Reaction as acids: reaction with active metals

WHAT ARE ACTIVE METALS?

 Active Metals is a collective name for metals that react

strongly or quickly with other substances.
 The elements toward the bottom left corner of the
periodic table are the metals that are the most active
in the sense of being the most reactive.
 Elements are characterized in their reactivity by their
"electron affinity" or "electronegativity".
 EXAMPLE: Alkali metals,

these are metals in the first column of the periodic

table, they are very reactive with other substances
because they have a single electron in their outermost
shell, just waiting to be stripped off to form a complete
shell in some other atom.

So in the case of sodium, it creates explosive reactions

with water kasi it wants to react so much with water
molecules that Sodium will displace one of the
hydrogens in the H2O molecule to make NaOH, for
example, and emit hydrogen gas, which then burns (or
explodes).

ALCOHOLS AS ACID

Alcohols are only slightly weaker acids

than water, with a K a value of
approximately 1 × 10 −16.

To get a clear view pa, on how weak

of an acid si Alcohol, lets compare its
Acid Dissociation Constant (Ka) of
other substances. There’s sulfuric acid with 7.5 multiplied by 10^-3 and so forth.

The acidity of alcohols decreases while going from primary to secondary to tertiary. Due to an
increase of electron density on the oxygen atom of the more highly‐substituted alcohol, which
also increases the activation energy for proton removal.
Hence, it is convenient to employ sodium metal or sodium hydride, which react vigorously but
controllably with alcohols

Alcohol can be synthesized with salts like, NaOH and KOH to produce an alkoxide salts, which is
a prerequisite compound for making Ethers.

Simple alkoxides such as sodium methoxide (NaOCH 3) can be purchased, but others are
prepared from alcohols by a Brønsted–Lowry acid–base reaction. For example, sodium
ethoxide (NaOCH2CH3) is prepared by treating ethanol with NaH.

// NaH is an especially good base for forming an alkoxide, because the by-product of the
reaction, H2, is a gas that just bubbles out of the reaction mixture. And of course, you
just have to deprotonate your alcohol and hydrides are pretty good with that.

Alkoxide ions are produced when metals like Na or K are added to alcohols.

The basicity of alkoxide ions increases while going from primary to tertiary. This increase in
basicity occurs because the conjugate base of a weak acid is strong. The weaker the acid, the
stronger the conjugate base.
// Next is Williamson Ether Synthesis but since the subtopic is about Alcohols reactions as acids,
we won’t delve too much about itWe will just properly define it here enough to know what will
happen after an alkoxide nucleophile.

Williamson Ether Synthesis

Alcohols and ethers are both common products of nucleophilic substitution. They are
synthesized from alkyl halides by SN2 reactions using strong nucleophiles. As in all SN2
reactions, highest yields of products are obtained with unhindered methyl and 1° alkyl halides.

The preparation of ethers by this method is called the Williamson ether synthesis, and,
although it was first reported in the 1800s, it is still the most general method to prepare an
ether.

// We start with some alcohol, and do some acid base reaction, we’re going to need to
deprotonate the alcohol

// Now that we understand the reactions, lets try to work out some problems where we look
for the potential products of a substrate and on another problem we will find the substrate that
lead us the given products.

//as you can see what happened here was, first the substrate was deprotonated then carbon
And the resulting alkoxide attacks the ethylbromide, so the carbon structure of the alkyl halide
becomes a part of the ether product.
What if we need it backwards?

\\*Its not that really hard anymore kasi we know na

Properties of Esters

 The name of an ester is derived from its carboxylic acid that takes part in the
esterification reaction.
 They have a pleasant smell.
 They have a wide application in the perfume and food industries.
 Esters are organic compounds found in oils and fats.

Uses of Esters
Some common uses of esters are mentioned below.

 Esters that have fragrance are used in perfumes, food flavourings, and cosmetics.
 Used as an organic solvent.
 Nitroglycerin is known and famous for its explosive properties.
 In the manufacturing of surfactants like detergents and soaps.
 Natural occurring esters are present in pheromones
 The backbone of DNA molecules is formed by phospo esters.
 Polyesters are used in the production of plastics

Ester formation
Alcohols can be converted to esters by means of the Fischer Esterification Process. In this
method, an alcohol is reacted with a carboxylic acid in the presence of an inorganic acid
catalyst.
Because this reaction is an equilibrium. According to Le Châtelier’s principle, to drive the
reaction forward, the alcohol is usually used in large excess, and it may also be necessary to
remove water as it is formed.

