Bioorganic chemistry. History of the development of bioorganic chemistry The role of bioorganic chemistry in the theoretical training of a doctor
Structure and isomerism of organic
connections.
Chemical bond and interaction
atoms in organic compounds.
Types of chemical reactions.
Poly- and heterofunctional
connections.
Basic textbook – Tyukavkina N.A., Baukov Yu.I.
Bioorganic chemistry.
Text of lectures and manual “Bioorganic chemistry in
questions and answers" see on the TSU website http://tgumed.ru
tab “Student Help”, section “Lectures on
disciplines of the curriculum." And, of course, VK
Bioorganic chemistry studies the structure and properties of substances involved in life processes in connection with the knowledge of their biological
Bioorganic chemistry studies the structure and properties of substancesparticipating in life processes, in connection with
knowledge of their biological functions.
The main objects of study are biological
polymers (biopolymers) and bioregulators.
Biopolymers
–
high molecular weight
natural
compounds that are the structural basis of all living things
organisms and playing a certain role in the processes
life activity. Biopolymers include peptides and
proteins, polysaccharides (carbohydrates), nucleic acids. IN
This group also includes lipids, which themselves are not
are high molecular weight compounds, but in
the body are usually associated with other biopolymers.
Bioregulators are compounds that chemically
regulate metabolism. These include vitamins,
hormones, many synthetic biologically active
compounds, including drugs.
The set of chemical reactions occurring in the body is called metabolism, or metabolism. Substances produced in cells
The set of chemical reactions occurring in the bodycalled metabolism, or metabolism. Substances
formed in cells, tissues and organs of plants and animals
during metabolism are called metabolites.
Metabolism includes two directions - catabolism and
anabolism.
Catabolism refers to the breakdown reactions of substances that enter
into the body with food. As a rule, they are accompanied by the oxidation of organic compounds and proceed with the release
energy.
Anabolism is the synthesis of complex molecules from
simpler ones, which results in the formation and renewal of the structural elements of a living organism.
Metabolic processes occur with the participation of enzymes,
those. specific proteins that are found in cells
organism and play the role of catalysts for biochemical
processes (biocatalysts).
Metabolism
catabolismanabolism
Decomposition of biopolymers
with highlighting
energy
Synthesis of biopolymers
with absorption
energy
Glycerin and
fatty acid
Basic principles of the theory of the structure of organic compounds A.M. Butlerov
1. Atoms in a molecule are located in a certainsequences according to their valency.
Valency of carbon atom in organic
connections is equal to four.
2. The properties of substances depend not only on what
atoms and in what quantities they are included in the composition
molecules, but also on the order in which they
connected to each other.
3. Atoms or groups of atoms that make up
molecules mutually influence each other, causing
depend on chemical activity and reaction
ability of molecules.
4. Studying the properties of substances allows us to determine them
chemical structure.
H o m o l o g h i c y r a y d
Homologousrow
A number of structurally similar compounds that have
similar chemical properties, in which individual
members of a series differ from each other only in quantity
groups -CH2- is called a homological series, and the group
CH2 – homological difference.
Members of any homologous series have an overwhelming
most reactions proceed the same way (exception
constitute only the first members of the series). Therefore, knowing
chemical reactions of only one member of the series, it is possible with
with a high degree of probability to assert that the same
type of transformations also occur with the remaining members
homologous series.
For any homologous series one can derive
general formula reflecting the relationship between atoms
carbon and hydrogen in members of this series; this is the formula
is called the general formula of the homological series.
Classification of organic compounds according to the structure of the carbon skeleton
Classification of organic compounds according to the presence of functional groups
Functional groupClass
Example
halogen atoms (F, Cl, Br, I) halogen derivatives CH3CH2Cl (chloroethane)
hydroxyl (–OH)
alcohols (phenols)
CH3CH2OH (ethanol)
thiol or mercapto- (– thiols (mercaptans) CH3CH2SH (ethanethiol)
SН)
ethereal (–O–)
ethers
CH3CH2–O–CH2CH3
(diethyl
ether)
ester
carboxyl –C UN
esters
CH3CH2COOCH3 (methyl acetate)
carboxylic acids CH3COOH (acetic acid)
amide –С ОНН2
amides
carbonyl (–C=O)
sulfo- (–SO3H)
amino- (–NH2)
aldehydes and
ketones
sulfonic acids
amines
nitro- (–NO2)
nitro compounds
acids
CH3CONH2 (acetamide)
CH3CHO (ethanal)
CH3COCH3 (propanone)
СН3SO3Н (methanesulfonic acid)
CH3CH2NH2
(ethylamine,
primary amine)
CH3NHCH3
(dimethylamine,
secondary amine)
CH3CH2NO2 (nitroethane)
Nomenclature of organic compounds
Isomerism of organic compounds
If two or more individual substances havethe same quantitative composition (molecular formula),
but differ from each other in the binding sequence
atoms and (or) their location in space, then in general
In this case they are called isomers.
Since the structure of these compounds is different, then
chemical or physical properties of isomers
are different.
Types of isomerism: structural (structure isomers) and
stereoisomerism (spatial).
Structural isomerism can be of three types:
- isomerism of the carbon skeleton (chain isomers),
- position isomers (multiple bonds or functional
groups),
- isomers of the functional group (interclass).
Stereoisomerism is subdivided
configuration
on
conformational
And
This is geometric isomerism
Plane polarized light
Signs of optical activity:- presence of an asymmetric carbon atom;
- absence of molecular symmetry elements
Enantiomers of adrenaline
protein
Anionic
Flat
center
surface
not occupied
Flat
Anionic
surface
center
busy
(+) - adrenaline
(-)- adrenaline
incomplete
correspondence
low
activity
complete
correspondence
high
activity
Biological activity of enantiomers
asparagineDARVON
analgesic
NOVRAD
antitussive drug
mirror
L-asparagine
D-asparagine
(from asparagus)
(from peas)
bitter taste
sweet taste
enantiomers
Thalidomide victims
Acidity and basicity of organic compounds
Bronsted acids (protic acids) -neutral molecules or ions that can
donate a proton (proton donors).
Typical Brønsted acids are carboxylic acids
acids. They have weaker acidic properties
hydroxyl groups of phenols and alcohols, as well as thio-,
amino and imino groups.
Bronsted bases are neutral molecules or
ions capable of accepting a proton (acceptors
protons).
Typical Bronsted bases are amines.
Ampholytes - compounds, in molecules
which contain both acidic and
main groups.
Types of acids and bases according to Brønsted
The main centers in the novocaine molecule
Use of basic properties to obtain water-soluble forms of drugs
Basicproperties
medicinal
drugs
are used to obtain their water-soluble forms.
When interacting with acids, compounds with
ionic bonds - salts that are highly soluble in water.
Yes, novocaine for injection
used in the form of hydrochloride.
the strongest main center,
which the proton joined
Acid-base properties of substances and their entry into the body
lipidmembrane
Stomach pH 1
UNS
lipid
membrane
blood plasma
pH 7.4
UNS
OSOSN3
Stomach pH 1
+
OSOSN3
NH3
SOOOOSCH3
SOO-
NH2
NH2
OSOSN3
Intestine pH 7-8
blood plasma
pH 7.4
Intestine pH 7-8
Acidic drugs are better absorbed from the stomach (pH 1-3),
and the absorption of drugs or xenobiotic bases occurs only
after they pass from the stomach to the intestines (pH 7-8). During
In one hour, almost 60% of acetylsalicylic acid is absorbed from the stomach of rats.
acid and only 6% aniline of the administered dose. In the intestines of rats
56% of the administered dose of aniline is already absorbed. Such a weak foundation
like caffeine (рKВH + 0.8), absorbed in the same time in a much greater
degree (36%), since even in the highly acidic environment of the stomach, caffeine
is predominantly in a non-ionized state.
Types of reactions in organic chemistry
Organic reactions are classified according tofollowing signs:
1. According to the electronic nature of the reagents.
2. By the change in the number of particles during the reaction.
3. Based on specific characteristics.
4. According to elementary mechanisms
stages of reactions.
Depending on the electronic nature of the reagents, reactions are distinguished: nucleophilic, electrophilic and free radical
Free radicals are electrically neutral particleshaving an unpaired electron, for example: Cl, NO2.
Free radical reactions are characteristic of alkanes.
Electrophilic reagents are cations or molecules
which by themselves or in the presence of a catalyst
have an increased affinity for an electron pair or
negatively charged centers of molecules. These include
cations H+, Cl+, +NO2, +SO3H, R+ and molecules with free
orbitals AlCl3, ZnCl2, etc.
Electrophilic reactions are characteristic of alkenes, alkynes,
aromatic compounds (addition at a double bond,
proton substitution).
Nucleophilic reagents are anions or molecules that
having centers with increased electron density. To them
include anions and molecules such as
HO-, RO-, Cl-, Br-, RCOO-, CN-, R-, NH3, C2H5OH, etc. By change
number of particles during
reactions are distinguished
substitution reactions,
accessions,
splitting off
(elimination),
decomposition
Classification of reactions according to particular characteristics
Reactivity is always considered
only in relation to the reactionary partner.
During a chemical transformation, it is usually
not the whole molecule is affected, but only part of it -
reaction center.
An organic compound may contain
several unequal reaction centers.
Reactions can lead to isomeric products.
Reaction selectivity – qualitative
characteristic meaning predominant
reaction proceeds in one direction from
several possible ones.
There are regioselectivity,
chemoselectivity, stereoselectivity of the reaction.
Selectivity of reactions in organic chemistry
Regioselectivity - preferential reaction according toone of several reaction centers of a molecule.
CH3-CH2-CH3 + Br2
СН3-СНВr-СН3 + НВr
The second isomer, 1-bromopropane, is practically not formed.
Chemoselectivity - preferential reaction according to
one of the related functional groups.
Stereoselectivity - preferential formation in a reaction
one of several possible stereoisomers. Multifunctional compounds contain
several identical functional groups.
Heterofunctional compounds contain
several different functional groups.
Heteropolyfunctional
compounds contain both
different and the same
functional groups.
Properties of poly- and heterofunctional compounds
Each group in poly- and heterofunctionalcompounds can undergo the same reactions as
corresponding group in monofunctional
connections Specific properties of poly- and
heterofunctional compounds
Cyclization reactions
Formation of chelate complexes Polyfunctional compounds as antidotes
The toxic effect of heavy metals is
binding of thiol groups of proteins. As a result, they are inhibited
vital enzymes of the body.
The principle of action of antidotes is the formation of strong
complexes with heavy metal ions.
Plan 1. Subject and significance of bioorganic chemistry 2. Classification and nomenclature of organic compounds 3. Methods of depicting organic molecules 4. Chemical bonding in bioorganic molecules 5. Electronic effects. Mutual influence of atoms in a molecule 6. Classification of chemical reactions and reagents 7. Concept of the mechanisms of chemical reactions 2
Subject of bioorganic chemistry 3 Bioorganic chemistry is an independent branch of chemical science that studies the structure, properties and biological functions of chemical compounds of organic origin that take part in the metabolism of living organisms.
The objects of study of bioorganic chemistry are low-molecular biomolecules and biopolymers (proteins, nucleic acids and polysaccharides), bioregulators (enzymes, hormones, vitamins and others), natural and synthetic physiologically active compounds, including drugs and substances with toxic effects. Biomolecules are bioorganic compounds that are part of living organisms and specialized for the formation of cellular structures and participation in biochemical reactions, form the basis of metabolism (metabolism) and the physiological functions of living cells and multicellular organisms in general. 4 Classification of bioorganic compounds
Metabolism is a set of chemical reactions that occur in the body (in vivo). Metabolism is also called metabolism. Metabolism can occur in two directions - anabolism and catabolism. Anabolism is the synthesis in the body of complex substances from relatively simple ones. It occurs with the expenditure of energy (endothermic process). Catabolism, on the contrary, is the breakdown of complex organic compounds into simpler ones. It occurs with the release of energy (exothermic process). Metabolic processes take place with the participation of enzymes. Enzymes play the role of biocatalysts in the body. Without enzymes, biochemical processes would either not occur at all, or would proceed very slowly, and the body would not be able to maintain life. 5
Bioelements. The composition of bioorganic compounds, in addition to carbon atoms (C), which form the basis of any organic molecule, also includes hydrogen (H), oxygen (O), nitrogen (N), phosphorus (P) and sulfur (S). These bioelements (organogens) are concentrated in living organisms in quantities that are over 200 times higher than their content in inanimate objects. The noted elements make up over 99% of the elemental composition of biomolecules. 6
Bioorganic chemistry arose from the depths of organic chemistry and is based on its ideas and methods. In the history of development, organic chemistry has the following stages: empirical, analytical, structural and modern. The period from man's first acquaintance with organic substances to the end of the 18th century is considered empirical. The main result of this period was that people realized the importance of elemental analysis and the establishment of atomic and molecular masses. The theory of vitalism - life force (Berzelius). The analytical period continued until the 60s of the 19th century. It was marked by the fact that from the end of the first quarter of the 19th century a number of promising discoveries were made that dealt a crushing blow to the vitalistic theory. The first in this series was Berzelius's student, the German chemist Wöhler. He made a number of discoveries in 1824 - the synthesis of oxalic acid from cyanogen: (CN) 2 HOOC - COOH r. – synthesis of urea from ammonium cyanate: NH 4 CNO NH 2 – C – NH 2 O 8
In 1853, C. Gerard developed the “theory of types” and used it to classify organic compounds. According to Gerard, more complex organic compounds can be produced from the following four main types of substances: HHHH type HHHH O type WATER H Cl type HYDROGEN CHLORIDE HHHHN N type AMMONIA Since 1857, at the suggestion of F. A. Kekule, hydrocarbons began to be classified as methane type HHHNNHH C 9
Basic provisions of the theory of the structure of organic compounds (1861) 1) atoms in molecules are connected to each other by chemical bonds in accordance with their valency; 2) atoms in molecules of organic substances are connected to each other in a certain sequence, which determines the chemical structure (structure) of the molecule; 3) the properties of organic compounds depend not only on the number and nature of their constituent atoms, but also on the chemical structure of the molecules; 4) in organic molecules there is interaction between atoms, both bound to each other and unbound; 5) the chemical structure of a substance can be determined by studying its chemical transformations and, conversely, its properties can be characterized by the structure of a substance. 10
Basic provisions of the theory of the structure of organic compounds (1861) A structural formula is an image of the sequence of bonds of atoms in a molecule. Gross formula - CH 4 O or CH 3 OH Structural formula Simplified structural formulas are sometimes called rational Molecular formula - the formula of an organic compound, which indicates the number of atoms of each element in the molecule. For example: C 5 H 12 - pentane, C 6 H 6 - gasoline, etc. eleven
Stages of development of bioorganic chemistry As a separate field of knowledge that combines the conceptual principles and methodology of organic chemistry on the one hand and molecular biochemistry and molecular pharmacology on the other hand, bioorganic chemistry was formed in the twentieth century based on developments in the chemistry of natural substances and biopolymers. Modern bioorganic chemistry has acquired fundamental significance thanks to the work of W. Stein, S. Moore, F. Sanger (analysis of amino acid composition and determination of the primary structure of peptides and proteins), L. Pauling and H. Astbury (clarification of the structure of the -helix and -structure and their significance in the implementation of the biological functions of protein molecules), E. Chargaff (deciphering the features of the nucleotide composition of nucleic acids), J. Watson, Fr. Crick, M. Wilkins, R. Franklin (establishing the patterns of the spatial structure of the DNA molecule), G. Corani (chemical gene synthesis), etc. 14
Classification of organic compounds according to the structure of the carbon skeleton and the nature of the functional group The huge number of organic compounds prompted chemists to classify them. The classification of organic compounds is based on two classification criteria: 1. The structure of the carbon skeleton 2. The nature of the functional groups Classification according to the method of structure of the carbon skeleton: 1. Acyclic (alkanes, alkenes, alkynes, alkadienes); 2. Cyclic 2.1. Carbocyclic (alicyclic and aromatic) 2.2. Heterocyclic 15 Acyclic compounds are also called aliphatic. These include substances with an open carbon chain. Acyclic compounds are divided into saturated (or saturated) C n H 2n+2 (alkanes, paraffins) and unsaturated (unsaturated). The latter include alkenes C n H 2n, alkynes C n H 2n -2, alkadienes C n H 2n -2.
