For new programs and textbooks, this issue becomes the most acute. Our school switched to the new textbooks by O.S. Gabrielyan and new program, like most schools in the Zavolzhsky district, therefore we present the calendar-thematic planning for the course "Organic Chemistry" grade 10. Thematic planning compiled according to the program developed by the Department educational programs And...
Activity. The search for methods and forms of teaching that contribute to the education of a creative personality has led to the emergence of some specific teaching methods, one of which is game methods. The implementation of gaming teaching methods in the study of chemistry in the conditions of compliance with didactic and psychological and pedagogical features, increases the level of training of students. The word "game" in Russian...
Secondly, a sufficient number of compounds are currently known that are insoluble in nonpolar solvents or, conversely, highly soluble in water, which, nevertheless, are classified as lipids. In modern organic chemistry, the definition of the term "lipids" is based on the biosynthetic relationship of these compounds - lipids include fatty acid and their derivatives. At the same time, in biochemistry...
The work is intended for teachers of chemistry, and may also be useful to students of pedagogical universities and colleges. 2.2. EXPLANATORY NOTE The need to develop an elective course for 10th grade students "Solving problems in organic chemistry advanced level complexity" due to several reasons. In accordance with the basic curriculum of a complete secondary school for the study of chemistry in 2 ...
Classification of organic substances
Depending on the type of structure of the carbon chain, organic substances are divided into:
- acyclic and cyclic.
- marginal (saturated) and unsaturated (unsaturated).
- carbocyclic and heterocyclic.
- alicyclic and aromatic.
Acyclic compounds are organic compounds in whose molecules there are no cycles and all carbon atoms are connected to each other in straight or branched open chains.
In turn, among acyclic compounds, limiting (or saturated) compounds are distinguished, which contain only single carbon-carbon (C-C) bonds in the carbon skeleton and unsaturated (or unsaturated) compounds containing multiples - double (C \u003d C) or triple (C ≡ C) communications.
Cyclic compounds are chemical compounds in which there are three or more bonded atoms forming a ring.
Depending on which atoms the rings are formed, carbocyclic compounds and heterocyclic compounds are distinguished.
Carbocyclic compounds (or isocyclic) contain only carbon atoms in their cycles. These compounds are in turn divided into alicyclic compounds (aliphatic cyclic) and aromatic compounds.
Heterocyclic compounds contain one or more heteroatoms in the hydrocarbon cycle, most often oxygen, nitrogen, or sulfur atoms.
The simplest class of organic substances are hydrocarbons - compounds that are formed exclusively by carbon and hydrogen atoms, i.e. formally do not have functional groups.
Since hydrocarbons do not have functional groups, they can only be classified according to the type of carbon skeleton. Hydrocarbons, depending on the type of their carbon skeleton, are divided into subclasses:
1) Limiting acyclic hydrocarbons are called alkanes. The general molecular formula of alkanes is written as C n H 2n+2, where n is the number of carbon atoms in a hydrocarbon molecule. These compounds do not have interclass isomers.
2) Acyclic unsaturated hydrocarbons are divided into:
a) alkenes - they contain only one multiple, namely one double C \u003d C bond, the general formula of alkenes is C n H 2n,
b) alkynes - in alkyne molecules there is also only one multiple, namely triple C≡C bond. The general molecular formula of alkynes is C n H 2n-2
c) alkadienes - in the molecules of alkadienes there are two double C=C bonds. The general molecular formula of alkadienes is C n H 2n-2
3) Cyclic saturated hydrocarbons are called cycloalkanes and have the general molecular formula C n H 2n.
The remaining organic substances in organic chemistry are considered as derivatives of hydrocarbons, formed upon the introduction of so-called functional groups into hydrocarbon molecules, which contain other chemical elements.
Thus, the formula of compounds with one functional group can be written as R-X, where R is a hydrocarbon radical, and X is a functional group. A hydrocarbon radical is a fragment of a hydrocarbon molecule without one or more hydrogen atoms.