The mechanism for the Fischer esterification involves the usual two steps of nucleophilic acyl
substitution—that is, addition of a nucleophile followed by elimination of a leaving group.
Because the reaction is acid catalyzed, however, there are additional protonation and
deprotonation steps. As always, though, the first step of any mechanism with an oxygen-
containing starting material and an acid is to protonate an oxygen atom as shown with a
general acid HA in Mechanism 22.6.
// First step is Protonation, where the carbonyl gets Hydrogen anywhere, from water, acidic
catalyst, or protonated alcohol.
Which leaves a good leaving group and this [point at oxygen] can act as a nucleophile then
attack the carbon on the carbonyl group
On the exact same time this happens, Oxygen wants to become neutral, the carbon here is
already hogging all the electrons
So these electrons [ point at the bond] will be taken up by oxygen
Esterification of a carboxylic acid occurs in the presence of acid but not in the presence of
base. Base removes a proton from the carboxylic acid, forming a carboxylate anion, which does
not react with an electron-rich nucleophile.
since this is a strong acid, the mixture is teeming with protons from sulfuric acid

OXIDATION OF ALCOHOL
The oxidation of alcohols is an important reaction in organic chemistry.

 Alcohols are oxidized to a variety of carbonyl compounds, depending on the type of

alcohol and reagent.
Examples:

Ethanol Butan-2-ol
2-methylpropan-2-ol

 Oxidation occurs by replacing the C– H bonds on the carbon bearing the OH group by C–
O bonds.

//* The key process here is that we’re forming a C-O bond and breaking a C-H bond on
the same carbon. That’s a sure sign of an oxidation reaction.
Important Notes:

 Primary alcohols can be oxidized to form aldehydes and carboxylic acids;

 secondary alcohols can be oxidized to give ketones.
 Tertiary alcohols, in contrast, cannot be oxidized without breaking the molecule's C–C
bonds.
//*there’s no C-H on the carbon of the tertiary alcohol and no oxidation occurs. We would
have to break a C-C bond in order for an oxidation to occur, and none of these reagents are
competent to do this

//according to the book we have the following

Reagents for Alcohol Oxidation
The oxidation of alcohols to carbonyl compounds is typically carried out with Cr 6+ oxidants,
which are reduced to Cr3+ products.
 STRONG OXIDIZING AGENTS
1. Sodium dichromate (Na2Cr2O7) used in aqueous acid (H2SO4 + H2O)
2. Potassium dichromate (K2Cr2O7) used in aqueous acid (H2SO4 + H2O)
3. Chromium trioxide (CrO3) used in aqueous acid (H2SO4 + H2O)
MILD OXIDIZING AGENTS
1. Pyridinium Chlorochromate (PCC) in Methylene Chloride

Oxidation of Secondary Alcohols

 Even if its Strong or mild the products will always be the same
 The mechanism for alcohol oxidation has two key parts: formation of a chromate
ester and loss of a proton. Mechanism 12.5 is drawn for the oxidation of a general
2° alcohol with CrO3.

Oxidation of Primary Alcohols

1° Alcohols are oxidized to either aldehydes or carboxylic acids, depending on the reagent.

 1° Alcohols are oxidized to aldehydes (RCHO) under mild reaction conditions—using

PCC in CH2Cl2.
 1° Alcohols are oxidized to carboxylic acids (RCOOH) under harsher reaction conditions:
Na2Cr2O7, K2Cr2O7, or CrO3 in the presence of H2O and H2SO4.
The mechanism for the oxidation of 1° alcohols to aldehydes parallels the oxidation of 2°
alcohols to ketones detailed in Section 12.12A. Oxidation of a 1 o alcohol to a carboxylic acid
requires three operations: oxidation first to the aldehyde, reaction with water, and then further
oxidation to the carboxylic acid, as shown in Mechanism 12.6.

Summary
Method for the routine testing of alcohol concentration in exhaled air
Cr6+ oxidations are characterized by a color change, as the red-orange Cr6+ reagent is reduced to
green Cr3+.

The first devices used to measure blood alcohol content in individuals suspected of “driving
under the influence” made use of this color change. Oxidation of CH 3CH2OH, the 1° alcohol in
alcoholic beverages, with orange K2Cr2O7 forms CH3COOH and green Cr3+.
Blood alcohol level can be determined by having an individual blow into a tube containing
K2Cr2O7, H2SO4, and an inert solid. The alcohol in the exhaled breath is oxidized by the Cr6+
reagent, which turns green in the tube (Figure 12.10). The higher the concentration of
CH3CH2OH in the breath, the more Cr 6+ is reduced, and the farther the green Cr3+ color
extends down the length of the sample tube. This value is then correlated with blood alcohol
content to determine if an individual has surpassed the legal blood alcohol limit.