16 Cyclic compounds contain rings (cycles) within their molecules. If the cycles contain only carbon atoms, then such compounds are called carbocyclic. In turn, carbocyclic compounds are divided into alicyclic and aromatic. Alicyclic hydrocarbons (cycloalkanes) include cyclopropane and its homologues - cyclobutane, cyclopentane, cyclohexane, and so on. If the cyclic system, in addition to the hydrocarbon, also includes other elements, then such compounds are classified as heterocyclic.
Classification by the nature of a functional group A functional group is an atom or a group of atoms connected in a certain way, the presence of which in a molecule of an organic substance determines the characteristic properties and its belonging to one or another class of compounds. Based on the number and homogeneity of functional groups, organic compounds are divided into mono-, poly- and heterofunctional. Substances with one functional group are called monofunctional; substances with several identical functional groups are called polyfunctional. Compounds containing several different functional groups are heterofunctional. It is important that compounds of the same class are combined into homologous series. A homologous series is a series of organic compounds with the same functional groups and the same structure; each representative of the homologous series differs from the previous one by a constant unit (CH 2), which is called the homologous difference. Members of a homologous series are called homologues. 17
Nomenclature systems in organic chemistry - trivial, rational and international (IUPAC) Chemical nomenclature is a set of names of individual chemical substances, their groups and classes, as well as rules for compiling their names. Chemical nomenclature is a set of names of individual chemical substances, their groups and classes, as well as rules compiling their names. The trivial (historical) nomenclature is associated with the process of obtaining substances (pyrogallol - a product of pyrolysis of gallic acid), the source of origin from which it was obtained (formic acid), etc. Trivial names of compounds are widely used in the chemistry of natural and heterocyclic compounds (citral, geraniol, thiophene, pyrrole, quinoline, etc.). Trivial (historical) nomenclature is associated with the process of obtaining substances (pyrogallol is a product of pyrolysis of gallic acid), the source of origin, from which was obtained (formic acid), etc. Trivial names of compounds are widely used in the chemistry of natural and heterocyclic compounds (citral, geraniol, thiophene, pyrrole, quinoline, etc.). Rational nomenclature is based on the principle of dividing organic compounds into homologous series. All substances in a certain homologous series are considered as derivatives of the simplest representative of this series - the first or sometimes the second. In particular, for alkanes - methane, for alkenes - ethylene, etc. The rational nomenclature is based on the principle of dividing organic compounds into homologous series. All substances in a certain homologous series are considered as derivatives of the simplest representative of this series - the first or sometimes the second. In particular, for alkanes - methane, for alkenes - ethylene, etc. 18
International nomenclature (IUPAC). The rules of modern nomenclature were developed in 1957 at the 19th Congress of the International Union of Pure and Applied Chemistry (IUPAC). Radical functional nomenclature. These names are based on the name of the functional class (alcohol, ether, ketone, etc.), which is preceded by the names of hydrocarbon radicals, for example: alyl chloride, diethyl ether, dimethyl ketone, propyl alcohol, etc. Substitute nomenclature. Nomenclature rules. The parent structure is the structural fragment of the molecule (molecular skeleton) underlying the name of the compound, the main carbon chain of atoms for alicyclic compounds, and the cycle for carbocyclic compounds. 19
Chemical bond in organic molecules Chemical bond is the phenomenon of interaction between the outer electron shells (valence electrons of atoms) and atomic nuclei, which determines the existence of a molecule or crystal as a whole. As a rule, an atom, accepting or donating an electron or forming a common electron pair, tends to acquire a configuration of the outer electron shell similar to that of noble gases. The following types of chemical bonds are characteristic of organic compounds: - ionic bond - covalent bond - donor - acceptor bond - hydrogen bond. There are also some other types of chemical bonds (metallic, one-electron, two-electron three-center), but they are practically not found in organic compounds. 20
Types of bonds in organic compounds The most characteristic of organic compounds is a covalent bond. A covalent bond is the interaction of atoms, which is realized through the formation of a common electron pair. This type of bond is formed between atoms that have comparable electronegativity values. Electronegativity is a property of an atom that shows the ability to attract electrons to itself from other atoms. A covalent bond can be polar or non-polar. A non-polar covalent bond occurs between atoms with the same electronegativity value
Types of bonds in organic compounds A polar covalent bond is formed between atoms that have different electronegativity values. In this case, the bonded atoms acquire partial charges δ+δ+ δ-δ- A special subtype of covalent bond is the donor-acceptor bond. As in previous examples, this type of interaction is due to the presence of a common electron pair, but the latter is provided by one of the atoms forming the bond (donor) and accepted by another atom (acceptor) 24
Types of bonds in organic compounds An ionic bond is formed between atoms that differ greatly in electronegativity values. In this case, the electron from the less electronegative element (often a metal) is completely transferred to the more electronegative element. This electron transition causes the appearance of a positive charge on the less electronegative atom and a negative charge on the more electronegative one. Thus, two ions with opposite charges are formed, between which there is an electrovalent interaction. 25
Types of Bonds in Organic Compounds A hydrogen bond is an electrostatic interaction between a hydrogen atom, which is bonded in a highly polar manner, and electron pairs of oxygen, fluorine, nitrogen, sulfur and chlorine. This type of interaction is a rather weak interaction. Hydrogen bonding can be intermolecular or intramolecular. Intermolecular hydrogen bond (interaction between two molecules of ethyl alcohol) Intramolecular hydrogen bond in salicylic aldehyde 26
Chemical bonding in organic molecules The modern theory of chemical bonding is based on the quantum mechanical model of a molecule as a system consisting of electrons and atomic nuclei. The cornerstone concept of quantum mechanical theory is the atomic orbital. An atomic orbital is a part of space in which the probability of finding electrons is maximum. Bonding can thus be viewed as the interaction (“overlap”) of orbitals that each carry one electron with opposite spins. 27
Hybridization of atomic orbitals According to quantum mechanical theory, the number of covalent bonds formed by an atom is determined by the number of one-electron atomic orbitals (the number of unpaired electrons). The carbon atom in its ground state has only two unpaired electrons, but the possible transition of an electron from 2s to 2 pz makes it possible to form four covalent bonds. The state of a carbon atom in which it has four unpaired electrons is called “excited.” Despite the fact that carbon orbitals are unequal, it is known that the formation of four equivalent bonds is possible due to the hybridization of atomic orbitals. Hybridization is a phenomenon in which the same number of orbitals of the same shape and number are formed from several orbitals of different shapes and similar in energy. 28
Hybrid states of the carbon atom in organic molecules FIRST HYBRID STATE The C atom is in a state of sp 3 hybridization, forms four σ bonds, forms four hybrid orbitals, which are arranged in the shape of a tetrahedron (bond angle) σ bond 31
Hybrid states of the carbon atom in organic molecules SECOND HYBRID STATE The C atom is in a state of sp 2 hybridization, forms three σ-bonds, forms three hybrid orbitals, which are arranged in the shape of a flat triangle (bond angle 120) σ-bonds π-bond 32
Hybrid states of the carbon atom in organic molecules THIRD HYBRID STATE The C atom is in a state of sp-hybridization, forms two σ-bonds, forms two hybrid orbitals, which are arranged in a line (bond angle 180) σ-bonds π-bonds 33
Characteristics of chemical bonds POLING scale: F-4.0; O – 3.5; Cl – 3.0; N – 3.0; Br – 2.8; S – 2.5; C-2.5; H-2.1. difference 1.7
Characteristics of chemical bonds Bond polarizability is a shift in electron density under the influence of external factors. Bond polarizability is the degree of electron mobility. As the atomic radius increases, the polarizability of electrons increases. Therefore, the polarizability of the Carbon - halogen bond increases as follows: C-F 
Electronic effects. Mutual influence of atoms in a molecule 39 According to modern theoretical concepts, the reactivity of organic molecules is predetermined by the displacement and mobility of electron clouds that form a covalent bond. In organic chemistry, two types of electron displacements are distinguished: a) electronic displacements occurring in the -bond system, b) electronic displacements transmitted by the -bond system. In the first case, the so-called inductive effect takes place, in the second - a mesomeric effect. The inductive effect is a redistribution of electron density (polarization) resulting from the difference in electronegativity between the atoms of a molecule in a system of bonds. Due to the insignificant polarizability of the -bonds, the inductive effect quickly fades away and after 3-4 bonds it almost does not appear.
Electronic effects. Mutual influence of atoms in a molecule 40 The concept of the inductive effect was introduced by K. Ingold, and he also introduced the following designations: –I-effect in the case of a decrease in electron density by a substituent +I-effect in the case of an increase in electron density by a substituent A positive inductive effect is exhibited by alkyl radicals (CH 3, C 2 H 5 - etc.). All other substituents bonded to the carbon atom exhibit a negative inductive effect.
Electronic effects. Mutual influence of atoms in a molecule 41 The mesomeric effect is the redistribution of electron density along a conjugated system. Conjugated systems include molecules of organic compounds in which double and single bonds alternate or when an atom with a lone pair of electrons in the p-orbital is located next to the double bond. In the first case, - conjugation takes place, and in the second case, p, -conjugation takes place. Coupled systems come in open and closed circuit configurations. Examples of such compounds are 1,3-butadiene and gasoline. In the molecules of these compounds, carbon atoms are in a state of sp 2 hybridization and, due to non-hybrid p-orbitals, form -bonds that mutually overlap and form a single electron cloud, that is, conjugation takes place.
Electronic effects. Mutual influence of atoms in a molecule 42 There are two types of mesomeric effect - positive mesomeric effect (+M) and negative mesomeric effect (-M). A positive mesomeric effect is exhibited by substituents that provide p-electrons to the conjugated system. These include: -O, -S -NH 2, -OH, -OR, Hal (halogens) and other substituents that have a negative charge or a lone pair of electrons. The negative mesomeric effect is characteristic of substituents that absorb electron density from the conjugated system. These include substituents that have multiple bonds between atoms with different electronegativity: - N0 2 ; -SO 3 H; >C=O; -COON and others. The mesomeric effect is graphically reflected by a bent arrow, which shows the direction of electron displacement. Unlike the induction effect, the mesomeric effect does not go out. It is transmitted completely throughout the system, regardless of the length of the interfacing chain. C=O; -COON and others. The mesomeric effect is graphically reflected by a bent arrow, which shows the direction of electron displacement. Unlike the induction effect, the mesomeric effect does not go out. It is transmitted completely throughout the system, regardless of the length of the interfacing chain."> 
Types of chemical reactions 43 A chemical reaction can be considered as the interaction of a reagent and substrate. Depending on the method of breaking and forming a chemical bond in molecules, organic reactions are divided into: a) homolytic b) heterolytic c) molecular Homolytic or free radical reactions are caused by homolytic cleavage of the bond, when each atom has one electron left, that is, radicals are formed . Homolytic cleavage occurs at high temperatures, the action of a light quantum, or catalysis.
Heterolytic or ionic reactions proceed in such a way that a pair of bonding electrons remains near one of the atoms and ions are formed. A particle with an electron pair is called nucleophilic and has a negative charge (-). A particle without an electron pair is called electrophilic and has a positive charge (+). 44 Types of chemical reactions
Mechanism of a chemical reaction 45 The mechanism of a reaction is the set of elementary (simple) stages that make up a given reaction. The reaction mechanism most often includes the following stages: activation of the reagent with the formation of an electrophile, nucleophile or free radical. To activate a reagent, a catalyst is usually needed. In the second stage, the activated reagent interacts with the substrate. In this case, intermediate particles (intermediates) are formed. The latter include -complexes, -complexes (carbocations), carbanions, and new free radicals. At the final stage, the addition or elimination of a particle to (from) the intermediate formed in the second stage takes place with the formation of the final reaction product. If a reagent generates a nucleophile upon activation, then these are nucleophilic reactions. They are marked with the letter N - (in the index). In the case where the reagent generates an electrophile, the reactions are classified as electrophilic (E). The same can be said about free radical reactions (R).
Nucleophiles are reagents that have a negative charge or an atom enriched in electron density: 1) anions: OH -, CN -, RO -, RS -, Hal - and other anions; 2) neutral molecules with lone pairs of electrons: NH 3, NH 2 R, H 2 O, ROH and others; 3) molecules with excess electron density (having - bonds). Electrophiles are reagents that have a positive charge or an atom depleted in electron density: 1) cations: H + (proton), HSO 3 + (hydrogen sulfonium ion), NO 2 + (nitronium ion), NO (nitrosonium ion) and other cations; 2) neutral molecules with a vacant orbital: AlCl 3, FeBr 3, SnCl 4, BF 4 (Lewis acids), SO 3; 3) molecules with depleted electron density on the atom. 46
49
50
51
52
Modern bioorganic chemistry is a branched field of knowledge, the foundation of many biomedical disciplines and, first of all, biochemistry, molecular biology, genomics, proteomics and
bioinformatics, immunology, pharmacology.
The program is based on a systematic approach to building the entire course on a single theoretical basis.
basis based on ideas about the electronic and spatial structure of organic
compounds and mechanisms of their chemical transformations. The material is presented in the form of 5 sections, the most important of which are: “Theoretical foundations of the structure of organic compounds and factors determining their reactivity”, “Biologically important classes of organic compounds” and “Biopolymers and their structural components. Lipids"
The program is aimed at specialized teaching of bioorganic chemistry at a medical university, and therefore the discipline is called “bioorganic chemistry in medicine.” The profiling of the teaching of bioorganic chemistry is served by consideration of the historical relationship between the development of medicine and chemistry, including organic, increased attention to classes of biologically important organic compounds (heterofunctional compounds, heterocycles, carbohydrates, amino acids and proteins, nucleic acids, lipids) as well as biologically important reactions of these classes of compounds ). A separate section of the program is devoted to consideration of the pharmacological properties of certain classes of organic compounds and the chemical nature of certain classes of drugs.
Considering the important role of “oxidative stress diseases” in the structure of modern human morbidity, the program pays special attention to free radical oxidation reactions, detection of end products of free radical lipid oxidation in laboratory diagnostics, natural antioxidants and antioxidant drugs. The program provides consideration of environmental problems, namely the nature of xenobiotics and the mechanisms of their toxic effect on living organisms.
1. The purpose and objectives of training.
1.1. The purpose of teaching the subject bioorganic chemistry in medicine is to develop an understanding of the role of bioorganic chemistry as the foundation of modern biology, a theoretical basis for explaining the biological effects of bioorganic compounds, the mechanisms of action of drugs and the creation of new drugs. To develop knowledge of the relationship between the structure, chemical properties and biological activity of the most important classes of bioorganic compounds, to teach how to apply the acquired knowledge when studying subsequent disciplines and in professional activities.
1.2. Objectives of teaching bioorganic chemistry:
1. Formation of knowledge of the structure, properties and reaction mechanisms of the most important classes of bioorganic compounds, which determine their medical and biological significance.
2. Formation of ideas about the electronic and spatial structure of organic compounds as a basis for explaining their chemical properties and biological activity.
3. Formation of skills and practical skills:
classify bioorganic compounds according to the structure of the carbon skeleton and functional groups;
use the rules of chemical nomenclature to indicate the names of metabolites, drugs, xenobiotics;
identify reaction centers in molecules;
be able to carry out qualitative reactions that have clinical and laboratory significance.
2. The place of discipline in the structure of OOP:
The discipline "Bioorganic chemistry" is an integral part of the discipline "Chemistry", which belongs to the mathematical, natural science cycle of disciplines.
The basic knowledge necessary to study the discipline is formed in the cycle of mathematical, natural science disciplines: physics, mathematics; medical informatics; chemistry; biology; anatomy, histology, embryology, cytology; normal physiology; microbiology, virology.
It is a prerequisite for studying the disciplines:
biochemistry;
pharmacology;
microbiology, virology;
immunology;
professional disciplines.
