D.

AMINES
1. AMINES (PROPERTIES, STRUCTURE AND NAMING)

Properties of amines

Ammonia
Amines are organic compounds which contain an
Amines are organic compounds which contain and are often actually based on one or more atoms of nitrogen. Structurally amines
resemble ammonia in that the nitrogen can bond up to three hydrogens, but amines also have additional properties based on their
carbon connectivity. In an amine, one or more of the hydrogen atoms from ammonia are replaced by organic substituents like alkyl
(alkane chain) and aryl (aromatic ring) groups.
Another type of organic molecule contains nitrogen without being, strictly speaking, an amine: carboxylic acid derivatives containing
a trivalent (three-bond) ammonia in ground state are actually amides instead of amines. Amides and amines have different structures
and properties, so the distinction is actually very important. Organic-nitrogen compounds containing metals are also called amides,
so if you see a molecule that has a nitrogen and either a carbonyl group or a metal next to that nitrogen, then you know that molecule
should be an amide instead of an amine.
Properties
Types of amines
Amines can be either primary, secondary or tertiary, depending on the number of carbon-containing groups that are attached to them.
If there is only one carbon-containing group (such as in the molecule CH3NH2) then that amine is considered primary. Two carbon-
containing groups makes an amine secondary, and three groups makes it tertiary. Utilizing the lone electron pair of nitrogen, it is
sometimes energetically favored to use the nitrogen as a nucleophile and thus bind a fourth carbon-containing group to the amine. In
this case, it could be called a quaternary ammonium ion.

Primary Amine Secondary Amine Tertiary Amine

An organic compound with multiple amine groups is called a diamine, triamine, tetraamine and so forth, based on the number of
amine groups (also called amino groups) attached to the molecule. The chemical formula for methylene diamine (also called
diaminomethane), for example, would be as follows: H2N-CH2-NH2
Aromatic amines
Aromatic amines have the nitrogen atom directly connected to an aromatic ring structure. Due to its electron withdrawing properties,
the aromatic ring greatly decreases the basicity of the amine – and this effect can be either strengthened or offset depending on what
substituents are on the ring and on the nitrogen. The presence of the lone electron pair from the nitrogen has the opposite effect on
the aromatic ring itself; because the nitrogen atom can “loan” electron density to the ring, the ring itself becomes much more reactive
to other types of chemistry.
Naming conventions
For primary amines, where the amine is not the principal characteristic group, the prefix “amino-” is used. For example: 4-
aminobenzoic acid where the carboxylic acid is the principal characteristic. Otherwise, the suffix “-amine” is used with with either
the parent hybride or the R group substituent name
. Example: ethanamine or ethylamine. Alternatively, the suffix “-azane” can be appended to the R group substituent name: Example:
propylazane.
For secondary, tertiary, and quarternary amines, the naming convention is a bit different, but the suffixes are the same. For symmetrical
amines, the “di” or “tri” prefix is used depending on whether there are 2 or 3 substituents. For example, dipropylamine is a secondary
amine, and triphenylamine is a tertiary amine. For asymmetric amines, the parent chain gets the “-amine” suffix. This name is then
prefixed with “N-” (indicating the nitrogen bond) and the substituent group name, for each substituent, using alphabetic order for
tertiary amides. For example, N-ethyl-N-methyl-propylamine, not N-methyl-N-ethyl-propylamine.
To sum up:
as prefix: “amino-“
as suffix: “-amine”
the prefix “N-” shows substitution on the nitrogen atom (in the case of secondary, tertiary and quaternary amines)
Systematic names for some common amines:

methylamine
Primary amines: ethanamine or ethylamine.
Secondary amines: dimethylamine
Tertiary amines: trimethylamine
Amine Structure
Nitrogen has 5 valence electrons and so is trivalent with a lone pair. As per VSEPR theory, nitrogen present in amines is sp3 hybridized
and due to the presence of lone pair, it is pyramidal in shape instead of tetrahedral shape which is a general structure for most sp3
hybridized molecules. Each of the three sp3 hybridized orbitals of nitrogen overlap with orbitals of hydrogen or carbon depending
upon the configuration of amines. Due to the presence of lone pair, the C-N-H angle in amines is less than 109 degrees which is a
characteristic angle of tetrahedral geometry. The angle of amines is near about 108 degrees.

2. HETEROCYCLIC AMINES
Heterocyclic structures are found in many natural products. Examples of some nitrogen compounds, known as alkaloids because of
their basic properties, were given in the amine chapter. Some other examples are displayed in the following diagram. Camptothecin
is a quinoline alkaloid which inhibits the DNA enzyme topoisomerase I. Reserpine is an indole alkaloid, which has been used for the
control of high blood pressure and the treatment of psychotic behavior. Ajmaline and strychnine are also indole alkaloids, the former
being an antiarrhythmic agent and latter an extremely toxic pesticide. The neurotoxins saxitoxin and tetrodotoxin both have marine
origins and are characterized by guanidiniun moieties. Aflatoxin B1 is a non-nitrogenous carcinogenic compound produced by the
Aspergillus fungus. Porphyrin is an important cyclic tertrapyrrole that is the core structure of heme and chlorophyll.

