this isn't of much concern and a 60-70% conversion is acceptable, or the equilibrium is driven by using a big excess of starting material.

Other times yield and purity are of paramount importance and there are any number of creative and clever techniques for driving the reaction to completion.

Vogel is an excellent and wonderfully useful book, but you have to remember that it's intended to teach general techniques and methods of organic synthesis and does not represent the best and most efficient means of synthesizing any compound. For that you want to see Organic Synthesis.

This particular synthesis is no doubt intended to demonstrate the use of a Dean-Stark trap and the azeotropic distillation of the ethanol-water mixture. There are certainly better and more effcient ways of effecting this synthesis.

[nox]

If you refluxed the reaction in ethanol, I have doubts as to whether that alpha chlorine will survive.

[Senny]

Seldom ppl do this esterification.. mostly do by china researcher
 so far only 2 papers for heterogeneous can be found in english..

Mostly use cyclohexane as solvent...

May i know what benefit form this esterification?