Summary
Green Chemistry
Green chemistry is the use of environmentally benign methods to synthesize compounds. It is
a developing practice established by the Environmental Protection Agency in the early 1990s,
and its purpose is to use safer reagents and less solvent, and develop reactions that form fewer
by-products and generate less waste.
Since many oxidation methods use toxic reagents (such as OsO 4 and O3) and corrosive acids
(such as H2SO4), or they generate carcinogenic by-products (such as Cr 3+), alternative reactions
have been developed.
HCrO4––Amberlyst A-26 resin

 a polymer-supported Cr6+ reagent

 avoids the use of strong acid, and forms a Cr3+ by-product that can be easily removed
from the product by filtration, without added solvent, it can also be regenerated and
reused in a subsequent reaction.
 The Amberlyst A-26 resin consists of a complex hydrocarbon network with cationic
ammonium ion appendages that serve as counterions to the anionic chromium oxidant,
HCrO4–. (?)
  Heating the insoluble polymeric reagent with an alcohol results in oxidation to a
carbonyl compound, with formation of an insoluble Cr 3+ by-product. Not only can the
metal by-product be removed by filtration

With HCrO4––Amberlyst A-26 resin, 1˚ alcohols are oxidized to aldehydes and 2˚ alcohols are
oxidized to ketones.

Application: The Oxidation of Ethanol

Many reactions in biological systems involve oxidation or reduction. Instead of using Cr 6+
reagents for oxidation, cells use two organic compounds—a high molecular weight enzyme and
a simpler coenzyme that serves as the oxidizing agent.
 Photo source: http://kmapublishing.org/books/chapter.php?no=1&ch=7
For example, when CH3CH2OH (ethanol) is ingested, it is oxidized in the liver first to CH 3CHO
(acetaldehyde), and then to CH3COO– (acetate anion, the conjugate base of acetic acid). Acetate
is the starting material for the synthesis of fatty acids and cholesterol. Both oxidations are
catalyzed by a dehydrogenase enzyme.
//* acetaldehyde is generally short-lived; it is quickly broken down to a less toxic compound
called acetate

If more ethanol is ingested than can be metabolized in a given time, the concentration of
acetaldehyde builds up. This toxic compound is responsible for the feelings associated with a
hangover.
//*  Some people do not have the ability to metabolize acetaldehyde very well. When they
drink alcohol, acetaldehyde (also a known carcinogenic) accumulates in the blood and makes
them feel sick. They have facial flushing, headaches, nausea, vomiting, and a rapid heart rate.
The reason that some people can’t metabolize acetaldehyde very well is because they have a
form of ALDH that has a mutation in the gene that codes for it. The alternative form of ALDH is
very inefficient at metabolizing acetaldehyde. People with this genetic mutation do not like to
drink alcohol. ALDH2 DEFIECIENCY (Asian Flush Syndrome)
Antabuse, a drug given to alcoholics to prevent them from consuming alcoholic beverages, acts
by interfering with the normal oxidation of ethanol. Antabuse inhibits the oxidation of
acetaldehyde to the acetate anion. Because the first step in ethanol metabolism occurs but the
second does not, the concentration of acetaldehyde rises, causing an individual to become
violently ill.

Like ethanol, methanol is oxidized by the same enzymes to give an aldehyde and an acid:
formaldehyde and formic acid. These oxidation products are extremely toxic because they
cannot be used by the body. As a result, the pH of the blood decreases, and blindness and
death can follow.

Because the enzymes have a higher affinity for ethanol than methanol, methanol poisoning is
treated by giving ethanol to the afflicted individual. With both methanol and ethanol in the
patient’s system, the enzymes react more readily with ethanol, allowing the methanol to be
excreted unchanged without the formation of methanol’s toxic oxidation products.

Reference
https://www.masterorganicchemistry.com/2015/05/06/alcohol-oxidation-strong-and-weak-
oxidants/
https://sites.duke.edu/apep/module-1-gender-matters/content/content-how-is-alcohol-
eliminated-from-the-body/
https://byjus.com/chemistry/esterification/
https://www.cliffsnotes.com/study-guides/chemistry/organic-chemistry-ii/alcohols-and-
ethers/reactions-of-alcohols
https://www.chemguide.co.uk/organicprops/alcohols/sodium.html
https://crab.rutgers.edu/~alroche/Ch11.pdf
https://van.physics.illinois.edu/qa/listing.php?id=470&t=active-metals
https://chemed.chem.purdue.edu/genchem/topicreview/bp/ch9/activity.php
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map
%3A_Organic_Chemistry_(Wade)/13%3A_Structure_and_Synthesis_of_Alcohols/
13.05%3A_Acidity_of_Alcohols_and_Phenols
https://www.youtube.com/watch?v=dbdVMThH1n8
https://www.youtube.com/watch?v=EqBfua_kQ70