Pyrrole and Imidazole

Pyrrole is obtained commercially by the reaction of furan with ammomia .
In a pyrrole ring, in contrast, the nitrogen lone pair is part of the aromatic sextet. This means that these electrons are very stable right
where they are (in the aromatic system), and are much less available for bonding to a proton (and if they do pick up a proton, the
aromic system is destroyed). For these reasons, pyrrole nitrogens are not strongly basic.
There is a clear preference for substitution at the 2-position (α) of the ring. Reactions of pyrrole require careful evaluation, since N-
protonation destroys its aromatic character. Indeed, N-substitution of this 2º-amine is often carried out prior to subsequent reactions.
For example, pyrrole reacts with acetic anhydride or acetyl chloride and triethyl amine to give N-acetylpyrrole
An explanation for the general α-selectivity of these substitution reactions is apparent from the mechanism outlined below. The
intermediate formed by electrophile attack at C-2 is stabilized by charge delocalization to a greater degree than the intermediate from
C-3 attack. From the Hammond postulate we may then infer that the activation energy for substitution at the former position is less
than the latter substitution.

Example
Another five-membered heterocyclic amine is imidazole which is part of the amino acid histidine.
Thiazole is a five-membered ring system which is found in biological systems, such as thiamine diphosphate (TPP).
3. AMIDES( PROPERTIES, STRUCTURE AND NAMNG)
With the exception of formamide (HCONH2), which is a liquid, all simple amides are solids (Table 15.14.115.14.1). The lower
members of the series are soluble in water, with borderline solubility occurring in those that have five or six carbon atoms. Like the
esters, solutions of amides in water usually are neutral—neither acidic nor basic.

Table 15.14.115.14.1: Physical Constants of Some Unsubstituted Amides

Melting Boiling
Condensed Structural Solubility
Name Point Point
Formula in Water
(°C) (°C)

HCONH2 formamide 2 193 soluble

CH3CONH2 acetamide 82 222 soluble

CH3CH2CONH2 propionamide 81 213 soluble

CH3CH2CH2CONH2 butyramide 115 216 soluble

C6H5CONH2 benzamide 132 290 slightly

soluble

The amides generally have high boiling points and melting points. These characteristics and their solubility in water result from the
polar nature of the amide group and hydrogen bonding (Figure 15.14.115.14.1). (Similar hydrogen bonding plays a critical role in
determining the structure and properties of proteins, deoxyribonucleic acid [DNA], ribonucleic acid [RNA], and other giant molecules
so important to life processes.

Figure 15.14.115.14.1: Hydrogen Bonding in Amides. Amide molecules can engage in hydrogen bonding with water molecules (a).
Those amides with a hydrogen atom on the nitrogen atom can also engage in hydrogen bonding (b). Both hydrogen bonding networks
extend in all directions.
The amide functional group has an nitrogen atom attached to a carbonyl carbon atom. If the two remaining bonds on the nitrogen
atom are attached to hydrogen atoms, the compound is a simple amide. If one or both of the two remaining bonds on the atom are
attached to alkyl or aryl groups, the compound is a substituted amide.
The carbonyl carbon-to-nitrogen bond is called an amide linkage. This bond is quite stable and is found in the repeating units of
protein molecules, where it is called a peptide linkage.
Simple amides are named as derivatives of carboxylic acids. The -ic ending of the common name or the -oic ending of the International
Union of Pure and Applied Chemistry (IUPAC) name of the carboxylic acid is replaced with the suffix -amide.

4. PREVIEW OF AMINO ACIDS, PROTEIN, AND PROTEIN SYNTHESIS

Amino acids
Amino acids are organic compounds that combine to form proteins. Amino acids and proteins are the building blocks of life.
When proteins are digested or broken down, amino acids are left. The human body uses amino acids to make proteins to help the
body:
 Break down food
 Grow
 Repair body tissue
 Perform many other body functions
Amino acids can also be used as a source of energy by the body.
Amino acids are classified into three groups:

 Essential amino acids

 Nonessential amino acids

 Conditional amino acids

ESSENTIAL AMINO ACIDS

 Essential amino acids cannot be made by the body. As a result, they must come from food.

 The 9 essential amino acids are: histidine, isoleucine, leucine, lysine, methionine, phenylalanine, threonine, tryptophan, and
valine.
NONESSENTIAL AMINO ACIDS
Nonessential means that our bodies produce an amino acid, even if we do not get it from the food we eat. Nonessential amino acids
include: alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, glycine, proline, serine, and tyrosine.
CONDITIONAL AMINO ACIDS
  Conditional amino acids are usually not essential, except in times of illness and stress.

 Conditional amino acids include: arginine, cysteine, glutamine, tyrosine, glycine, ornithine, proline, and serine.