According to the presence of certain functional groups, the compounds are divided into classes. The main functional groups and classes of compounds in which they are included are presented in the table:
Thus, various combinations of types of carbon skeletons with different functional groups give a wide variety of variants of organic compounds.
Halogen derivatives of hydrocarbons
Halogen derivatives of hydrocarbons are compounds obtained by replacing one or more hydrogen atoms in a molecule of any initial hydrocarbon with one or more atoms of a halogen, respectively.
Let some hydrocarbon have the formula C n H m, then when replacing in its molecule X hydrogen atoms on X halogen atoms, the formula for the halogen derivative will look like C n H m-X Hal X. Thus, monochlorine derivatives of alkanes have the formula C n H 2n+1 Cl, dichloro derivatives C n H 2n Cl 2 etc.
Alcohols and phenols
Alcohols are derivatives of hydrocarbons in which one or more hydrogen atoms are replaced by the hydroxyl group -OH. Alcohols with one hydroxyl group are called monatomic, with two - diatomic, with three triatomic etc. For example:
Alcohols with two or more hydroxyl groups are also called polyhydric alcohols. The general formula of limiting monohydric alcohols is C n H 2n+1 OH or C n H 2n+2 O. The general formula of limiting polyhydric alcohols is C n H 2n+2 O x, where x is the atomicity of the alcohol.
Alcohols can also be aromatic. For example:
benzyl alcoholThe general formula of such monohydric aromatic alcohols is C n H 2n-6 O.
However, it should be clearly understood that derivatives of aromatic hydrocarbons in which one or more hydrogen atoms at the aromatic nucleus are replaced by hydroxyl groups do not apply to alcohols. They belong to the class phenols . For example, this given compound is an alcohol:
And this is phenol:
The reason why phenols are not classified as alcohols lies in their specific chemical properties, which greatly distinguish them from alcohols. It is easy to see that monohydric phenols are isomeric to monohydric aromatic alcohols, i.e. also have the general molecular formula C n H 2n-6 O.
Amines
Amines called ammonia derivatives in which one, two or all three hydrogen atoms are replaced by a hydrocarbon radical.
Amines in which only one hydrogen atom is replaced by a hydrocarbon radical, i.e. having the general formula R-NH 2 are called primary amines.
Amines in which two hydrogen atoms are replaced by hydrocarbon radicals are called secondary amines. The formula for a secondary amine can be written as R-NH-R'. In this case, the radicals R and R' can be either the same or different. For example:
If there are no hydrogen atoms at the nitrogen atom in amines, i.e. all three hydrogen atoms of the ammonia molecule are replaced by a hydrocarbon radical, then such amines are called tertiary amines. In general, the formula of a tertiary amine can be written as:
In this case, the radicals R, R', R'' can be either completely identical, or all three are different.
The general molecular formula of primary, secondary and tertiary limiting amines is C n H 2 n +3 N.
Aromatic amines with only one unsaturated substituent have the general formula C n H 2 n -5 N
Aldehydes and ketones
Aldehydes called derivatives of hydrocarbons, in which, at the primary carbon atom, two hydrogen atoms are replaced by one oxygen atom, i.e. derivatives of hydrocarbons in the structure of which there is an aldehyde group –CH=O. The general formula for aldehydes can be written as R-CH=O. For example:
Ketones called derivatives of hydrocarbons, in which two hydrogen atoms at the secondary carbon atom are replaced by an oxygen atom, i.e. compounds in the structure of which there is a carbonyl group -C (O) -.
The general formula for ketones can be written as R-C(O)-R'. In this case, the radicals R, R' can be either the same or different.
For example:
| propane He | butane He |
As you can see, aldehydes and ketones are very similar in structure, but they are still distinguished as classes, since they have significant differences in chemical properties.
The general molecular formula of saturated ketones and aldehydes is the same and has the form C n H 2 n O
carboxylic acids
carboxylic acids called derivatives of hydrocarbons in which there is a carboxyl group -COOH.
If an acid has two carboxyl groups, the acid is called dicarboxylic acid.