Disciplines studied in parallel, providing interdisciplinary connections within the framework of the basic part of the curriculum:
chemistry, physics, biology, 3. List of disciplines and topics that students need to master to study bioorganic chemistry.
General chemistry. The structure of the atom, the nature of a chemical bond, types of bonds, classes of chemical substances, types of reactions, catalysis, reaction of the medium in aqueous solutions.
Organic chemistry. Classes of organic substances, nomenclature of organic compounds, configuration of the carbon atom, polarization of atomic orbitals, sigma and pi bonds. Genetic relationship of classes of organic compounds. Reactivity of different classes of organic compounds.
Physics. The structure of the atom. Optics - ultraviolet, visible and infrared regions of the spectrum.
Interaction of light with matter - transmission, absorption, reflection, scattering. Polarized light.
Biology. Genetic code. Chemical basis of heredity and variability.
Latin language. Mastering terminology.
Foreign language. Ability to work with foreign literature.
4. Sections of the discipline and interdisciplinary connections with the provided (subsequent) disciplines No. sections of this discipline necessary for studying the provided No. Name of the provided sub-disciplines (subsequent) disciplines (subsequent) disciplines 1 2 3 4 5 1 Chemistry + + + + + Biology + - - + + Biochemistry + + + + + + 4 Microbiology, virology + + - + + + 5 Immunology + - - - + Pharmacology + + - + + + 7 Hygiene + - + + + Professional disciplines + - - + + + 5. Requirements for the level of mastery of the discipline content Achieving the learning goal The discipline “Bioorganic Chemistry” involves the implementation of a number of targeted problem tasks, as a result of which students must develop certain competencies, knowledge, skills, and must acquire certain practical skills.
5.1. The student must have:
5.1.1. General cultural competencies:
the ability and willingness to analyze socially significant problems and processes, to use in practice the methods of the humanities, natural sciences, biomedical and clinical sciences in various types of professional and social activities (OK-1);
5.1.2. Professional competencies (PC):
ability and willingness to apply basic methods, methods and means of obtaining, storing, processing scientific and professional information; receive information from various sources, including the use of modern computer tools, network technologies, databases and the ability and willingness to work with scientific literature, analyze information, conduct searches, turn what you read into a tool for solving professional problems (highlight the main provisions, consequences from them and suggestions);
ability and readiness to participate in setting scientific problems and their experimental implementation (PC-2, PC-3, PC-5, PC-7).
5.2. The student must know:
Principles of classification, nomenclature and isomerism of organic compounds.
Fundamentals of theoretical organic chemistry, which are the basis for studying the structure and reactivity of organic compounds.
The spatial and electronic structure of organic molecules and the chemical transformations of substances that are participants in life processes, in direct connection with their biological structure, chemical properties and biological role of the main classes of biologically important organic compounds.
5.3. The student must be able to:
Classify organic compounds according to the structure of the carbon skeleton and the nature of the functional groups.
Compose formulas by name and name typical representatives of biologically important substances and drugs by structural formula.
Identify functional groups, acidic and basic centers, conjugated and aromatic fragments in molecules to determine the chemical behavior of organic compounds.
Predict the direction and result of chemical transformations of organic compounds.
5.4. The student must have:
Skills of independent work with educational, scientific and reference literature; conduct a search and draw general conclusions.
Have skills in handling chemical glassware.
Have the skills to work safely in a chemical laboratory and the ability to handle caustic, toxic, highly volatile organic compounds, work with burners, alcohol lamps and electric heating devices.
5.5. Forms of knowledge control 5.5.1. Current control:
Diagnostic control of material assimilation. It is carried out periodically mainly to control knowledge of formulaic material.
Educational computer control in every lesson.
Test tasks requiring the ability to analyze and generalize (see Appendix).
Scheduled colloquiums upon completion of the study of large sections of the program (see Appendix).
5.5.2 Final control:
Test (carried out in two stages):
C.2 - Mathematical, natural science and medical-biological General labor intensity:
2 Classification, nomenclature and Classification and classification characteristics of organic modern physical compounds: the structure of the carbon skeleton and the nature of the functional group.
chemical methods Functional groups, organic radicals. Biologically important studies of bioorganic classes of organic compounds: alcohols, phenols, thiols, ethers, sulfides, aldehyde compounds, ketones, carboxylic acids and their derivatives, sulfonic acids.
IUPAC nomenclature. Varieties of international nomenclature: substitutive and radical-functional nomenclature. The value of knowledge 3 Theoretical foundations of the structure of organic compounds and the Theory of the structure of organic compounds by A.M. Butlerov. The main factors determining their positions. Structural formulas. The nature of the carbon atom by position and reactivity. chains. Isomerism as a specific phenomenon of organic chemistry. Types of Stereoisomerism.
Chirality of molecules of organic compounds as a cause of optical isomerism. Stereoisomerism of molecules with one center of chirality (enantiomerism). Optical activity. Glyceraldehyde as a configuration standard. Fischer projection formulas. D and L System of Stereochemical Nomenclature. Ideas about R, S-nomenclature.
Stereoisomerism of molecules with two or more chirality centers: enantiomerism and diastereomerism.
Stereoisomerism in a series of compounds with a double bond (Pydiastereomerism). Cis and trans isomers. Stereoisomerism and biological activity of organic compounds.
Mutual influence of atoms: causes of occurrence, types and methods of its transmission in molecules of organic compounds.
Pairing. Pairing in open circuits (Pi-Pi). Conjugated bonds. Diene structures in biologically important compounds: 1,3-dienes (butadiene), polyenes, alpha, beta-unsaturated carbonyl compounds, carboxyl group. Coupling as a system stabilization factor. Conjugation energy. Conjugation in arenes (Pi-Pi) and heterocycles (p-Pi).
Aromaticity. Aromaticity criteria. Aromaticity of benzenoid (benzene, naphthalene, anthracene, phenanthrene) and heterocyclic (furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, purine) compounds. Widespread occurrence of conjugated structures in biologically important molecules (porphin, heme, etc.).
Bond polarization and electronic effects (inductive and mesomeric) as the cause of the uneven distribution of electron density in the molecule. Substituents are electron donors and electron acceptors.
The most important substituents and their electronic effects. Electronic effects of substituents and reactivity of molecules. Orientation rule in the benzene ring, substituents of the first and second kind.
Acidity and basicity of organic compounds.
Acidity and basicity of neutral molecules of organic compounds with hydrogen-containing functional groups (amines, alcohols, thiols, phenols, carboxylic acids). Acids and bases according to Bronsted-Lowry and Lewis. Conjugate pairs of acids and bases. Anion acidity and stability. Quantitative assessment of the acidity of organic compounds based on Ka and pKa values.
Acidity of various classes of organic compounds. Factors that determine the acidity of organic compounds: electronegativity of the nonmetal atom (C-H, N-H, and O-H acids); polarizability of a nonmetal atom (alcohols and thiols, thiol poisons); nature of the radical (alcohols, phenols, carboxylic acids).
Basicity of organic compounds. n-bases (heterocycles) and pi-bases (alkenes, alkanedienes, arenes). Factors that determine the basicity of organic compounds: electronegativity of the heteroatom (O- and N bases); polarizability of a nonmetal atom (O- and S-base); nature of the radical (aliphatic and aromatic amines).
The importance of the acid-base properties of neutral organic molecules for their reactivity and biological activity.
Hydrogen bonding as a specific manifestation of acid-base properties. General patterns of reactivity of organic compounds as the chemical basis of their biological functioning.
Reaction mechanisms of organic compounds.
Classification of reactions of organic compounds according to the result of substitution, addition, elimination, rearrangement, redox and according to the mechanism - radical, ionic (electrophilic, nucleophilic). Types of covalent bond cleavage in organic compounds and the resulting particles: homolytic cleavage (free radicals) and heterolytic cleavage (carbocations and carbonanions).
Electronic and spatial structure of these particles and factors determining their relative stability.
Homolytic radical substitution reactions in alkanes involving C-H bonds of the sp 3-hybridized carbon atom. Free radical oxidation reactions in a living cell. Reactive (radical) forms of oxygen. Antioxidants. Biological significance.
Electrophilic addition reactions (Ae): heterolytic reactions involving the Pi bond. Mechanism of ethylene halogenation and hydration reactions. Acid catalysis. Influence of static and dynamic factors on the regioselectivity of reactions. Peculiarities of reactions of addition of hydrogen-containing substances to the Pi bond in unsymmetrical alkenes. Markovnikov's rule. Features of electrophilic addition to conjugated systems.
Electrophilic substitution reactions (Se): heterolytic reactions involving an aromatic system. Mechanism of electrophilic substitution reactions in arenes. Sigma complexes. Reactions of alkylation, acylation, nitration, sulfonation, halogenation of arenes. Orientation rule.
Substitutes of the 1st and 2nd kind. Features of electrophilic substitution reactions in heterocycles. Orienting influence of heteroatoms.
Reactions of nucleophilic substitution (Sn) at sp3-hybridized carbon atom: heterolytic reactions caused by polarization of the carbon-heteroatom sigma bond (halogen derivatives, alcohols). The influence of electronic and spatial factors on the reactivity of compounds in nucleophilic substitution reactions.
Hydrolysis reaction of halogen derivatives. Alkylation reactions of alcohols, phenols, thiols, sulfides, ammonia and amines. The role of acid catalysis in nucleophilic substitution of the hydroxyl group.
Deamination of compounds with a primary amino group. Biological role of alkylation reactions.
Elimination reactions (dehydrohalogenation, dehydration).
Increased CH acidity as a cause of elimination reactions accompanying nucleophilic substitution at the sp3-hybridized carbon atom.
Nucleophilic addition reactions (An): heterolytic reactions involving the pi carbon-oxygen bond (aldehydes, ketones). Classes of carbonyl compounds. Representatives. Preparation of aldehydes, ketones, carboxylic acids. Structure and reactivity of the carbonyl group. Influence of electronic and spatial factors. Mechanism of An reactions: role of protonation in increasing carbonyl reactivity. Biologically important reactions of aldehydes and ketones: hydrogenation, oxidation-reduction of aldehydes (dismutation reaction), oxidation of aldehydes, formation of cyanohydrins, hydration, formation of hemiacetals, imines. Aldol addition reactions. Biological significance.
Nucleophilic substitution reactions at the sp2-hybridized carbon atom (carboxylic acids and their functional derivatives).
The mechanism of nucleophilic substitution reactions (Sn) at the sp2 hybridized carbon atom. Acylation reactions - the formation of anhydrides, esters, thioesters, amides - and their reverse hydrolysis reactions. Biological role of acylation reactions. Acidic properties of carboxylic acids according to the O-H group.
Oxidation and reduction reactions of organic compounds.
Redox reactions, electronic mechanism.
Oxidation states of carbon atoms in organic compounds. Oxidation of primary, secondary and tertiary carbon atoms. Oxidability of various classes of organic compounds. Ways of oxygen utilization in the cell.
Energetic oxidation. Oxidase reactions. Oxidation of organic substances is the main source of energy for chemotrophs. Plastic oxidation.
4 Biologically important classes of organic compounds Polyhydric alcohols: ethylene glycol, glycerol, inositol. Education Hydroxy acids: classification, nomenclature, representatives of lactic, betahydroxybutyric, gammahydroxybutyric, malic, tartaric, citric, reductive amination, transamination and decarboxylation.
Amino acids: classification, representatives of beta and gamma isomers: aminopropane, gamma-aminobutyric, epsilonaminocaproic. Reaction Salicylic acid and its derivatives (acetylsalicylic acid, antipyretic, anti-inflammatory and anti-rheumatic agent, enteroseptol and 5-NOK. The isoquinoline core as the basis of opium alkaloids, antispasmodics (papaverine) and analgesics (morphine). Acridine derivatives are disinfectants.
xanthine derivatives - caffeine, theobromine and theophylline, indole derivatives reserpine, strychnine, pilocarpine, quinoline derivatives - quinine, isoquinoline morphine and papaverine.
cephalosproins are derivatives of cephalosporanic acid, tetracyclines are derivatives of naphthacene, streptomycins are amyloglycosides. Semi-synthetic 5 Biopolymers and their structural components. Lipids. Definition. Classification. Functions.
Cyclo-oxotautomerism. Mutarotation. Derivatives of monosaccharides deoxysugar (deoxyribose) and amino sugar (glucosamine, galactosamine).
Oligosaccharides. Disaccharides: maltose, lactose, sucrose. Structure. Oglycosidic bond. Restorative properties. Hydrolysis. Biological (pathway of amino acid breakdown); radical reactions - hydroxylation (formation of oxy-derivatives of amino acids). Peptide bond formation.
Peptides. Definition. Structure of the peptide group. Functions.
Biologically active peptides: glutathione, oxytocin, vasopressin, glucagon, neuropeptides, kinin peptides, immunoactive peptides (thymosin), inflammatory peptides (difexin). The concept of cytokines. Antibiotic peptides (gramicidin, actinomycin D, cyclosporine A). Peptide toxins. Relationship between the biological effects of peptides and certain amino acid residues.
Squirrels. Definition. Functions. Levels of protein structure. The primary structure is the sequence of amino acids. Research methods. Partial and complete hydrolysis of proteins. The importance of determining the primary structure of proteins.
Directed site-specific mutagenesis as a method for studying the relationship between the functional activity of proteins and the primary structure. Congenital disorders of the primary structure of proteins - point mutations. Secondary structure and its types (alpha helix, beta structure). Tertiary structure.
Denaturation. The concept of active centers. Quaternary structure of oligomeric proteins. Cooperative properties. Simple and complex proteins: glycoproteins, lipoproteins, nucleoproteins, phosphoproteins, metalloproteins, chromoproteins.
Nitrogen bases, nucleosides, nucleotides and nucleic acids.
Definition of the concepts nitrogenous base, nucleoside, nucleotide and nucleic acid. Purine (adenine and guanine) and pyrimidine (uracil, thymine, cytosine) nitrogenous bases. Aromatic properties. Resistance to oxidative degradation as a basis for fulfilling a biological role.
Lactim - lactam tautomerism. Minor nitrogenous bases (hypoxanthine, 3-N-methyluracil, etc.). Derivatives of nitrogenous bases - antimetabolites (5-fluorouracil, 6-mercaptopurine).
Nucleosides. Definition. Formation of a glycosidic bond between a nitrogenous base and a pentose. Hydrolysis of nucleosides. Nucleosides antimetabolites (adenine arabinoside).
Nucleotides. Definition. Structure. Formation of a phosphoester bond during the esterification of the C5 hydroxyl of pentose with phosphoric acid. Hydrolysis of nucleotides. Macroerg nucleotides (nucleoside polyphosphates - ADP, ATP, etc.). Nucleotides-coenzymes (NAD+, FAD), structure, role of vitamins B5 and B2.
Nucleic acids - RNA and DNA. Definition. Nucleotide composition of RNA and DNA. Primary structure. Phosphodiester bond. Hydrolysis of nucleic acids. Definition of the concepts triplet (codon), gene (cistron), genetic code (genome). International Human Genome Project.
Secondary structure of DNA. The role of hydrogen bonds in the formation of secondary structure. Complementary pairs of nitrogenous bases. Tertiary structure of DNA. Changes in the structure of nucleic acids under the influence of chemicals. The concept of mutagenic substances.
Lipids. Definition, classification. Saponifiable and unsaponifiable lipids.
Natural higher fatty acids are components of lipids. The most important representatives: palmitic, stearic, oleic, linoleic, linolenic, arachidonic, eicosapentaenoic, docosohexaenoic (vitamin F).
Neutral lipids. Acylglycerols - natural fats, oils, waxes.
Artificial edible hydrofats. Biological role of acylglycerols.
Phospholipids. Phosphatidic acids. Phosphatidylcholines, phosphatidiethanolamines and phosphatidylserines. Structure. Participation in the formation of biological membranes. Lipid peroxidation in cell membranes.
Sphingolipids. Sphingosine and sphingomyelins. Glycolipids (cerebrosides, sulfatides and gangliosides).