Protein is a macronutrient that is essential to building muscle mass. It is commonly found in animal products, though is also present
in other sources, such as nuts and legumes. Chemically, protein is composed of amino acids, which are organic compounds made of
carbon, hydrogen, nitrogen, oxygen or sulfur. Amino acids are the building blocks of proteins, and proteins are the building blocks of
muscle mass, according to the National Institutes of Health (NIH).
Protein synthesis
The creation of proteins by cells that uses DNA, RNA and various enzymes Protein synthesis is a process of creating protein
molecules. In biological systems, it involves amino acid synthesis, transcription, and translation. In amino acid synthesis, there is a
set of biochemical processes that produce amino acids from carbon sources like glucose. Not all amino acids are produced by the
body; other amino acids are obtained from diet. Within the cells, proteins are generated involving transcription and translation
processes.
Transcription is the process by which mRNA template, encoding the sequence of the protein in the form of a trinucleotide code, is
transcribed from DNA to provide a template for translation.
Translation is the process in which amino acids are linked together in a specific order according to the rules specified by the genetic
code. It occurs in the cytoplasm where the ribosomes are located. It consists of four phases: (1) activation (the amino acid is covalently
bonded to the tRNA), (2) initiation (the small subunit of the ribosome binds to 5' end of mRNA with the help of initiation factors),
(3) elongation (the next aminoacyl-tRNA in line binds to the ribosome along with GTP and an elongation factor), and
(4) termination (the A site of the ribosome faces a stop codon)
5. NEUTRANSMITTER
Neurotransmitters are chemical messengers produced by the nervous systems of higher organisms in order to relay a nerve impulse
from one cell to another cell. The two cells may be nerve cells, also called neurons, or one of the cells may be a different type, such
as a muscle or gland cell. A chemical messenger is necessary for rapid communication between cells if there are small gaps of 20 to
50 nanometers (7.874 × 10 −7 –19.69 ×10 −7 inches), called synapses or synaptic clefts, between the two cells. The two cells are referred
to as either presynaptic or postsynaptic. The term "presynaptic" refers to the neuron that produces and releases the neurotransmitter,
whereas "postsynaptic" refers to the cell that receives this chemical message.
Neurotransmitters include small molecules with amine functional groups such as acetylcholin , certain amino acids, amino acid
derivatives, and peptides. Through a series of chemical reactions, the amino acid tyrosine is converted into the catecholamine
neurotransmitters dopamine and norepinephrine or into the hormone epinephrine. Other neurotransmitters that are amino acid
derivatives include γ -aminobutyric acid, made from glutamate, and serotonin, made from the amino acid tryptophan.

PERSPECTIVE
-NICOTIVE PATCH
- METHAMPHETAMINE
-SEMISYNTHETIC PENICILLINS
-OPIATE BIOSYNTHESIS AND THE MUTANT POPPY
Reference:
Amines(properties and naming)
https://courses.lumenlearning.com/suny-potsdam-organicchemistry2/chapter/23-1-properties-of-amines/ December 1, 2019 8:08
AM
amines (structure )
https://byjus.com/chemistry/amines/ December 1, 2019 10:40 am
Heterocyclic amines
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Map%3A_Organic_Chemistry_(McMurry)/Chapter_24%3A_Amines_
and_Heterocycles/24.09_Heterocyclic_Amines December 1,2019 8: 18 AM

physical properties of amides

https://chem.libretexts.oarg/Bookshelves/Introductory_Chemistry/Book%3A_The_Basics_of_GOB_Chemistry_(Ball_et_al.)/15%3
A_Organic_Acids_and_Bases_and_Some_of_Their_Derivatives/15.14%3A_Physical_Properties_of_Amides#:~:targetText=Like%
20the%20esters%2C%20solutions%20of,neutral%E2%80%94neither%20acidic%20nor%20basic.&targetText=The%20amides%20
generally%20have%20high,and%20hydrogen%20bonding%20(Figure%2015.14. December 1, 2019 8:20 am
structure and naming
https://chem.libretexts.org/Bookshelves/Introductory_Chemistry/Book%3A_The_Basics_of_GOB_Chemistry_(Ball_et_al.)/15%3A
_Organic_Acids_and_Bases_and_Some_of_Their_Derivatives/15.13%3A_Amides%3A_Structures_and_Names#:~:targetText=Am
ides%20have%20a%20general%20structure,acid%20is%20replaced%20by%20%2Damide. December 1, 2019 8:25 am
Amino acid
https://medlineplus.gov/ency/article/002222.htm#:~:targetText=Amino%20acids%20are%20organic%20compounds,Break%20dow
n%20food December 1, 2019 11:02 am
proteins
https://www.livescience.com/53044-protein.html December 1, 11:03 am
protein synthesis
https://www.biology-
online.org/dictionary/Protein_synthesis#:~:targetText=Protein%20synthesis%20is%20a%20process,synthesis%2C%20transcription
%2C%20and%20translation.&targetText=Translation%20is%20the%20process%20in,specified%20by%20the%20genetic%20code.
December 1, 2019 11: 19 am
neurotransmitter
http://www.chemistryexplained.com/Ne-Nu/Neurotransmitters.html December 1, 2019 11: 45 am