Limit monocarboxylic acids (with one -COOH group) have a general molecular formula of the form C n H 2 n O 2
Aromatic monocarboxylic acids have the general formula C n H 2 n -8 O 2
Ethers
Ethers - organic compounds in which two hydrocarbon radicals are indirectly connected through an oxygen atom, i.e. have a formula of the form R-O-R'. In this case, the radicals R and R' can be either the same or different.
For example:
The general formula of saturated ethers is the same as for saturated monohydric alcohols, i.e. C n H 2 n +1 OH or C n H 2 n +2 O.
Esters
Esters are a class of compounds based on organic carboxylic acids, in which the hydrogen atom in the hydroxyl group is replaced by the hydrocarbon radical R. The general form of esters can be written as:
For example:
Nitro compounds
Nitro compounds- derivatives of hydrocarbons, in which one or more hydrogen atoms are replaced by a nitro group -NO 2.
Limit nitro compounds with one nitro group have the general molecular formula C n H 2 n +1 NO 2
Amino acids
Compounds that simultaneously have two functional groups in their structure - amino NH 2 and carboxyl - COOH. For example,
NH 2 -CH 2 -COOH
Limiting amino acids with one carboxyl and one amino group are isomeric to the corresponding limiting nitro compounds i.e. like they have the general molecular formula C n H 2 n +1 NO 2
IN USE assignments For the classification of organic substances, it is important to be able to write down the general molecular formulas of the homologous series of different types of compounds, knowing the structural features of the carbon skeleton and the presence of certain functional groups. In order to learn how to determine the general molecular formulas of organic compounds of different classes, material on this topic will be useful.
Nomenclature of organic compounds
Features of the structure and chemical properties of compounds are reflected in the nomenclature. The main types of nomenclature are systematic And trivial.
Systematic nomenclature actually prescribes algorithms, according to which one or another name is compiled in strict accordance with the structural features of an organic substance molecule or, roughly speaking, its structural formula.
Consider the rules for naming organic compounds according to systematic nomenclature.
When naming organic substances according to systematic nomenclature, the most important thing is to correctly determine the number of carbon atoms in the longest carbon chain or count the number of carbon atoms in a cycle.
Depending on the number of carbon atoms in the main carbon chain, compounds will have a different root in their name:
| Number of C atoms in the main carbon chain | Name root |
| prop- |
|
| pent- |
|
| hex- |
|
| hept- |
|
| dec(c)- |
The second important component taken into account when compiling names is the presence / absence of multiple bonds or a functional group, which are listed in the table above.
Let's try to give a name to a substance that has a structural formula:
1. The main (and only) carbon chain of this molecule contains 4 carbon atoms, so the name will contain the root but-;
2. There are no multiple bonds in the carbon skeleton, therefore, the suffix to be used after the root of the word will be -an, as in the case of the corresponding saturated acyclic hydrocarbons (alkanes);
3. The presence of a functional group -OH, provided that there are no more senior functional groups, adds after the root and suffix from paragraph 2. another suffix - "ol";
4. In molecules containing multiple bonds or functional groups, the numbering of carbon atoms of the main chain starts from the side of the molecule to which they are closer.
Let's look at another example:
The presence of four carbon atoms in the main carbon chain tells us that the root “but-” is the basis of the name, and the absence of multiple bonds indicates the suffix “-an”, which will follow immediately after the root. Senior group in this compound - carboxylic acid, it determines whether this substance belongs to the class of carboxylic acids. Therefore, the ending at the name will be "-ovoic acid". At the second carbon atom is an amino group NH2 -, therefore, this substance belongs to amino acids. Also at the third carbon atom we see the hydrocarbon radical methyl ( CH 3 -). Therefore, according to the systematic nomenclature, this compound is called 2-amino-3-methylbutanoic acid.