Unsaponifiable lipids. Terpenes. Mono- and bicyclic terpenes 6 Pharmacological properties Pharmacological properties of some classes of mono-poly and some classes of heterofunctional compounds (hydrogen halides, alcohols, oxy- and organic compounds. oxoacids, benzene derivatives, heterocycles, alkaloids.). Chemical The chemical nature of some of the anti-inflammatory drugs, analgesics, antiseptics and classes of drugs. antibiotics.
6.3. Sections of disciplines and types of classes 1. Introduction to the subject. Classification, nomenclature and research of bioorganic compounds 2. Theoretical foundations of the structure of organic reactivity.
3. Biologically important classes of organic 5 Pharmacological properties of some classes of organic compounds. The chemical nature of some classes of drugs L-lectures; PZ – practical exercises; LR – laboratory work; C – seminars; SRS – independent work of students;
6.4 Thematic plan of lectures on discipline 1 1 Introduction to the subject. History of the development of bioorganic chemistry, significance for 3 2 Theory of the structure of organic compounds by A.M. Butlerov. Isomerism as 4 2 Mutual influence of atoms: causes of occurrence, types and methods of its transmission in 7 1.2 Test work in the sections “Classification, nomenclature and modern physicochemical methods for studying bioorganic compounds” and “Theoretical foundations of the structure of organic compounds and factors determining their reaction 15 5 Pharmacological properties of some classes of organic compounds. Chemical 19 4 14 Detection of insoluble calcium salts of higher carbonates 1 1 Introduction to the subject. Classification and Working with recommended literature.
nomenclature of bioorganic compounds. Completing a written assignment for 3 2 Mutual influence of atoms in molecules Work with recommended literature.
4 2 Acidity and basicity of organic materials Work with recommended literature.
5 2 Mechanisms of organic reactions Work with recommended literature.
6 2 Oxidation and reduction of organic materials Work with recommended literature.
7 1.2 Test work by section Work with recommended literature. * modern physical and chemical methods on the proposed topics, conducting research on bioorganic compounds”, information search in various organic compounds and factors, INTERNET and work with English-language databases 8 3 Heterofunctional bioorganic Work with recommended literature.
9 3 Biologically important heterocycles. Work with recommended literature.
10 3 Vitamins (laboratory work). Work with recommended literature.
12 4 Alpha amino acids, peptides and proteins. Work with recommended literature.
13 4 Nitrogen bases, nucleosides, Work with recommended literature.
nucleotides and nucleic acids. Completing a written writing task 15 5 Pharmacological properties of some Work with recommended literature.
classes of organic compounds. Completing a written assignment to write The chemical nature of some classes of chemical formulas of some medicinal * - tasks of the student's choice.
organic compounds.
organic molecules.
organic molecules.
organic compounds.
organic compounds.
connections. Stereoisomerism.
certain classes of drugs.
During the semester, a student can score a maximum of 65 points in practical classes.
In one practical lesson, a student can score a maximum of 4.3 points. This number consists of points scored for attending a class (0.6 points), completing an assignment for extracurricular independent work (1.0 points), laboratory work (0.4 points) and points awarded for an oral answer and a test task (from 1 .3 to 2.3 points). Points for attending classes, completing assignments for extracurricular independent work and laboratory work are awarded on a “yes” - “no” basis. Points for the oral answer and the test task are awarded differentiated from 1.3 to 2.3 points in the case of positive answers: 0-1.29 points correspond to the rating “unsatisfactory”, 1.3-1.59 - “satisfactory”, 1.6 -1.99 – “good”, 2.0-2.3 – “excellent”. On the test, a student can score a maximum of 5.0 points: attending class 0.6 points and giving an oral answer 2.0-4.4 points.
To be admitted to the test, a student must score at least 45 points, while the student’s current performance is assessed as follows: 65-75 points – “excellent”, 54-64 points – “good”, 45-53 points – “satisfactory”, less than 45 points – unsatisfactory. If a student scores from 65 to 75 points (“excellent” result), then he is exempt from the test and receives a “pass” mark in the grade book automatically, gaining 25 points for the test.
On the test, a student can score a maximum of 25 points: 0-15.9 points correspond to the grade “unsatisfactory”, 16-17.5 – “satisfactory”, 17.6-21.2 – “good”, 21.3-25 – “ Great".
Distribution of bonus points (up to 10 points per semester in total) 1. Lecture attendance – 0.4 points (100% lecture attendance – 6.4 points per semester);
2. Participation in UIRS up to 3 points, including:
writing an abstract on the proposed topic – 0.3 points;
preparation of a report and multimedia presentation for the final educational and theoretical conference 3. Participation in research work – up to 5 points, including:
attending a meeting of the student scientific circle at the department - 0.3 points;
preparing a report for a meeting of the student scientific circle – 0.5 points;
giving a report at a university student scientific conference – 1 point;
presentation at a regional, all-Russian and international student scientific conference – 3 points;
publication in collections of student scientific conferences – 2 points;
publication in a peer-reviewed scientific journal – 5 points;
4. Participation in educational work at the department up to 3 points, including:
participation in the organization of educational activities carried out by the department during extracurricular hours - 2 points for one event;
attending educational activities held by the department during extracurricular hours – 1 point for one event;
Distribution of penalty points (up to 10 points per semester in total) 1. Absence from lectures for an unexcused reason - 0.66-0.67 points (0% attendance at lectures - 10 points for If a student missed a lesson for a valid reason, he has the right to work out the lesson to improve your current rating.
If the absence is unexcused, the student must complete the class and receive a grade with a reduction factor of 0.8.
If a student is exempt from physical presence in classes (by order of the academy), then he is awarded maximum points if he completes the assignment for extracurricular independent work.
6. Educational, methodological and information support of the discipline 1. N.A. Tyukavkina, Yu.I. Baukov, S.E. Zurabyan. Bioorganic chemistry. M.:DROFA, 2009.
2. Tyukavkina N.A., Baukov Yu.I. Bioorganic chemistry. M.:DROFA, 2005.
1. Ovchinikov Yu.A. Bioorganic chemistry. M.: Education, 1987.
2. Riles A., Smith K., Ward R. Fundamentals of organic chemistry. M.: Mir, 1983.
3. Shcherbak I.G. Biological chemistry. Textbook for medical schools. S.-P. St. Petersburg State Medical University publishing house, 2005.
4. Berezov T.T., Korovkin B.F. Biological chemistry. M.: Medicine, 2004.
5. Berezov T.T., Korovkin B.F. Biological chemistry. M.: Medicine, Postupaev V.V., Ryabtseva E.G. Biochemical organization of cell membranes (textbook for students of pharmaceutical faculties of medical universities). Khabarovsk, Far Eastern State Medical University. 2001
7. Soros educational magazine, 1996-2001.
8. Guide to laboratory classes in bioorganic chemistry. Edited by N.A. Tyukavkina, M.:
Medicine, 7.3 Educational and methodological materials prepared by the department 1. Methodological development of practical classes in bioorganic chemistry for students.
2. Methodological developments for independent extracurricular work of students.
3. Borodin E.A., Borodina G.P. Biochemical diagnosis (physiological role and diagnostic value of biochemical parameters of blood and urine). Textbook 4th edition. Blagoveshchensk, 2010.
4. Borodina G.P., Borodin E.A. Biochemical diagnosis (physiological role and diagnostic value of biochemical parameters of blood and urine). Electronic textbook. Blagoveshchensk, 2007.
5. Assignments for computer testing of students’ knowledge in bioorganic chemistry (Compiled by Borodin E.A., Doroshenko G.K., Egorshina E.V.) Blagoveshchensk, 2003.
6. Test assignments in bioorganic chemistry for the exam in bioorganic chemistry for students of the medical faculty of medical universities. Toolkit. (Compiled by Borodin E.A., Doroshenko G.K.). Blagoveshchensk, 2002.
7. Test assignments in bioorganic chemistry for practical classes in bioorganic chemistry for students of the Faculty of Medicine. Toolkit. (Compiled by Borodin E.A., Doroshenko G.K.). Blagoveshchensk, 2002.
8. Vitamins. Toolkit. (Compiled by Egorshina E.V.). Blagoveshchensk, 2001.
8.5 Providing discipline with equipment and educational materials 1 Chemical glassware:
Glassware:
1.1 chemical test tubes 5000 Chemical experiments and analyzes in practical classes, UIRS, 1.2 centrifuge tubes 2000 Chemical experiments and analyzes in practical classes, UIRS, 1.3 glass rods 100 Chemical experiments and analyzes in practical classes, UIRS, 1.4. flasks of various volumes (for 200 Chemical experiments and analyzes in practical classes, UIRS, 1.5 large volume flasks - 0.5-2.0 30 Chemical experiments and analyzes in practical classes, UIRS, 1.6 chemical beakers of various 120 Chemical experiments and analyzes in practical classes, UIRS, 1.7 large chemical beakers 50 Chemical experiments and analyzes in practical classes, UIRS, preparation of workers 1.8 flasks of various sizes 2000 Chemical experiments and analyzes in practical classes, UIRS, 1.9 filter funnels 200 Chemical experiments and analyzes in practical classes, UIRS , 1.10 glassware Chemical experiments and analyzes in practical classes, CIRS, chromatography, etc.).
1.11 alcohol lamps 30 Chemical experiments and analyzes in practical classes, UIRS, Porcelain dishes 1.12 glasses different volumes (0.2- 30 Preparation of reagents for practical classes 1.13 mortars and pestles Preparation of reagents for practical classes, chemical experiments and 1.15 cups for evaporation 20 Chemical experiments and analyzes for practical classes, UIRS, Measuring glassware:
1.16 volumetric flasks of various 100 Preparation of reagents for practical classes, Chemical experiments 1.17 graduated cylinders of various 40 Preparation of reagents for practical classes, Chemical experiments 1.18 beakers of various volumes 30 Preparation of reagents for practical classes, Chemical experiments 1.19 measuring pipettes for 2000 Chemical experiments and analyzes for practical classes, UIRS, micropipettes) 1.20 mechanical automatic 15 Chemical experiments and analyzes in practical classes, UIRS, 1.21 mechanical automatic 2 Chemical experiments and analyzes in practical classes, UIRS, variable volume dispensers NIRS 1.22 electronic automatic 1 Chemical experiments and analyzes in practical classes, UIRS, 1.23 AC microsyringes 5 Chemical experiments and analyzes in practical classes, UIRS, 2 Technical equipment:
2.1 racks for test tubes 100 Chemical experiments and analyzes in practical classes, UIRS, 2.2 racks for pipettes 15 Chemical experiments and analyzes in practical classes, UIRS, 2.3 metal racks 15 Chemical experiments and analyzes in practical classes, UIRS, Heating devices:
2.4 drying cabinets 3 Drying chemical glassware, holding chemicals 2.5 air thermostats 2 Thermostating of the incubation mixture when determining 2.6 water thermostats 2 Thermostating of the incubation mixture when determining 2.7 electric stoves 3 Preparation of reagents for practical exercises, chemical experiments and 2.8 Refrigerators with freezers 5 Storage of chemical reagents, solutions and biological material for chambers “Chinar”, “Biryusa”, practical exercises , UIRS, NIRS "Stinol"
2.9 Storage cabinets 8 Storage of chemical reagents 2.10 Metal safe 1 Storage of toxic reagents and ethanol 3 General purpose equipment:
3.1 analytical damper 2 Gravimetric analysis in practical classes, UIRS, NIRS 3.6 Ultracentrifuge 1 Demonstration of the method of sedimentation analysis in practical classes (Germany) 3.8 Magnetic stirrers 2 Preparation of reagents for practical classes 3.9 Electric distiller DE - 1 Obtaining distilled water for preparing reagents for 3.10 Thermometers 10 Temperature control during chemical analyzes 3.11 Set of hydrometers 1 Measuring the density of solutions 4 Special-purpose equipment:
4.1 Apparatus for electrophoresis at 1 Demonstration of the method of electrophoresis of serum proteins at 4.2 Apparatus for electrophoresis at 1 Demonstration of the method for separating serum lipoproteins 4.3 Equipment for column Demonstration of the method for separating proteins using chromatography 4.4 Equipment for Demonstration of the TLC method for separating lipids at practical thin chromatography layer. classes, NIRS Measuring equipment:
Photoelectric colorimeters:
4.8 Photometer “SOLAR” 1 Measurement of light absorption of colored solutions at 4.9 Spectrophotometer SF 16 1 Measurement light absorption of solutions in the visible and UV regions 4.10 Clinical spectrophotometer 1 Measurement of light absorption of solutions in the visible and UV regions of the “Schimadzu - CL–770” spectrum using spectral methods of determination 4.11 Highly efficient 1 Demonstration of the HPLC method (practical exercises, UIRS, NIRS) liquid chromatograph "Milichrome - 4".
4.12 Polarimeter 1 Demonstration of the optical activity of enantiomers, 4.13 Refractometer 1 Demonstration refractometric method of determination 4.14 pH meters 3 Preparation of buffer solutions, demonstration of buffer 5 Projection equipment:
5.1 Multimedia projector and 2 Demonstration of multimedia presentations, photo and overhead projectors: Demonstration slides during lectures and practical classes 5.3 “Semi-automatic bearing” 5.6 Device for demonstration Assigned to the morphological educational building. Demonstration of transparent films (overhead) and illustrative material at lectures, during UIRS and NIRS film projector.
6 Computer technology:
6.1 Departmental network of 1 Access to educational resources of the INTERNET (national and personal computers with international electronic databases on chemistry, biology and access to INTERNET medicine) for teachers of the department and students in educational and 6.2 Personal computers 8 Creation by teachers of the department of printed and electronic staff of the department didactic materials during educational and methodological work, 6.3 Computer class for 10 1 Programmed testing of students’ knowledge in practical classes, during tests and exams (current, 7 Educational tables:
1. Peptide bond.
2. Regularity of the structure of the polypeptide chain.
3. Types of bonds in a protein molecule.
4. Disulfide bond.
5. Species specificity of proteins.
6. Secondary structure of proteins.
7. Tertiary structure of proteins.
8. Myoglobin and hemoglobin.
9. Hemoglobin and its derivatives.
10. Blood plasma lipoproteins.
11. Types of hyperlipidemia.
12. Electrophoresis of proteins on paper.
13. Scheme of protein biosynthesis.
14. Collagen and tropocollagen.
15. Myosin and actin.
16. Vitamin deficiency RR (pellagra).
17. Vitamin B1 deficiency.
18. Vitamin deficiency C.
19. Vitamin deficiency A.
20. Vitamin deficiency D (rickets).
21. Prostaglandins are physiologically active derivatives of unsaturated fatty acids.
22. Neuroxins formed from catechalamines and indolamines.
23. Products of non-enzymatic reactions of dopamine.
24. Neuropeptides.
25. Polyunsaturated fatty acids.
26. Interaction of liposomes with the cell membrane.
27. Free oxidation (differences from tissue respiration).
28. PUFAs of the omega 6 and omega 3 families.
2 Sets of slides for various sections of the program 8.6 Interactive learning tools (Internet technologies), multimedia materials, Electronic libraries and textbook, photo and video materials 1 Interactive learning tools (Internet technologies) 2 Multimedia materials Stonik V.A. (TIBOH DSC SB RAS) “Natural compounds are the basis 5 Borodin E.A. (AGMA) “Human genome. Genomics, proteomics and Author's presentation 6 Pivovarova E.N (Institute of Cytology and Genetics, Siberian Branch of the Russian Academy of Medical Sciences) “The role of regulation of gene expression Author’s presentation of a person.”
3 Electronic libraries and textbooks:
2 MEDLINE. CD version of electronic databases on chemistry, biology and medicine.
3 Life Sciences. CD version of electronic databases on chemistry and biology.
4 Cambridge Scientific Abstracts. CD version of electronic databases on chemistry and biology.
5 PubMed - electronic database of the National Institute of Health http://www.ncbi.nlm.nih.gov/pubmed/ Organic chemistry. Digital library. (Compiled by N.F. Tyukavkina, A.I. Khvostova) - M., 2005.
