Carboxylic acid and derivatives

Ultraviolet and Visible Spectra Reactions of Carboxylic Acids Carboxylic acids undergo reactions to produce derivatives of the acid.

Carboxylic acid and derivatives

Nitrosation - Nitroso Compounds and Diazonium Salts Last time we looked at the behavior of amines as bases, at their involvement in hydrogen bonds, and at the ways they can be synthesized. This time, we'll continue our study of amines by examining some of their reactions.

Let's begin reviewing reactions of amines with carbonyl compounds. When we first looked at aldehydes and ketones, we learned that the characteristic pattern of many reactions of the carbonyl group begins with the formation of a bond between the carbonyl carbon and an attacking nucleophile.

The nucleophile provides the electrons to form the new bond and the pi bond of the carbonyl group is broken as it "gets out of the way. Here's an early example in which the nucleophile is an OH- group.

This reaction step works because the OH- group is a strong nucleophile and a strong base very capable of using one of its unshared pairs of electrons to make a new covalent bond. If a weak nucleophile is involved, like water, the reaction needs help in the form of acid catalysis.

The electrons which make this bond can be envisioned as coming from the carbonyl pi bond, which leaves a positive charge on the what was the carbonyl carbon. Once the pi electrons have been "gotten out of the way" by forming a new bond to the hydrogen, even a fairly weak nucleophile like water can us one of its unshared electron pairs to make a new bond to the former carbonyl carbon.

The idea which emerges from this is that a strong nucleophile can attack directly, without help from an acid catalyst. For a weak nucleophile, an acid catalyst is needed so that the carbonyl carbon is prepared to share a pair of electrons as a new covalent bond. If we look at the mechanism of reaction between an aldehyde and an amine, we see how these factors balance.

It is an experimental fact that this reaction -- imine formation -- is acid catalyzed. The weaker nucleophile would be more likely to need a little help from acid catalysis.

It's also an experimental fact that if we put in too much acid, the reaction stops. How do we make sense of this? The key is to remember that an amine is a base. Yes, sometimes it's easy to forget that something is a base if we've gotten fixated on its nucleophilic behavior, but that's our problem, not the amine's problem.

Being a base means that an amine will react with an acid to form an ammonium ion. For each molecule of amine which does this, the unshared electron pair has been used to make the N-H bond and is not available to act as a nucleophile.

That molecule of amine has been "benched" and is not available to react with the carbonyl compound. If this happens to all of the amine molecules we've added too much acid the reaction has to stop since one of its reactants is gone.

What's the best compromise? We need some amine to make the reaction go, so we want to add fewer acid molecules than there are amine molecules.

We need some acid, though because it is important both to "jump start" the reaction and to catalyze the removal of the water molecule later in the mechanism.

It turns out that the fastest rate happens if we control the pH so that half of the amine molecules are available to act as nucleophiles and the other half are present as the conjugate acid ammonium salt.

Any stronger acid would just react with the amine to make more ammonium ion. Now let's turn our attention to the reactions of amines with carboxylic acids and their derivatives.

Again, the nitrogen serves as a nucleophile in making a new bond to the carbonyl carbon. The pi bond is broken to "make room for" the nitrogen's pair of electrons. This step is just like the attack of a nitrogen nucleophile on a carbonyl carbon in an aldehyde or ketone, but what happens next is different.

The structural difference between aldehydes and ketones on one hand and carboxylic acid derivatives on the other is that a carboxylic acid derivative has a "leaving group. Pertinent examples include the chlorine in an acyl chloride and the -OR' group in an ester.

Since the bond between one of these groups and the carbonyl carbon is polarized so that the electrons are closer to the leaving group atom than to the carbonyl carbon, it is already somewhat ionic and can cleave more easily than a carbon-carbon or carbon-hydrogen bond.

Carboxylic acid and derivatives

This pathway is not available to aldehydes and ketones, but it dominates the reaction of carboxylic acid derivatives. The overall result is that when an amine or any nucleophile reacts with a carboxylic acid derivative the outcome is that the amine replaces the leaving group a hydrogen is lost from the amine nitrogen too.

The overall reaction is a substitution. Now let's recall some examples of the reaction of amines with carboxylic acid derivatives. The details here are usually designed to overcome the fact that carboxylic acids and esters and amides too are less reactive than aldehydes or ketones.

This is due to the fact that the "leaving group" atom in these derivatives also is electron rich one or more unshared electron pairs which tends to make the carbonyl carbon less "accepting" of a nucleophile's attempt to add an electron pair to it.UK Hs Tariff Code of Chapter Acyclic hydrocarbons and Cyclic hydrocarbons in Halogenated derivatives like Sulphonated, Nitrated, Cyclic alcohols, Phenols, Ethers, peroxides, ketone, Epoxides, epoxyalcohols, epoxyphenols, epoxyethers, Glycosides sugar and Antibiotics organic compounds.

The carbonyl group draws electrons away from the alkene, and the alkene group is, therefore, deactivated towards an electrophile, such as bromine or hydrochloric acid. As a general rule with asymmetric electrophiles, hydrogen attaches itself at the α-position in an electrophilic addition.

CHAPTER 21 • THE CHEMISTRY OF CARBOXYLIC ACID DERIVATIVES As in other acid-catalyzed reactions at the carbonyl group, protonation makes the carbonyl carbon more electrophilic by making the carbonyl oxygen a better acceptor of electrons.

A carboxylic acid / Carboxylic acids often have strong odors, especially the volatile derivatives. Most common are acetic acid (vinegar) and butyric acid (human vomit).

Conversely esters of carboxylic acids tend to have pleasant odors and many are used in perfume. Oct 27,  · This video provides a fast review of carboxylic acid derivatives. It shows you how you can convert an acid chloride into an amide, ester, carboxylic acid or. In organic chemistry, functional groups are specific groups of atoms within molecules, that are responsible for the characteristic chemical reactions of those molecules.

The same functional group will undergo the same or similar chemical reaction(s) regardless of the size of the molecule it is a part of.

The Concept of Functional Groups