The trivial nomenclature, in contrast to the systematic one, as a rule, has no connection with the structure of the substance, but is mainly due to its origin, as well as chemical or physical properties.
| Formula | Name according to systematic nomenclature | Trivial name |
| hydrocarbons | ||
| CH 4 | methane | marsh gas |
| CH 2 \u003d CH 2 | ethene | ethylene |
| CH 2 \u003d CH-CH 3 | propene | propylene |
| CH≡CH | ethin | acetylene |
| CH 2 \u003d CH-CH \u003d CH 2 | butadiene-1,3 | divinyl |
| 2-methylbutadiene-1,3 | isoprene | |
| methylbenzene | toluene | |
| 1,2-dimethylbenzene | ortho-xylene (O-xylene) |
|
| 1,3-dimethylbenzene | meta-xylene (m-xylene) |
|
| 1,4-dimethylbenzene | pair-xylene (P-xylene) |
|
| vinylbenzene | styrene | |
| Alcohols | ||
| CH3OH | methanol | methyl alcohol, wood alcohol |
| CH 3 CH 2 OH | ethanol | ethanol |
| CH 2 \u003d CH-CH 2 -OH | propen-2-ol-1 | allyl alcohol |
| ethanediol-1,2 | ethylene glycol | |
| propanetriol-1,2,3 | glycerol | |
| phenol (hydroxybenzene) | carbolic acid | |
| 1-hydroxy-2-methylbenzene | ortho-cresol (O-cresol) |
|
| 1-hydroxy-3-methylbenzene | meta-cresol (m-cresol) |
|
| 1-hydroxy-4-methylbenzene | pair-cresol (P-cresol) |
|
| phenylmethanol | benzyl alcohol | |
| Aldehydes and ketones | ||
| methanal | formaldehyde | |
| ethanal | acetaldehyde, acetaldehyde | |
| propenal | acrylic aldehyde, acrolein | |
| benzaldehyde | benzoic aldehyde | |
| propanone | acetone | |
| carboxylic acids | ||
| (HCOOH) | methane acid | formic acid (salts and esters - formates) |
| (CH3COOH) | ethanoic acid | acetic acid (salts and esters - acetates) |
| (CH 3 CH 2 COOH) | propanoic acid | propionic acid (salts and esters - propionates) |
| C 15 H 31 COOH | hexadecanoic acid | palmitic acid (salts and esters - palmitates) |
| C 17 H 35 COOH | octadecanoic acid | stearic acid (salts and esters - stearates) |
| propenoic acid | acrylic acid (salts and esters - acrylates) |
|
| HOOC-COOH | ethanedioic acid | oxalic acid (salts and esters - oxalates) |
| 1,4-benzenedicarboxylic acid | terephthalic acid | |
| Esters | ||
| HCOOCH 3 | methylmethanoate | methyl formate, formic acid methyl ester |
| CH 3 COOK 3 | methyl ethanoate | methyl acetate, acetic acid methyl ester |
| CH 3 COOC 2 H 5 | ethyl ethanoate | ethyl acetate, acetic acid ethyl ester |
| CH 2 \u003d CH-COOCH 3 | methyl propenoate | methyl acrylate, acrylic acid methyl ester |
| Nitrogen compounds | ||
| aminobenzene, phenylamine | aniline | |
| NH 2 -CH 2 -COOH | aminoethanoic acid | glycine, aminoacetic acid |
| 2-aminopropionic acid | alanine | |
Alkanes(saturated hydrocarbons, paraffins) - acyclic saturated hydrocarbons of the general formula C n H 2n+2 . In accordance with the general formula, alkanes form homologous series.
The first four representatives have semi-systematic names - methane (CH 4), ethane (C 2 H 6), propane (C 3 H 8), butane (C 4 H 10). The names of the subsequent members of the series are built from the root (Greek numerals) and the suffix - en: pentane (C 5 H 12), hexane (C 6 H 14), heptane (C 7 H 16), etc.
The carbon atoms in alkanes are in sp 3- hybrid state. axes four sp3- orbitals are directed to the vertices of the tetrahedron, the bond angles are 109°28.