Organic and general chemistry. Medicine. Lectures for students, course. (Electronic manual). M., 2005
4 Videos:
3 MES TIBOKH DSC FEB RAS CD
5 Photo and video materials:Author's photos and video materials of the head. department prof. E.A. Borodin about 1 universities of Uppsala (Sweden), Granada (Spain), medical schools of universities in Japan (Niigata, Osaka, Kanazawa, Hirosaki), Institute of Biomedical Chemistry of the Russian Academy of Medical Sciences, Institute of Physical Chemistry and Chemistry of the Ministry of Health of Russia, TIBOKHE DSC. FEB RAS.
8.1. Examples of current control test items (with standard answers) for lesson No. 4 “Acidity and basicity organic molecules"
1. Select the characteristic features of Bronsted-Lowry acids:
1. increase the concentration of hydrogen ions in aqueous solutions 2. increase the concentration of hydroxide ions in aqueous solutions 3. are neutral molecules and ions - proton donors 4. are neutral molecules and ions - proton acceptors 5. do not affect the reaction of the medium 2. Specify the factors , affecting the acidity of organic molecules:
1. electronegativity of the heteroatom 2. polarizability of the heteroatom 3. nature of the radical 4. ability to dissociate 5. solubility in water 3. Select the strongest Bronsted acids from the listed compounds:
1. alkanes 2. amines 3. alcohols 4. thiols 5. carboxylic acids 4. Indicate the characteristic features of organic compounds that have the properties of bases:
1. proton acceptors 2. proton donors 3. upon dissociation give hydroxyl ions 4. do not dissociate 5. basic properties determine reactivity 5. Select the weakest base from the given compounds:
1. ammonia 2. methylamine 3. phenylamine 4. ethylamine 5. propylamine 8.2 Examples of situational tasks of current control (with answer standards) 1. Determine the parent structure in the compound:
Solution. The choice of parent structure in the structural formula of an organic compound is regulated in the IUPAC substitutive nomenclature by a number of consistently applied rules (see Textbook, 1.2.1).
Each subsequent rule is applied only when the previous one does not allow making a clear choice. Compound I contains aliphatic and alicyclic fragments. According to the first rule, the structure with which the senior characteristic group is directly related is chosen as the parent structure. Of the two characteristic groups present in compound I (OH and NH), the hydroxyl group is the oldest. Therefore, the initial structure will be cyclohexane, which is reflected in the name of this compound - 4-aminomethylcyclohexanol.
2. The basis of a number of biologically important compounds and drugs is a condensed heterocyclic purine system, including pyrimidine and imidazole nuclei. What explains the increased resistance of purine to oxidation?
Solution. Aromatic compounds have high conjugation energy and thermodynamic stability. One of the manifestations of aromatic properties is resistance to oxidation, although “externally”
aromatic compounds have a high degree of unsaturation, which usually makes them prone to oxidation. To answer the question posed in the problem statement, it is necessary to establish whether purine belongs to aromatic systems.
According to the definition of aromaticity, a necessary (but not sufficient) condition for the emergence of a conjugated closed system is the presence in the molecule of a flat cyclic skeleton with a single electron cloud. In the purine molecule, all carbon and nitrogen atoms are in a state of sp2 hybridization, and therefore all the bonds lie in the same plane. Due to this, the orbitals of all atoms included in the cycle are located perpendicular to the skeletal plane and parallel to each other, which creates conditions for their mutual overlap with the formation of a single closed delocalized ti-electron system covering all the atoms of the cycle (circular conjugation).
Aromaticity is also determined by the number of -electrons, which must correspond to the formula 4/7 + 2, where n is a series of natural numbers O, 1, 2, 3, etc. (Hückel's rule). Each carbon atom and the pyridine nitrogen atoms in positions 1, 3 and 7 contribute one p-electron to the conjugated system, and the pyrrole nitrogen atom in position 9 contributes a lone pair of electrons. The conjugated purine system contains 10 electrons, which corresponds to Hückel's rule at n = 2.
Thus, the purine molecule has an aromatic character and its resistance to oxidation is associated with this.
The presence of heteroatoms in the purine cycle leads to uneven distribution of electron density. Pyridine nitrogen atoms exhibit an electron-withdrawing character and reduce the electron density on carbon atoms. In this regard, the oxidation of purine, generally considered as the loss of electrons by the oxidizing compound, will be even more difficult compared to benzene.
8.3 Test tasks for testing (one option in full with answer standards) 1.Name the organogenic elements:
7.Si 8.Fe 9.Cu 2.Indicate functional groups that have a Pi bond:
1.Carboxyl 2.amino group 3.hydroxyl 4.oxo group 5.carbonyl 3.Indicate the senior functional group:
1.-C=O 2.-SO3H 3.-CII 4.-COOH 5.-OH 4.What class of organic compounds does lactic acid CH3-CHOH-COOH, formed in tissues as a result of the anaerobic breakdown of glucose, belong to?
1.Carboxylic acids 2.Hydroxy acids 3.Amino acids 4.Keto acids 5.Name by substitution nomenclature the substance that is the main energy fuel of the cell and has the following structure:
CH2-CH -CH -CH -CH -C=O
I I III I
OH OH OH OH OH H
1. 2,3,4,5,6-pentahydroxyhexanal 2.6-oxohexanepnentanol 1,2,3,4, 3. Glucose 4. Hexose 5.1,2,3,4,5-pentahydroxyhexanal- 6. Indicate the characteristic features of conjugated systems:1. Equalization of the electron density of sigma and pi bonds 2. Stability and low reactivity 3. Instability and high reactivity 4. Contain alternating sigma and pi bonds 5. Pi bonds are separated by -CH2 groups 7. For which compounds characteristic Pi-Pi conjugation:
1. carotenes and vitamin A 2. pyrrole 3. pyridine 4. porphyrins 5. benzpyrene 8. Select substituents of the first kind, orienting to the ortho- and para-positions:
1.alkyl 2.- OH 3.- NH 4.- COOH 5.- SO3H 9. What effect does the -OH group have in aliphatic alcohols:
1. Positive inductive 2. Negative inductive 3. Positive mesomeric 4. Negative mesomeric 5. The type and sign of the effect depend on the position of the -OH group 10. Select the radicals that have a negative mesomeric effect 1. Halogens 2. Alkyl radicals 3. Amino group 4. Hydroxy group 5. Carboxy group 11. Select the characteristic features of Bronsted-Lowry acids:
1. increase the concentration of hydrogen ions in aqueous solutions 2. increase the concentration of hydroxide ions in aqueous solutions 3. are neutral molecules and ions - proton donors 4. are neutral molecules and ions - proton acceptors 5. do not affect the reaction of the medium 12. Specify the factors , affecting the acidity of organic molecules:
1. electronegativity of the heteroatom 2. polarizability of the heteroatom 3. nature of the radical 4. ability to dissociate 5. solubility in water 13. Select the strongest Bronsted acids from the listed compounds:
1. alkanes 2. amines 3. alcohols 4. thiols 5. carboxylic acids 14. Indicate the characteristic features of organic compounds that have the properties of bases:
1. proton acceptors 2. proton donors 3. upon dissociation they give hydroxyl ions 4. do not dissociate 5. basic properties determine reactivity 15. Select the weakest base from the given compounds:
1. ammonia 2. methylamine 3. phenylamine 4. ethylamine 5. propylamine 16. What features are used to classify reactions of organic compounds:
1. The mechanism of breaking a chemical bond 2. The final result of the reaction 3. The number of molecules participating in the stage that determines the rate of the entire process 4. The nature of the reagent attacking the bond 17. Select the active forms of oxygen:
1. singlet oxygen 2. peroxide diradical -O-O-Superoxide ion 4. hydroxyl radical 5. triplet molecular oxygen 18. Select the characteristic features of electrophilic reagents:
1.particles that carry a partial or complete positive charge 2.are formed by the homolytic cleavage of a covalent bond 3.particles that carry an unpaired electron 4.particles that carry a partial or complete negative charge 5.are formed by the heterolytic cleavage of a covalent bond 19.Select compounds for which Characteristic reactions are electrophilic substitution:
1. alkenes 2. arenes 3. alkadienes 4. aromatic heterocycles 5. alkanes 20. Indicate the biological role of free radical oxidation reactions:
1. phagocytic activity of cells 2. universal mechanism of destruction of cell membranes 3. self-renewal of cellular structures 4. play a decisive role in the development of many pathological processes 21. Select which classes of organic compounds are characterized by nucleophilic substitution reactions:
1. alcohols 2. amines 3. halogen derivatives of hydrocarbons 4. thiols 5. aldehydes 22. In what order does the reactivity of substrates decrease in nucleophilic substitution reactions:
1. halogen derivatives of hydrocarbons, amine alcohols 2. amine alcohols, halogen derivatives of hydrocarbons 3. amine alcohols, halogen derivatives of hydrocarbons 4. halogen derivatives of hydrocarbons, amine alcohols 23. Select polyhydric alcohols from the listed compounds:
1. ethanol 2. ethylene glycol 3. glycerol 4. xylitol 5. sorbitol 24. Choose what is characteristic of this reaction:
CH3-CH2OH --- CH2=CH2 + H2O 1. elimination reaction 2. intramolecular dehydration reaction 3. occurs in the presence of mineral acids when heated 4. occurs under normal conditions 5. intermolecular dehydration reaction 25. What properties appear when an organic substance is introduced into a molecule chlorine substances:
1. narcotic properties 2. lachrymatory (tearing) 3. antiseptic properties 26. Select the reactions characteristic of the SP2-hybridized carbon atom in oxo compounds:
1. nucleophilic addition 2. nucleophilic substitution 3. electrophilic addition 4. homolytic reactions 5. heterolytic reactions 27. In what order does the ease of nucleophilic attack of carbonyl compounds decrease:
1. aldehydes ketones anhydrides esters amides salts of carboxylic acids 2. ketones aldehydes anhydrides esters amides salts of carboxylic acids 3. anhydrides aldehydes ketones esters amides salts of carboxylic acids 28. Determine what is characteristic of this reaction:
1.qualitative reaction to aldehydes 2.aldehyde is a reducing agent, silver oxide (I) is an oxidizing agent 3.aldehyde is an oxidizing agent, silver oxide (I) is a reducing agent 4.redox reaction 5.occurs in an alkaline medium 6.characteristic of ketones 29 .Which of the following carbonyl compounds undergo decarboxylation to form biogenic amines?
1. carboxylic acids 2. amino acids 3. oxo acids 4. hydroxy acids 5. benzoic acid 30. How do acid properties change in the homologous series of carboxylic acids:
1. increase 2. decrease 3. do not change 31. Which of the proposed classes of compounds are heterofunctional:
1. hydroxy acids 2. oxo acids 3. amino alcohols 4. amino acids 5. dicarboxylic acids 32. Hydroxy acids include:
1. citric 2. butyric 3. acetoacetic 4. pyruvic 5. malic 33. Select medications - derivatives of salicylic acid:
1. paracetamol 2. phenacetin 3. sulfonamides 4. aspirin 5. PAS 34. Select drugs - p-aminophenol derivatives:
1. paracetamol 2. phenacetin 3. sulfonamides 4. aspirin 5. PAS 35. Select drugs - sulfanilic acid derivatives:
1. paracetamol 2. phenacetin 3. sulfonamides 4. aspirin 5. PASK 36. Select the main provisions of the theory of A.M. Butlerov:
1. carbon atoms are connected by simple and multiple bonds 2. carbon in organic compounds is tetravalent 3. the functional group determines the properties of the substance 4. carbon atoms form open and closed cycles 5. in organic compounds carbon is in a reduced form 37. Which isomers are classified as spatial:
1. chains 2. position of multiple bonds 3. functional groups 4. structural 5. configurational 38. Choose what is characteristic of the concept “conformation”:
1. the possibility of rotation around one or more sigma bonds 2. conformers are isomers 3. a change in the sequence of bonds 4. a change in the spatial arrangement of substituents 5. a change in the electronic structure 39. Choose the similarity between enantiomers and diastereomers:
1. have the same physicochemical properties 2. are able to rotate the plane of polarization of light 3. are not able to rotate the plane of polarization of light 4. are stereoisomers 5. are characterized by the presence of a center of chirality 40. Select the similarity between configurational and conformational isomerism:
1. Isomerism is associated with different positions in space of atoms and groups of atoms 2. Isomerism is due to the rotation of atoms or groups of atoms around a sigma bond 3. Isomerism is due to the presence of a center of chirality in the molecule 4. Isomerism is due to different arrangements of substituents relative to the pi bond plane.
41.Name the heteroatoms that make up biologically important heterocycles:
1.nitrogen 2.phosphorus 3.sulfur 4.carbon 5.oxygen 42.Indicate the 5-membered heterocycle that is part of porphyrins:
1.pyrrolidine 2.imidazole 3.pyrrole 4.pyrazole 5.furan 43.Which heterocycle with one heteroatom is part of nicotinic acid:
1. purine 2. pyrazole 3. pyrrole 4. pyridine 5. pyrimidine 44. Name the final product of purine oxidation in the body:
1. hypoxanthine 2. xanthine 3. uric acid 45. Specify opium alkaloids:
1. strychnine 2. papaverine 4. morphine 5. reserpine 6. quinine 6. What oxidation reactions are characteristic of the human body:
1.dehydrogenation 2.addition of oxygen 3.donation of electrons 4.addition of halogens 5.interaction with potassium permanganate, nitric and perchloric acids 47.What determines the degree of oxidation of a carbon atom in organic compounds:
1. the number of its bonds with atoms of elements more electronegative than hydrogen 2. the number of its bonds with oxygen atoms 3. the number of its bonds with hydrogen atoms 48. What compounds are formed during the oxidation of the primary carbon atom?
1. primary alcohol 2. secondary alcohol 3. aldehyde 4. ketone 5. carboxylic acid 49. Determine what is characteristic of oxidase reactions:
1. oxygen is reduced to water 2. oxygen is included in the composition of the oxidized molecule 3. oxygen goes to the oxidation of hydrogen split off from the substrate 4. reactions have an energetic value 5. reactions have a plastic value 50. Which of the proposed substrates is oxidized more easily in the cell and why?
1. glucose 2. fatty acid 3. contains partially oxidized carbon atoms 4. contains fully hydrogenated carbon atoms 51. Select aldoses:
1. glucose 2. ribose 3. fructose 4. galactose 5. deoxyribose 52. Select the reserve forms of carbohydrates in a living organism:
1. fiber 2. starch 3. glycogen 4. hyaluric acid 5. sucrose 53. Select the most common monosaccharides in nature:
1. trioses 2. tetroses 3. pentoses 4. hexoses 5. heptoses 54. Select amino sugars:
1. beta-ribose 2. glucosamine 3. galactosamine 4. acetylgalactosamine 5. deoxyribose 55. Select the products of monosaccharide oxidation:
1. glucose-6-phosphate 2. glyconic (aldonic) acids 3. glycuronic (uronic) acids 4. glycosides 5. esters 56. Select disaccharides:
1. maltose 2. fiber 3. glycogen 4. sucrose 5. lactose 57. Select homopolysaccharides:
1. starch 2. cellulose 3. glycogen 4. dextran 5. lactose 58. Select which monosaccharides are formed during the hydrolysis of lactose:
1.beta-D-galactose 2.alpha-D-glucose 3.alpha-D-fructose 4.alpha-D-galactose 5.alpha-D-deoxyribose 59. Choose what is characteristic of cellulose:
1. linear, plant polysaccharide 2. structural unit is beta-D-glucose 3. necessary for normal nutrition, is a ballast substance 4. the main carbohydrate in humans 5. does not break down in the gastrointestinal tract 60. Select the carbohydrate derivatives that make up muramin:
1.N-acetylglucosamine 2.N-acetylmuramic acid 3.glucosamine 4.glucuronic acid 5.ribulose-5-phosphate 61.Choose the correct statements from the following: Amino acids are...
1. compounds containing both amino and hydroxy groups in the molecule 2. compounds containing hydroxyl and carboxyl groups 3. are derivatives of carboxylic acids in the radical of which hydrogen is replaced by an amino group 4. compounds containing oxo and carboxyl groups in the molecule 5. compounds containing hydroxy and aldehyde groups 62. How are amino acids classified?
1. by the chemical nature of the radical 2. by physicochemical properties 3. by the number of functional groups 4. by the degree of unsaturation 5. by the nature of additional functional groups 63. Select an aromatic amino acid:
1. glycine 2. serine 3. glutamic 4. phenylalanine 5. methionine 64. Select an amino acid that exhibits acidic properties:
1. leucine 2. tryptophan 3. glycine 4. glutamic acid 5. alanine 65. Select a basic amino acid:
1. serine 2. lysine 3. alanine 4. glutamine 5. tryptophan 66. Select purine nitrogenous bases:
1. thymine 2. adenine 3. guanine 4. uracil 5. cytosine 67. Select pyrimidine nitrogenous bases:
1.uracil 2.thymine 3.cytosine 4.adenine 5.guanine 68.Select the components of the nucleoside:
1.purine nitrogenous bases 2.pyrimidine nitrogenous bases 3.ribose 4.deoxyribose 5.phosphoric acid 69.Indicate the structural components of nucleotides:
1. purine nitrogenous bases 2. pyrimidine nitrogenous bases 3. ribose 4. deoxyribose 5. phosphoric acid 70. Indicate the distinctive features of DNA:
1. formed by one polynucleotide chain 2. formed by two polynucleotide chains 3. contains ribose 4. contains deoxyribose 5. contains uracil 6. contains thymine 71. Select saponifiable lipids:
1. neutral fats 2. triacylglycerols 3. phospholipids 4. sphingomyelins 5. steroids 72. Select unsaturated fatty acids:
1. palmitic 2. stearic 3. oleic 4. linoleic 5. arachidonic 73. Specify the characteristic composition of neutral fats:
1.mericyl alcohol + palmitic acid 2.glycerol + butyric acid 3.sphingosine + phosphoric acid 4.glycerol + higher carboxylic acid + phosphoric acid 5.glycerol + higher carboxylic acids 74. Choose what function phospholipids perform in the human body:
1. regulatory 2. protective 3. structural 4. energetic 75. Select glycolipids:
1.phosphatidylcholine 2.cerebrosides 3.sphingomyelins 4.sulfatides 5.gangliosides
ANSWERS TO TEST TASKS
8.4 List of practical skills and tasks (in full) required for passing 1. The ability to classify organic compounds according to the structure of the carbon skeleton and 2. The ability to draw up formulas by name and name typical representatives of biologically important substances and drugs by structural formula.3. The ability to isolate functional groups, acidic and basic centers, conjugated and aromatic fragments in molecules to determine chemical behavior 4. The ability to predict the direction and result of organic chemical transformations 5. Possession of the skills of independent work with educational, scientific and reference literature; conduct a search and draw general conclusions.
6. Possession of skills in handling chemical glassware.
7. Possession of safe work skills in a chemical laboratory and the ability to handle caustic, poisonous, highly volatile organic compounds, work with burners, alcohol lamps and electric heating devices.
1. Subject and tasks of bioorganic chemistry. Implications in medical education.
2. The elemental composition of organic compounds, as the reason for their compliance with biological processes.
3. Classification of organic compounds. Classes, general formulas, functional groups, individual representatives.
4. Nomenclature of organic compounds. Trivial names. Substitute IUPAC nomenclature.
5. Main functional groups. Parental structure. Deputies. Seniority of groups, deputies. Names of functional groups and substituents as prefixes and endings.
6. Theoretical foundations of the structure of organic compounds. Theory of A.M. Butlerov.
Structural formulas. Structural isomerism. Chain and position isomers.
7. Spatial structure of organic compounds. Stereochemical formulas.
Molecular models. The most important concepts in stereochemistry are the configuration and conformation of organic molecules.
8. Conformations of open chains - eclipsed, inhibited, oblique. Energy and reactivity of different conformations.
9. Conformations of cycles using the example of cyclohexane (chair and bath). Axial and equatorial connections.
10. Mutual influence of atoms in molecules of organic compounds. Its causes, types of manifestation. Influence on the reactivity of molecules.
11.Pairing. Conjugate systems, conjugate connections. Pi-pi conjugation in dienes. Conjugation energy. Stability of coupled systems (vitamin A).
12. Pairing in arenas (pi-pi pairing). Aromaticity. Hückel's rule. Benzene, naphthalene, phenanthrene. Reactivity of the benzene ring.
13. Conjugation in heterocycles (p-pi and pi-pi conjugation using the example of pyrrole and pyridine).
Stability of heterocycles - biological significance using the example of tetrapyrrole compounds.
14.Polarization of bonds. Causes. Polarization in alcohols, phenols, carbonyl compounds, thiols. Influence on the reactivity of molecules.\ 15.Electronic effects. Inductive effect in molecules containing sigma bonds. Sign of the inductive effect.
16.Mesomeric effect in open chains with conjugated pi bonds using the example of 1,3 butadiene.
17.Mesomeric effect in aromatic compounds.
18.Electron-donating and electron-withdrawing substituents.
19. Deputies of the 1st and 2nd kind. Rule of orientation in the benzene ring.
20.Acidity and basicity of organic compounds. Brendstet-Lowry acids and bases.
Acid-base pairs are conjugate acids and bases. Ka and pKa are quantitative characteristics of the acidity of organic compounds. The importance of acidity for the functional activity of organic molecules.
21.Acidity of various classes of organic compounds. Factors that determine the acidity of organic compounds are the electronegativity of the non-metal atom bonded to hydrogen, the polarizability of the non-metal atom, the nature of the radical bonded to the non-metal atom.
22.Organic bases. Amines. Reason for basicity. The influence of radicals on the basicity of aliphatic and aromatic amines.
23. Classification of reactions of organic compounds according to their mechanism. Concepts of homolytic and heterolytic reactions.
24. Radical substitution reactions in alkanes. Free radical oxidation in living organisms. Reactive oxygen species.
25. Electrophilic addition in alkenes. Formation of Pi-complexes, carbocations. Reactions of hydration, hydrogenation.
26.Electrophilic substitution in the aromatic ring. Formation of intermediate sigma complexes. Benzene bromination reaction.
27.Nucleophilic substitution in alcohols. Reactions of dehydration, oxidation of primary and secondary alcohols, formation of esters.
28.Nucleophilic addition of carbonyl compounds. Biologically important reactions of aldehydes: oxidation, formation of hemiacetals when interacting with alcohols.
29.Nucleophilic substitution in carboxylic acids. Biologically important reactions of carboxylic acids.
30. Oxidation of organic compounds, biological significance. The degree of oxidation of carbon in organic molecules. Oxidability of different classes of organic compounds.
31.Energetic oxidation. Oxidase reactions.
32.Non-energetic oxidation. Oxygenase reactions.
33. The role of free radical oxidation in the bactericidal action of phagocytic cells.
34. Restoration of organic compounds. Biological significance.
35.Multifunctional compounds. Polyhydric alcohols - ethylene glycol, glycerin, xylitol, sorbitol, inositol. Biological significance. Biologically important reactions of glycerol are oxidation and formation of esters.
36.Dibasic dicarboxylic acids: oxalic, malonic, succinic, glutaric.
The conversion of succinic acid to fumaric acid is an example of biological dehydrogenation.
37. Amines. Classification:
By the nature of the radical (aliphatic and aromatic); -by the number of radicals (primary, secondary, tertiary, quaternary ammonium bases); -by the number of amino groups (mono- and diamines-). Diamines: putrescine and cadaverine.
38. Heterofunctional compounds. Definition. Examples. Features of the manifestation of chemical properties.
39. Amino alcohols: ethanolamine, choline, acetylcholine. Biological significance.
40.Hydroxyacids. Definition. General formula. Classification. Nomenclature. Isomerism.
Representatives of monocarboxylic hydroxy acids: lactic, beta-hydroxybutyric, gamma-xibutyric;
dicarbonate: apple, wine; tricarboxylic: lemon; aromatic: salicylic.
41. Chemical properties of hydroxy acids: by carboxyl, by hydroxyl group, dehydration reactions of alpha, beta and gamma isomers, difference in reaction products (lactides, unsaturated acids, lactones).
42.Stereoisomerism. Enantiomers and diastereomers. Chirality of molecules of organic compounds as a cause of optical isomerism.
43. Enantiomers with one chirality center (lactic acid). Absolute and relative configuration of enantiomers. Oxyacid key. D and L glyceraldehyde. D and L isomers.
Racemates.
44. Enantiomers with several centers of chirality. Tartaric and mesotartaric acids.
45.Stereoisomerism and biological activity of stereoisomers.
46.Cis-and trans-isomerism using the example of fumaric and maleic acids.
47.Oxoacids. Definition. Biologically important representatives: pyruvic acid, acetoacetic acid, oxaloacetic acid. Ketoenol tautomerism using the example of pyruvic acid.
48. Amino acids. Definition. General formula. Isomers of amino group position (alpha, beta, gamma). Biological significance of alpha amino acids. Representatives of beta-, gamma- and other isomers (beta-aminopropionic, gamma-aminobutyric, epsilonaminocaproic). Dehydration reaction of gamma isomers with the formation of cyclic lactones.
49. Heterofunctional benzene derivatives as the basis of medicines. Derivatives of p-aminobenzoic acid - PABA (folic acid, anesthesin). PABA antagonists are sulfanilic acid derivatives (sulfonamides - streptocide).
50. Heterofunctional benzene derivatives - medicines. Raminophenol derivatives (paracetamol), salicylic acid derivatives (acetylsalicylic acid). Raminosalicylic acid - PAS.
51.Biologically important heterocycles. Definition. Classification. Features of structure and properties: conjugation, aromaticity, stability, reactivity. Biological significance.
52. Five-membered heterocycles with one heteroatom and their derivatives. Pyrrole (porphin, porphyrins, heme), furan (medicines), thiophene (biotin).
53. Five-membered heterocycles with two heteroatoms and their derivatives. Pyrazole (5-oxo derivatives), imidazole (histidine), thiazole (vitamin B1-thiamine).
54. Six-membered heterocycles with one heteroatom and their derivatives. Pyridine (nicotinic acid - participation in redox reactions, vitamin B6-pyridoxal), quinoline (5-NOK), isoquinoline (alkaloids).
55. Six-membered heterocycles with two heteroatoms. Pyrimidine (cytosine, uracil, thymine).
56.Fused heterocycles. Purine (adenine, guanine). Purine oxidation products hypoxanthine, xanthine, uric acid).
57. Alkaloids. Definition and general characteristics. The structure of nicotine and caffeine.
58.Carbohydrates. Definition. Classification. Functions of carbohydrates in living organisms.
59.Monosugars. Definition. Classification. Representatives.
60.Pentoses. Representatives are ribose and deoxyribose. Structure, open and cyclic formulas. Biological significance.
61.Hexoses. Aldoses and ketoses. Representatives.
62.Open formulas of monosaccharides. Determination of stereochemical configuration. Biological significance of the configuration of monosaccharides.
63. Formation of cyclic forms of monosaccharides. Glycosidic hydroxyl. Alpha and beta anomers. Haworth's formulas.
64. Derivatives of monosaccharides. Phosphorus esters, glyconic and glycuronic acids, amino sugars and their acetyl derivatives.
65. Maltose. Composition, structure, hydrolysis and significance.
66.Lactose. Synonym. Composition, structure, hydrolysis and significance.
67.Sucrose. Synonyms. Composition, structure, hydrolysis and significance.
68. Homopolysaccharides. Representatives. Starch, structure, properties, hydrolysis products, significance.
69.Glycogen. Structure, role in the animal organism.
70. Fiber. Structure, role in plants, significance for humans.
72. Heteropolysaccharides. Synonyms. Functions. Representatives. Structural features: dimer units, composition. 1,3- and 1,4-glycosidic bonds.
73.Hyaluronic acid. Composition, structure, properties, significance in the body.
74.Chondroitin sulfate. Composition, structure, significance in the body.
75.Muramin. Composition, meaning.
76. Alpha amino acids. Definition. General formula. Nomenclature. Classification. Individual representatives. Stereoisomerism.
77. Chemical properties of alpha amino acids. Amphotericity, reactions of decarboxylation, deamination, hydroxylation in the radical, formation of a peptide bond.
78.Peptides. Individual peptides. Biological role.
79. Squirrels. Functions of proteins. Levels of structure.
80. Nitrogen bases of nucleic acids - purines and pyrimidines. Modified nitrogenous bases - antimetabolites (fluorouracil, mercaptopurine).
81.Nucleosides. Nucleoside antibiotics. Nucleotides. Mononucleotides in the composition of nucleic acids and free nucleotides are coenzymes.
82. Nucleic acids. DNA and RNA. Biological significance. Formation of phosphodiester bonds between mononucleotides. Levels of nucleic acid structure.
83. Lipids. Definition. Biological role. Classification.
84.Higher carboxylic acids - saturated (palmitic, stearic) and unsaturated (oleic, linoleic, linolenic and arachidonic).
85. Neutral fats - acylglycerols. Structure, meaning. Animal and vegetable fats.
Hydrolysis of fats - products, meaning. Hydrogenation of vegetable oils, artificial fats.
86. Glycerophospholipids. Structure: phosphatidic acid and nitrogenous bases.
Phosphatidylcholine.
87. Sphingolipids. Structure. Sphingosine. Sphingomyelin.
88.Steroids. Cholesterol - structure, meaning, derivatives: bile acids and steroid hormones.
89.Terpenes and terpenoids. Structure and biological significance. Representatives.
90.Fat-soluble vitamins. General characteristics.
91. Anesthesia. Diethyl ether. Chloroform. Meaning.
92. Drugs that stimulate metabolic processes.
93. Sulfonamides, structure, significance. White streptocid.
94. Antibiotics.
95. Anti-inflammatory and antipyretic drugs. Paracetamol. Structure. Meaning.
96. Antioxidants. Characteristic. Meaning.
96. Thiols. Antidotes.
97. Anticoagulants. Characteristic. Meaning.
98. Barbiturates. Characteristic.
99. Analgesics. Meaning. Examples. Acetylsalicylic acid (aspirin).
100. Antiseptics. Meaning. Examples. Furacilin. Characteristic. Meaning.
101. Antiviral drugs.
102. Diuretics.
103. Means for parenteral nutrition.
104. PABC, PASK. Structure. Characteristic. Meaning.
105. Iodoform. Xeroform.Meaning.
106. Poliglyukin. Characteristic. Value 107.Formalin. Characteristic. Meaning.
108. Xylitol, sorbitol. Structure, meaning.
109. Resorcinol. Structure, meaning.
110. Atropine. Meaning.
111. Caffeine. Structure. Value 113. Furacilin. Furazolidone. Characteristic.Value.
114. GABA, GHB, succinic acid.. Structure. Meaning.
115. Nicotinic acid. Structure, meaning
| year, a seminar was held on Improving mechanisms for regulating the labor market in the Republic of Sakha (Yakutia) with international participation, organized by the Center for Strategic Studies of the Republic of Sakha (Yakutia). Representatives of leading scientific institutions abroad, the Russian Federation, the Far Eastern Federal..." took part in the seminar. “Novosibirsk State Academy of Water Transport Discipline code: F.02, F.03 Materials Science. Technology of structural materials Work program for specialties: 180400 Electric drive and automation of industrial installations and technological complexes and 240600 Operation of ship electrical equipment and automation Novosibirsk 2001 Work program compiled by Associate Professor S.V. Gorelov on the basis of the State educational standard of higher professional..." "RUSSIAN STATE UNIVERSITY OF OIL AND GAS named after I.M. Gubkina Approved by the vice-rector for scientific work prof. A.V. Muradov March 31, 2014 PROGRAM of the entrance test in the direction of 06.15.01 - Mechanical Engineering for applicants to graduate school at the Russian State University of Oil and Gas named after I.M. Gubkin in the 2014/2015 academic year. year Moscow 2014 The entrance test program for the direction 06/15/01 Mechanical Engineering was developed on the basis of the requirements established by the passports of scientific specialties (02/05/04,..." “Appendix 5A: Work program of the special discipline Psychology of Mental Development FEDERAL STATE BUDGET EDUCATIONAL INSTITUTION OF HIGHER PROFESSIONAL EDUCATION PYATIGORSK STATE LINGUISTIC UNIVERSITY Approved by the Vice-Rector for Scientific Work and Development of Intellectual Potential of the University, Professor Z.A. Zavrumov _2012 Postgraduate studies in the specialty 19.00.07 Pedagogical psychology branch of science: 19.00.00 Psychological sciences Department...” “Ministry of Education and Science of the Kabardino-Balkaria State Educational Institution of Secondary Vocational Education Kabardino-Balkarian Automobile and Highway College Approved by: Director of the State Educational Institution of Secondary Professional Education KBADK M.A. Abregov 2013 Training program for qualified workers, employees by profession 190631.01.01 Auto mechanic Qualification Car repair mechanic. Car driver, gas station operator training form - full-time Nalchik, 2013 CONTENTS 1. CHARACTERISTICS..." “is expounded an essence of the ischemic heart disease mathematical model based on traditional view on organs’ blood supply mechanism, that has been worked out in “Medical Scientific Center” joint-venture (Novgorod). 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“ … There were so many amazing incidents,
That nothing seemed at all possible to her now ”
L. Carroll "Alice in Wonderland"
Bioorganic chemistry developed on the border between two sciences: chemistry and biology. Currently, medicine and pharmacology have joined them. All four of these sciences use modern methods of physical research, mathematical analysis and computer modeling.