Spatial structure of methane:
Energy C-C connections E s - With\u003d 351 kJ / mol, the length of the C-C bond is 0.154 nm.
The C-C bond in alkanes is covalent non-polar. S-N connection - covalent weakly polar.
For alkanes, starting with butane, there are structural isomers(structure isomers) that differ in the order of binding between carbon atoms, with the same qualitative and quantitative composition and molecular weight, but differing in physical properties.
Methods for obtaining alkanes
1. C n H 2n+2 > 400-700°C> С p H 2p+2 + С m H 2m ,
Oil cracking (industrial method). Alkanes are also isolated from natural sources (natural and associated gases, oil, coal).
(hydrogenation of unsaturated compounds)
3. nCO + (2n + 1)H 2 > C n H 2n+2 + nH 2 O (obtained from synthesis gas (CO + H 2))
4. (Wurtz reaction)
5. (Dumas reaction) CH 3 COONa + NaOH > t> CH 4 + Na 2 CO 3
6. (Kolbe reaction)
Chemical properties of alkanes Alkanes are not capable of addition reactions, since all bonds in their molecules are saturated, they are characterized by reactions of radical substitution, thermal decomposition, oxidation, isomerization.
1. (reactivity decreases in the series: F 2 > Cl 2 > Br 2 > (I 2 does not go), R 3 C > R 2 CH > RCH 2 > RCH 3)
2. (Konovalov's reaction)
3. C n H 2n+2 + SO 2 + ?O 2 > h?> C n H 2n+1 SO 3 H - alkyl sulfonic acid
(sulfonic oxidation, reaction conditions: UV irradiation)
4.CH4> 1000°C> C + 2H 2; 2CH4> t>1500 °C> C 2 H 2 + ZN 2 (methane decomposition - pyrolysis)
5. CH 4 + 2H 2 O> Ni, 1300 °C> CO 2 + 4H 2 (methane conversion)
6. 2С n H 2n + 2 + (Зn + 1) O 2 > 2nCO 2 + (2n + 2) Н 2 O (burning of alkanes)
7. 2n- C 4 H 10 + 5O 2 > 4CH 3 COOH + 2H 2 O (oxidation of alkanes in industry; production of acetic acid)
8. n- C 4 H 10 > iso- C 4 H 10 (isomerization, AlCl 3 catalyst)
2. Cycloalkanes
Cycloalkanes(cycloparaffins, naphthenes, cyclanes, polymethylenes) are saturated hydrocarbons with a closed (cyclic) carbon chain. General formula C n H 2n.
The carbon atoms in cycloalkanes, as in alkanes, are in sp 3-hybridized state. homologous series cycloalkanes begins with the simplest cycloalkane - cyclopropane C 3 H 6, which is a flat three-membered carbocycle. According to the rules of international nomenclature in cycloalkanes, the main chain of carbon atoms forming a cycle is considered. The name is built on the name of this closed chain with the addition of the prefix "cyclo" (cyclopropane, cyclobutane, cyclopentane, cyclohexane, etc.).
Structural isomerism of cycloalkanes is associated with different ring sizes (structures 1 and 2), structure and type of substituents (structures 5 and 6), and their mutual arrangement (structures 3 and 4).
Methods for obtaining cycloalkanes
1. Obtaining from dihalogen derivatives of hydrocarbons
2. Preparation from aromatic hydrocarbons
Chemical properties of cycloalkanes The chemical properties of cycloalkanes depend on the ring size, which determines its stability. Three- and four-membered cycles (small cycles), being saturated, differ sharply from all other saturated hydrocarbons. Cyclopropane, cyclobutane enter into addition reactions. For cycloalkanes (C 5 and above), due to their stability, reactions are characteristic in which the cyclic structure is preserved, i.e., substitution reactions.
1. Action of halogens
2. Action of hydrogen halides
Hydrogen halogens do not react with cycloalkanes containing five or more carbon atoms in the cycle.