In 1807 J.Ya. Berzelius proposed that substances like olive oil or sugar, which are common in living nature, should be called organic.
By this time, many natural compounds were already known, which later began to be defined as carbohydrates, proteins, lipids, and alkaloids.
In 1812, a Russian chemist K.S. Kirchhoff converted starch by heating it with acid into sugar, later called glucose.
In 1820, a French chemist A. Braconno, by treating protein with gelatin, he obtained the substance glycine, which belongs to a class of compounds that later Berzelius named amino acids.
The birth date of organic chemistry can be considered the work published in 1828 F. Velera, who was the first to synthesize a substance of natural origin – urea- from the inorganic compound ammonium cyanate.
In 1825, the physicist Faraday isolated benzene from a gas that was used to illuminate the city of London. The presence of benzene may explain the smoky flames of London lamps.
In 1842 N.N. Zinin carried out synthe z aniline,
In 1845 A.V. Kolbe, a student of F. Wöhler, synthesized acetic acid - undoubtedly a natural organic compound - from starting elements (carbon, hydrogen, oxygen)
In 1854 P. M. Bertlot heated glycerin with stearic acid and obtained tristearin, which turned out to be identical to the natural compound isolated from fats. Further P.M. Berthelot took other acids that were not isolated from natural fats and obtained compounds very similar to natural fats. With this, the French chemist proved that it is possible to obtain not only analogues of natural compounds, but also create new ones, similar and at the same time different from natural ones.
Many major achievements in organic chemistry in the second half of the 19th century are associated with the synthesis and study of natural substances.
In 1861, the German chemist Friedrich August Kekule von Stradonitz (always called simply Kekule in scientific literature) published a textbook in which he defined organic chemistry as the chemistry of carbon.
During the period 1861-1864. Russian chemist A.M. Butlerov created a unified theory of the structure of organic compounds, which made it possible to transfer all existing achievements to a single scientific basis and opened the way to the development of the science of organic chemistry.
During the same period, D.I. Mendeleev. known throughout the world as a scientist who discovered and formulated the periodic law of changes in the properties of elements, published the textbook “Organic Chemistry”. We have at our disposal its 2nd edition (corrected and expanded, Publication of the Partnership “Public Benefit”, St. Petersburg, 1863. 535 pp.)
In his book, the great scientist clearly defined the connection between organic compounds and vital processes: “We can reproduce many of the processes and substances that are produced by organisms artificially, outside the body. Thus, protein substances, being destroyed in animals under the influence of oxygen absorbed by the blood, are converted into ammonium salts, urea, mucus sugar, benzoic acid and other substances usually excreted in urine... Taken separately, each vital phenomenon is not the result of some special force , but occurs according to the general laws of nature" At that time, bioorganic chemistry and biochemistry had not yet emerged as
independent directions, at first they were united physiological chemistry, but gradually they grew on the basis of all achievements into two independent sciences.
The science of bioorganic chemistry studies connection between the structure of organic substances and their biological functions, using mainly methods of organic, analytical, physical chemistry, as well as mathematics and physics
The main distinguishing feature of this subject is the study of the biological activity of substances in connection with the analysis of their chemical structure
Objects of study of bioorganic chemistry: biologically important natural biopolymers - proteins, nucleic acids, lipids, low molecular weight substances - vitamins, hormones, signal molecules, metabolites - substances involved in energy and plastic metabolism, synthetic drugs.
The main tasks of bioorganic chemistry include:
1. Development of methods for isolating and purifying natural compounds, using medical methods to assess the quality of a drug (for example, a hormone based on the degree of its activity);
2. Determination of the structure of a natural compound. All methods of chemistry are used: determination of molecular weight, hydrolysis, analysis of functional groups, optical research methods;
3. Development of methods for the synthesis of natural compounds;
4. Study of the dependence of biological action on structure;
5. Clarification of the nature of biological activity, molecular mechanisms of interaction with various cell structures or with its components.
The development of bioorganic chemistry over the decades is associated with the names of Russian scientists: D.I.Mendeleeva, A.M. Butlerov, N.N. Zinin, N.D. Zelinsky A.N. Belozersky N.A. Preobrazhensky M.M. Shemyakin, Yu.A. Ovchinnikova.
The founders of bioorganic chemistry abroad are scientists who have made many major discoveries: the structure of the secondary structure of proteins (L. Pauling), the complete synthesis of chlorophyll, vitamin B 12 (R. Woodward), the use of enzymes in the synthesis of complex organic substances. including gene (G. Koran) and others
In the Urals in Yekaterinburg in the field of bioorganic chemistry from 1928 to 1980. worked as the head of the department of organic chemistry of UPI, academician I.Ya. Postovsky, known as one of the founders in our country of the scientific direction of search and synthesis of drugs and the author of a number of drugs (sulfonamides, antitumor, anti-radiation, anti-tuberculosis). His research is continued by students who work under the leadership of academicians O.N. Chupakhin, V.N. Charushin at USTU-UPI and at the Institute of Organic Synthesis named after. AND I. Postovsky Russian Academy of Sciences.
Bioorganic chemistry is closely related to the tasks of medicine and is necessary for the study and understanding of biochemistry, pharmacology, pathophysiology, and hygiene. All the scientific language of bioorganic chemistry, the notation adopted and the methods used are no different from the organic chemistry you studied in school
Bioorganic chemistry is a science that studies the structure and properties of substances involved in life processes in direct connection with the knowledge of their biological functions.
Bioorganic chemistry is the science that studies the structure and reactivity of biologically significant compounds. The subject of bioorganic chemistry is biopolymers and bioregulators and their structural elements.
Biopolymers include proteins, polysaccharides (carbohydrates) and nucleic acids. This group also includes lipids, which are not BMCs, but are usually associated with other biopolymers in the body.
Bioregulators are compounds that chemically regulate metabolism. These include vitamins, hormones, and many synthetic compounds, including medicinal substances.
Bioorganic chemistry is based on the ideas and methods of organic chemistry.
Without knowledge of the general principles of organic chemistry, it is difficult to study bioorganic chemistry. Bioorganic chemistry is closely related to biology, biological chemistry, and medical physics.
The set of reactions occurring under the conditions of an organism is called metabolism.
Substances formed during metabolism are called - metabolites.
Metabolism has two directions:
Catabolism is the reaction of the breakdown of complex molecules into simpler ones.
Anabolism is the process of synthesizing complex molecules from simpler substances using energy.
The term biosynthesis is applied to a chemical reaction IN VIVO (in the body), IN VITRO (outside the body)
There are antimetabolites - competitors of metabolites in biochemical reactions.
Conjugation as a factor in increasing the stability of molecules. Mutual influence of atoms in molecules of organic compounds and methods of its transmission
Lecture outline:
Pairing and its types:
p, p - pairing,
r,p - conjugation.
Conjugation energy.
Open circuit coupled systems.
Vitamin A, carotenes.
Conjugation in radicals and ions.
Coupled closed-circuit systems. Aromaticity, aromaticity criteria, heterocyclic aromatic compounds.
Covalent bond: non-polar and polar.
Inductive and mesomeric effects. EA and ED are substitutes.
The main type of chemical bonds in organic chemistry are covalent bonds. In organic molecules, atoms are connected by s and p bonds.
Atoms in molecules of organic compounds are connected by covalent bonds, which are called s and p bonds.
Single s - bond in SP 3 - hybridized state is characterized by l - length (C-C 0.154 nm), E-energy (83 kcal/mol), polarity and polarizability. For example:
A double bond is characteristic of unsaturated compounds, in which, in addition to the central s-bond, there is also an overlap perpendicular to the s-bond, which is called a π-bond).
Double bonds are localized, that is, the electron density covers only 2 nuclei of the bonded atoms.
Most often you and I will deal with conjugated systems. If double bonds alternate with single bonds (and in the general case, an atom connected to a double bond has a p-orbital, then the p-orbitals of neighboring atoms can overlap each other, forming a common p-electron system). Such systems are called conjugated or delocalized . For example: butadiene-1,3
p, p - conjugate systems
All atoms in butadiene are in the SP 2 hybridized state and lie in the same plane (Pz is not a hybrid orbital). Рz – orbitals are parallel to each other. This creates conditions for their mutual overlap. The overlap of the Pz orbital occurs between C-1 and C-2 and C-3 and C-4, as well as between C-2 and C-3, that is, it occurs delocalized covalent bond. This is reflected in changes in bond lengths in the molecule. The length of the bond between C-1 and C-2 is increased, and between C-2 and C-3 is shortened, compared to a single bond.
l-C -С, 154 nm l С=С 0.134 nm
l С-N 1.147 nm l С =O 0.121 nm
r, p - pairing
An example of a p, π conjugated system is a peptide bond.
r, p - conjugate systems
The C=0 double bond is extended to 0.124 nm compared to the usual length of 0.121, and the C–N bond becomes shorter and becomes 0.132 nm compared to 0.147 nm in the normal case. That is, the process of electron delocalization leads to equalization of bond lengths and a decrease in the internal energy of the molecule. However, ρ,p – conjugation occurs in acyclic compounds, not only when alternating = bonds with single C-C bonds, but also when alternating with a heteroatom:
An X atom with a free p-orbital may be located near the double bond. Most often, these are O, N, S heteroatoms and their p-orbitals that interact with p-bonds, forming p, p-conjugation.
For example:
CH 2 = CH – O – CH = CH 2
Conjugation can occur not only in neutral molecules, but also in radicals and ions:
Based on the above, in open systems, pairing occurs under the following conditions:
All atoms participating in the conjugated system are in the SP 2 - hybridized state.
Pz – the orbitals of all atoms are perpendicular to the s-skeleton plane, that is, parallel to each other.
When a conjugated multicenter system is formed, the bond lengths are equalized. There are no “pure” single and double bonds here.
Delocalization of p-electrons in a conjugated system is accompanied by the release of energy. The system moves to a lower energy level, becomes more stable, more stable. Thus, the formation of a conjugated system in the case of butadiene - 1,3 leads to the release of energy in the amount of 15 kJ/mol. It is due to conjugation that the stability of allylic-type ion radicals and their prevalence in nature increases.
The longer the conjugation chain, the greater the release of energy of its formation.
This phenomenon is quite widespread in biologically important compounds. For example:
We will constantly encounter issues of thermodynamic stability of molecules, ions, and radicals in the course of bioorganic chemistry, which includes a number of ions and molecules widespread in nature. For example: 
Closed-loop coupled systems
Aromaticity. In cyclic molecules, under certain conditions, a conjugated system can arise. An example of a p, p - conjugated system is benzene, where the p - electron cloud covers carbon atoms, such a system is called - aromatic.
The energy gain due to conjugation in benzene is 150.6 kJ/mol. Therefore, benzene is thermally stable up to a temperature of 900 o C.
The presence of a closed electron ring was proven using NMR. If a benzene molecule is placed in an external magnetic field, an inductive ring current occurs.
Thus, the criterion for aromaticity formulated by Hückel is:
the molecule has a cyclic structure;
all atoms are in SP 2 – hybridized state;
there is a delocalized p - electron system containing 4n + 2 electrons, where n is the number of cycles.
For example: 
A special place in bioorganic chemistry is occupied by the question aromaticity of heterocyclic compounds.
In cyclic molecules containing heteroatoms (nitrogen, sulfur, oxygen), a single p-electron cloud is formed with the participation of p-orbitals of carbon atoms and a heteroatom.
Five-membered heterocyclic compounds
The aromatic system is formed by the interaction of 4 p-orbitals C and one orbital of a heteroatom, which has 2 electrons. Six p electrons form the aromatic skeleton. Such a conjugated system is electronically redundant. In pyrrole, the N atom is in the SP 2 hybridized state.
Pyrrole is part of many biologically important substances. Four pyrrole rings form porphine, an aromatic system with 26 p - electrons and high conjugation energy (840 kJ/mol)
The porphin structure is part of hemoglobin and chlorophyll 
Six-membered heterocyclic compounds
The aromatic system in the molecules of these compounds is formed by the interaction of five p-orbitals of carbon atoms and one p-orbital of a nitrogen atom. Two electrons in two SP 2 orbitals are involved in the formation of s - bonds with the carbon atoms of the ring. The P orbital with one electron is included in the aromatic skeleton. SP 2 – an orbital with a lone pair of electrons lies in the s-skeleton plane.
The electron density in pyrimidine is shifted towards N, that is, the system is depleted of p - electrons, it is electron deficient.
Many heterocyclic compounds may contain one or more heteroatoms 
Pyrrole, pyrimidine, and purine nuclei are part of many biologically active molecules.
Mutual influence of atoms in molecules of organic compounds and methods of its transmission
As already noted, bonds in molecules of organic compounds are carried out due to s and p bonds; electron density is evenly distributed between bonded atoms only when these atoms are the same or close in electronegativity. Such connections are called non-polar. 
CH 3 -CH 2 →CI polar bond
More often in organic chemistry we deal with polar bonds.
If the electron density is shifted towards a more electronegative atom, then such a bond is called polar. Based on the values of bond energy, the American chemist L. Pauling proposed a quantitative characteristic of the electronegativity of atoms. Below is the Pauling scale.
Na Li H S C J Br Cl N O F
0,9 1,0 2,1 2,52,5 2,5 2,8 3,0 3,0 3,5 4,0
Carbon atoms in different states of hybridization differ in electronegativity. Therefore, s - the bond between SP 3 and SP 2 hybridized atoms - is polar 
Inductive effect
The transfer of electron density through the mechanism of electrostatic induction along a chain of s-bonds is called by induction, the effect is called inductive and is denoted by J. The effect of J, as a rule, is attenuated through three bonds, but closely located atoms experience a rather strong influence of the nearby dipole.
Substituents that shift the electron density along the s-bond chain in their direction exhibit a -J – effect, and vice versa +J effect. 
An isolated p-bond, as well as a single p-electron cloud of an open or closed conjugated system, can easily be polarized under the influence of EA and ED substituents. In these cases, the inductive effect is transferred to the p-connection, therefore denoted by Jp. 
Mesomeric effect (conjugation effect)
The redistribution of electron density in a conjugated system under the influence of a substituent that is a member of this conjugated system is called mesomeric effect(M-effect). 
In order for a substituent to be part of a conjugated system, it must have either a double bond (p,p conjugation) or a heteroatom with a lone pair of electrons (r,p conjugation). M – the effect is transmitted through the coupled system without attenuation.