4. Dehydrogenation
Alkenes(unsaturated hydrocarbons, ethylene hydrocarbons, olefins) - unsaturated aliphatic hydrocarbons, the molecules of which contain a double bond. The general formula for a number of alkenes C n H 2n.
According to the systematic nomenclature, the names of alkenes are derived from the names of the corresponding alkanes (with the same number of carbon atoms) by replacing the suffix – en on - en: ethane (CH 3 -CH 3) - ethene (CH 2 \u003d CH 2), etc. The main chain is chosen so that it necessarily includes a double bond. The numbering of carbon atoms starts from the end of the chain closest to the double bond.
In an alkene molecule, the unsaturated carbon atoms are in sp 2-hybridization, and the double bond between them is formed by?- and?-bond. sp 2-Hybrid orbitals are directed to each other at an angle of 120 °, and one unhybridized 2p-orbital, located at an angle of 90 ° to the plane of hybrid atomic orbitals.
Spatial structure of ethylene:
C=C bond length 0.134 nm, C=C bond energy E c=c\u003d 611 kJ / mol, energy?-bond E? = 260 kJ/mol.
Types of isomerism: a) chain isomerism; b) double bond position isomerism; V) Z, E (cis, trans) - isomerism, a type of spatial isomerism.
Methods for obtaining alkenes1. CH 3 -CH 3> Ni, t> CH 2 \u003d CH 2 + H 2 (dehydrogenation of alkanes)
2. C 2 H 5 OH >H,SO 4 , 170 °C> CH 2 \u003d CH 2 + H 2 O (dehydration of alcohols)
3. (dehydrohalogenation of alkyl halides according to the Zaitsev rule)
4. CH 2 Cl-CH 2 Cl + Zn > ZnCl 2 + CH 2 \u003d CH 2 (dehalogenation of dihalogen derivatives)
5. HC?CH + H2> Ni, t> CH 2 \u003d CH 2 (alkyne reduction)
Chemical properties of alkenesFor alkenes, addition reactions are most characteristic; they are easily oxidized and polymerized.
1. CH 2 \u003d CH 2 + Br 2\u003e CH 2 Br-CH 2 Br
(addition of halogens, qualitative reaction)
2. (addition of hydrogen halides according to the Markovnikov rule)
3. CH 2 \u003d CH 2 + H 2> Ni, t> CH 3 -CH 3 (hydrogenation)
4. CH 2 \u003d CH 2 + H 2 O> H+> CH 3 CH 2 OH (hydration)
5. ZCH 2 \u003d CH 2 + 2KMnO 4 + 4H 2 O\u003e ZCH 2 OH-CH 2 OH + 2MnO 2 v + 2KOH (mild oxidation, qualitative reaction)
6. CH 2 \u003d CH-CH 2 -CH 3 + KMnO 4> H+> CO 2 + C 2 H 5 COOH (hard oxidation)
7. CH 2 \u003d CH-CH 2 -CH 3 + O 3\u003e H 2 C \u003d O + CH 3 CH 2 CH \u003d O formaldehyde + propanal> (ozonolysis)
8. C 2 H 4 + 3O 2 > 2CO 2 + 2H 2 O (combustion reaction)
9. (polymerization)
10. CH 3 -CH \u003d CH 2 + HBr\u003e peroxide> CH 3 -CH 2 -CH 2 Br (addition of hydrogen bromide against Markovnikov's rule)
11. (substitution reaction in?-position)
Alkynes(acetylenic hydrocarbons) - unsaturated hydrocarbons that have a triple C?C bond in their composition. The general formula of alkynes with one triple bond is C n H 2n-2. The simplest representative of the CH?CH series of alkynes has the trivial name acetylene. According to the systematic nomenclature, the names of acetylenic hydrocarbons are derived from the names of the corresponding alkanes (with the same number of carbon atoms) by replacing the suffix - en on -in: ethane (CH 3 -CH 3) - ethine (CH? CH), etc. The main chain is chosen so that it necessarily includes a triple bond. The numbering of carbon atoms starts from the end of the chain closest to the triple bond.