Substituents that lower the electron density in a conjugated system (displaced electron density in its direction) exhibit an -M effect, and substituents that increase the electron density in a conjugated system exhibit a +M effect.
Electronic effects of substituents 
The reactivity of organic substances largely depends on the nature of the J and M effects. Knowledge of the theoretical possibilities of electronic effects allows us to predict the course of certain chemical processes.
Acid-base properties of organic compounds Classification of organic reactions.
Lecture outline
The concept of substrate, nucleophile, electrophile.
Classification of organic reactions.
reversible and irreversible
radical, electrophilic, nucleophilic, synchronous.
mono- and bimolecular
substitution reactions
addition reactions
elimination reactions
oxidation and reduction
acid-base interactions
Reactions are regioselective, chemoselective, stereoselective.
Electrophilic addition reactions. Morkovnikov's rule, anti-Morkovnikov's accession.
Electrophilic substitution reactions: orientants of the 1st and 2nd kind.
Acid-base properties of organic compounds.
Bronsted acidity and basicity
Lewis acidity and basicity
Theory of hard and soft acids and bases.
Classification of organic reactions
Systematization of organic reactions makes it possible to reduce the diversity of these reactions to a relatively small number of types. Organic reactions can be classified:
towards: reversible and irreversible
by the nature of changes in bonds in the substrate and reagent.
Substrate– a molecule that provides a carbon atom to form a new bond
Reagent- a compound acting on the substrate.
Reactions based on the nature of changes in bonds in the substrate and reagent can be divided into:
radical R
electrophilic E
nucleophilic N(Y)
synchronous or coordinated 
Mechanism of SR reactions
Initiation
Chain growth
Open circuit 
CLASSIFICATION BY FINAL RESULT
Correspondence to the final result of the reaction is:
A) substitution reactions
B) addition reactions
B) elimination reactions
D) regroupings
D) oxidation and reduction
E) acid-base interactions
Reactions also happen:
Regioselective– preferably flowing through one of several reaction centers.
Chemoselective– preferential reaction for one of the related functional groups.
Stereoselective– preferential formation of one of several stereoisomers.
Reactivity of alkenes, alkanes, alkadienes, arenes and heterocyclic compounds
The basis of organic compounds are hydrocarbons. We will consider only those reactions carried out under biological conditions and, accordingly, not with hydrocarbons themselves, but with the participation of hydrocarbon radicals.
Unsaturated hydrocarbons include alkenes, alkadienes, alkynes, cycloalkenes and aromatic hydrocarbons. The unifying principle for them is π – the electron cloud. Under dynamic conditions, organic compounds also tend to be attacked by E+
However, interaction reactions for alkynes and arenes with reagents lead to different results, since in these compounds the nature of the π - electron cloud is different: localized and delocalized.
We will begin our consideration of reaction mechanisms with reactions A E. As we know, alkenes interact with 
Mechanism of hydration reaction
According to Markovnikov's rule - the addition to unsaturated hydrocarbons of an asymmetrical structure of compounds with the general formula HX - a hydrogen atom is added to the most hydrogenated carbon atom, if the substituent is ED. In anti-Markovnikov addition, a hydrogen atom is added to the least hydrogenated one if the substituent is EA.
Electrophilic substitution reactions in aromatic systems have their own characteristics. The first feature is that interaction with a thermodynamically stable aromatic system requires strong electrophiles, which are usually generated using catalysts.
Reaction mechanism S E 
ORIENTING INFLUENCE
DEPUTY
If there is any substituent in the aromatic ring, then it necessarily affects the distribution of the electron density of the ring. ED - substituents (orientants of the 1st row) CH 3, OH, OR, NH 2, NR 2 - facilitate substitution compared to unsubstituted benzene and direct the incoming group to the ortho- and para-position. If the ED substituents are strong, then a catalyst is not required; these reactions proceed in 3 stages.
EA substituents (orientants of the second kind) hinder electrophilic substitution reactions compared to unsubstituted benzene. The SE reaction occurs under more stringent conditions; the incoming group enters a meta position. Type II substituents include:
COOH, SO 3 H, CHO, halogens, etc.
SE reactions are also typical for heterocyclic hydrocarbons. Pyrrole, furan, thiophene and their derivatives belong to π-excess systems and quite easily enter into SE reactions. They are easily halogenated, alkylated, acylated, sulfonated, and nitrated. When choosing reagents, it is necessary to take into account their instability in a strongly acidic environment, i.e. acidophobicity.
Pyridine and other heterocyclic systems with a pyridine nitrogen atom are π-insufficient systems, they are much more difficult to enter into SE reactions, and the incoming electrophile occupies the β-position relative to the nitrogen atom. 
Acidic and basic properties of organic compounds
The most important aspects of the reactivity of organic compounds are the acid-base properties of organic compounds.
Acidity and basicity also important concepts that define many functional physicochemical and biological properties of organic compounds. Acid and base catalysis is one of the most common enzymatic reactions. Weak acids and bases are common components of biological systems that play an important role in metabolism and its regulation.
There are several concepts of acids and bases in organic chemistry. The Brønsted theory of acids and bases, generally accepted in inorganic and organic chemistry. According to Brønsted, acids are substances that can donate a proton, and bases are substances that can accept a proton. 
Bronsted acidity
In principle, most organic compounds can be considered as acids, since in organic compounds H is bonded to C, N O S
Organic acids are accordingly divided into C – H, N – H, O – H, S-H – acids. 
Acidity is assessed in the form of Ka or - log Ka = pKa, the lower the pKa, the stronger the acid.
Quantitative assessment of the acidity of organic compounds has not been determined for all organic substances. Therefore, it is important to develop the ability to conduct a qualitative assessment of the acidic properties of various acid sites. For this purpose, a general methodological approach is used.
The strength of the acid is determined by the stability of the anion (conjugate base). The more stable the anion, the stronger the acid.
The stability of the anion is determined by a combination of a number of factors:
electronegativity and polarizability of the element in the acid center.
the degree of delocalization of the negative charge in the anion.
the nature of the radical associated with the acid center.
solvation effects (influence of solvent)
Let us consider the role of all these factors sequentially:
Effect of electronegativity of elements
The more electronegative the element, the more delocalized the charge and the more stable the anion, the stronger the acid.
C (2.5) N (3.0) O (3.5) S (2.5)
Therefore, acidity changes in the series CH< NН < ОН For SH acids, another factor predominates - polarizability. The sulfur atom is larger in size and has vacant d orbitals. therefore, the negative charge is able to delocalize over a large volume, resulting in greater stability of the anion. Thiols, as stronger acids, react with alkalis, as well as with oxides and salts of heavy metals, while alcohols (weak acids) can only react with active metals The relatively high acidity of tols is used in medicine and in the chemistry of drugs. For example: Used for poisoning with As, Hg, Cr, Bi, the effect of which is due to the binding of metals and their removal from the body. For example: When assessing the acidity of compounds with the same atom in the acid center, the determining factor is the delocalization of the negative charge in the anion. The stability of the anion increases significantly with the emergence of the possibility of delocalization of the negative charge along the system of conjugated bonds. A significant increase in acidity in phenols, compared to alcohols, is explained by the possibility of delocalization in ions compared to the molecule. The high acidity of carboxylic acids is due to the resonance stability of the carboxylate anion Charge delocalization is facilitated by the presence of electron-withdrawing substituents (EA), they stabilize anions, thereby increasing acidity. For example, introducing a substituent into an EA molecule Effect of substituent and solvent a - hydroxy acids are stronger acids than the corresponding carboxylic acids. ED - substituents, on the contrary, reduce acidity. Solvents have a greater influence on the stabilization of the anion; as a rule, small ions with a low degree of charge delocalization are better solvated. The effect of solvation can be traced, for example, in the series: If an atom in an acid center carries a positive charge, this leads to increased acidity. Question to the audience: which acid - acetic or palmitic C 15 H 31 COOH - should have a lower pKa value? If the atom at the acid center carries a positive charge, this leads to increased acidity. One can note the strong CH - acidity of the σ - complex formed in the electrophilic substitution reaction. Bronsted basicity In order to form a bond with a proton, an unshared electron pair is necessary on the heteroatom, or be anions. There are p-bases and π bases, where the center of basicity is electrons of a localized π bond or π electrons of a conjugated system (π components) The strength of the base depends on the same factors as acidity, but their influence is opposite. The greater the electronegativity of an atom, the more tightly it holds a lone pair of electrons, and the less available it is for bonding with a proton. Then, in general, the strength of n-bases with the same substituent changes in the series: The most basic organic compounds are amines and alcohols: Salts of organic compounds with mineral acids are highly soluble. Many medicines are used in the form of salts. Acid-base center in one molecule (amphoteric) Hydrogen bonds as acid-base interactions For all α - amino acids there is a predominance of cationic forms in strongly acidic and anionic in strongly alkaline environments. The presence of weak acidic and basic centers leads to weak interactions - hydrogen bonds. For example: imidazole, with a low molecular weight, has a high boiling point due to the presence of hydrogen bonds. J. Lewis proposed a more general theory of acids and bases, based on the structure of electronic shells. A Lewis acid can be an atom, molecule, or cation that has a vacant orbital capable of accepting a pair of electrons to form a bond. Representatives of Lewis acids are the halides of elements of groups II and III of the periodic system D.I. Mendeleev. Lewis bases are an atom, molecule, or anion capable of donating a pair of electrons. Lewis bases include amines, alcohols, ethers, thiols, thioethers, and compounds containing π bonds. For example, the interaction below can be represented as a Lewis acid-base interaction An important consequence of Lewis's theory is that any organic substance can be represented as an acid-base complex. In organic compounds, intramolecular hydrogen bonds occur much less frequently than intermolecular ones, but they also occur in bioorganic compounds and can be considered as acid-base interactions. The concepts of “hard” and “soft” are not identical to strong and weak acids and bases. These are two independent characteristics. The essence of LCMO is that hard acids react with hard bases and soft acids react with soft bases. According to Pearson's principle of hard and soft acids and bases (HABP), Lewis acids are divided into hard and soft. Hard acids are acceptor atoms with small size, large positive charge, high electronegativity and low polarizability. Soft acids are large acceptor atoms with a small positive charge, low electronegativity and high polarizability. The essence of LCMO is that hard acids react with hard bases and soft acids react with soft bases. For example: Oxidation and reduction of organic compounds Redox reactions are of utmost importance for life processes. With their help, the body satisfies its energy needs, since the oxidation of organic substances releases energy. On the other hand, these reactions serve to convert food into cell components. Oxidation reactions promote detoxification and removal of drugs from the body. Oxidation is the process of removing hydrogen to form a multiple bond or new more polar bonds. Reduction is the reverse process of oxidation. The oxidation of organic substrates proceeds more easily, the stronger its tendency to give up electrons. Oxidation and reduction must be considered in relation to specific classes of compounds. Oxidation of C–H bonds (alkanes and alkyls) When alkanes burn completely, CO 2 and H 2 O are formed and heat is released. Other ways of their oxidation and reduction can be represented by the following schemes: The oxidation of saturated hydrocarbons occurs under harsh conditions (the chromium mixture is hot); softer oxidizers do not affect them. Intermediate oxidation products are alcohols, aldehydes, ketones, and acids. Hydroperoxides R – O – OH are the most important intermediate products of the oxidation of C – H bonds under mild conditions, in particular in vivo An important oxidation reaction of C–H bonds under body conditions is enzymatic hydroxylation. An example would be the production of alcohols through the oxidation of food. Due to molecular oxygen and its active forms. carried out in vivo. Hydrogen peroxide can serve as a hydroxylating agent in the body. Excess peroxide must be decomposed by catalase into water and oxygen. The oxidation and reduction of alkenes can be represented by the following transformations: Alkene reduction Oxidation and reduction of aromatic hydrocarbons Benzene is extremely difficult to oxidize even under harsh conditions according to the following scheme: The ability to oxidize increases markedly from benzene to naphthalene and further to anthracene. ED substituents facilitate the oxidation of aromatic compounds. EA – hinder oxidation. Benzene recovery. C 6 H 6 + 3 H 2 Enzymatic hydroxylation of aromatic compounds Oxidation of alcohols Compared to hydrocarbons, the oxidation of alcohols occurs under milder conditions The most important reaction of diols under body conditions is the transformation in the quinone-hydroquinone system The transfer of electrons from the substrate to oxygen occurs in metachondria. Oxidation and reduction of aldehydes and ketones One of the most easily oxidized classes of organic compounds 2H 2 C = O + H 2 O CH 3 OH + HCOOH flows especially easily in the light Oxidation of nitrogen-containing compounds Amines oxidize quite easily; the end products of oxidation are nitro compounds Exhaustive reduction of nitrogen-containing substances leads to the formation of amines. Oxidation of amines in vivo Oxidation and reduction of thiols Comparative characteristics of O-B properties of organic compounds. Thiols and 2-atomic phenols are most easily oxidized. Aldehydes oxidize quite easily. Alcohols are more difficult to oxidize, and primary ones are easier than secondary and tertiary ones. Ketones are resistant to oxidation or oxidize with the cleavage of the molecule. Alkynes oxidize easily even at room temperature. The most difficult to oxidize are compounds containing carbon atoms in the Sp3-hybridized state, that is, saturated fragments of molecules. ED – substituents facilitate oxidation EA – hinder oxidation. Specific properties of poly- and heterofunctional compounds. Lecture outline Poly- and heterofunctionality as a factor increasing the reactivity of organic compounds. Specific properties of poly- and heterofunctional compounds: amphotericity formation of intramolecular salts. intramolecular cyclization of γ, δ, ε – heterofunctional compounds. intermolecular cyclization (lactides and deketopypyrosines) chelation. elimination reactions of beta-heterofunctional connections. keto-enol tautomerism. Phosphoenolpyruvate, as macroergic compound. decarboxylation. stereoisomerism Poly- and heterofunctionality as the reason for the appearance of specific properties in hydroxy, amino and oxo acids. The presence of several identical or different functional groups in a molecule is a characteristic feature of biologically important organic compounds. A molecule may contain two or more hydroxyl groups, amino groups, or carboxyl groups. For example: An important group of substances involved in vital activity are heterofunctional compounds that have a pairwise combination of different functional groups. For example: In aliphatic compounds, all of the above functional groups exhibit an EA character. Due to their influence on each other, their reactivity is mutually enhanced. For example, in oxoacids, the electrophilicity of each of the two carbonyl carbon atoms is enhanced by the -J of the other functional group, leading to easier attack by nucleophilic reagents. Since the I effect fades after 3–4 bonds, an important circumstance is the proximity of the location of functional groups in the hydrocarbon chain. Heterofunctional groups can be located on the same carbon atom (α - arrangement), or on different carbon atoms, both neighboring (β arrangement) and more distant from each other (γ, delta, epsilon) locations. Each heterofunctional group retains its own reactivity; more precisely, heterofunctional compounds enter into a “double” number of chemical reactions. When the mutual arrangement of heterofunctional groups is sufficiently close, the reactivity of each of them is mutually enhanced. With the simultaneous presence of acidic and basic groups in the molecule, the compound becomes amphoteric. For example: amino acids. Interaction of heterofunctional groups The molecule of gerofunctional compounds may contain groups capable of interacting with each other. For example, in amphoteric compounds, such as α-amino acids, the formation of internal salts is possible. Therefore, all α - amino acids occur in the form of biopolar ions and are highly soluble in water. In addition to acid-base interactions, other types of chemical reactions become possible. For example, the reaction S N at SP 2 is a hybrid of a carbon atom in the carbonyl group due to interaction with the alcohol group, the formation of esters, a carboxyl group with an amino group (formation of amides). Depending on the relative arrangement of functional groups, these reactions can occur both within one molecule (intramolecular) and between molecules (intermolecular). Since the reaction results in the formation of cyclic amides and esters. then the determining factor becomes the thermodynamic stability of the cycles. In this regard, the final product usually contains six-membered or five-membered rings. In order for intramolecular interaction to form a five or six-membered ester (amide) ring, the heterofunctional compound must have a gamma or sigma arrangement in the molecule. Then in class
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