The formation of a triple bond involves carbon atoms in sp-hybridized state. Each of them has two sp- hybrid orbitals directed to each other at an angle of 180 °, and two non-hybrid p orbitals at 90° to each other and to sp hybrid orbitals.
Spatial structure of acetylene:
Types of isomerism: 1) isomerism of the position of the triple bond; 2) isomerism of the carbon skeleton; 3) interclass isomerism with alkadienes and cycloalkenes.
Methods for obtaining alkynes1. CaO + GL > t> CaC 2 + CO;
CaC 2 + 2H 2 O > Ca (OH) 2 + CH? CH (production of acetylene)
2.2CH4> t>1500 °C> HC = CH + ZN 2 (hydrocarbon cracking)
3. CH 3 -CHCl 2 + 2KOH> in alcohol> HC?CH + 2KCl + H 2 O (dehalogenation)
CH 2 Cl-CH 2 Cl + 2KOH> in alcohol> HC?CH + 2KCl + H 2 O
Chemical properties of alkynesAlkynes are characterized by addition, substitution reactions. Alkynes polymerize, isomerize, enter into condensation reactions.
1. (hydrogenation)
2. HC?CH + Br 2 > CHBr=CHBr;
CHBr \u003d CHBr + Br 2\u003e CHBr 2 -CHBr 2 (addition of halogens, qualitative reaction)
3. CH 3 -C? CH + HBr> CH 3 -CBr \u003d CH 2;
CH 3 -CBr \u003d CH 2 + HBr\u003e CH 3 -CBr 2 -CHg (addition of hydrogen halides according to the Markovnikov rule)
4. (hydration of alines, Kucherov's reaction)
5.(addition of alcohols)
6.(attaching carbon islot)
7.CH?CH + 2Ag2O> NH3> AgC?CAgv + H 2 O (formation of acetylenides, qualitative reaction for terminal triple bond)
8.CH?CH + [O]> KMnO 4> HOOC-COOH > HCOOH + CO 2 (oxidation)
9. CH?CH + CH?CH > CH 2 \u003d CH-C?CH (catalyst - CuCl and NH 4 Cl, dimerization)
10.3HC?CH> C, 600°C> C 6 H 6 (benzene) (cyclooligomerization, Zelinsky reaction)
5. Diene hydrocarbons
Alkadienes(dienes) - unsaturated hydrocarbons, the molecules of which contain two double bonds. The general formula of alkadienes C n H 2n _ 2. The properties of alkadienes largely depend on the mutual arrangement of double bonds in their molecules.
Methods for obtaining dienes1. (SV. Lebedev's method)
2. (dehydration)
3. (dehydrogenation)
Chemical properties of dienes
For conjugated dienes, addition reactions are characteristic. Conjugated dienes are able to attach not only to double bonds (to C 1 and C 2, C 3 and C 4), but also to the terminal (C 1 and C 4) carbon atoms to form a double bond between C 2 and C 3.
6. Aromatic hydrocarbons
arenas, or aromatic hydrocarbons,- cyclic compounds, the molecules of which contain stable cyclic groups of atoms with a closed system of conjugated bonds, united by the concept of aromaticity, which determines common features in the structure and chemical properties.
All C-C bonds in benzene are equivalent, their length is 0.140 nm. This means that in the benzene molecule there are no purely simple and double bonds between carbon atoms (as in the formula proposed in 1865 by the German chemist F. Kekule), and all of them are aligned (they are localized).
Kekule formula Benzene homologues are compounds formed by replacing one or more hydrogen atoms in a benzene molecule with hydrocarbon radicals (R): C 6 H 5 -R, R-C 6 H 4 -R. The general formula for the homologous series of benzene C n H 2n _ 6 (n> 6). Trivial names (toluene, xylene, cumene, etc.) are widely used for the names of aromatic hydrocarbons. Systematic names are built from the name of the hydrocarbon radical (prefix) and the word "benzene" (root): C 6 H 5 -CH 3 (methylbenzene), C 6 H 5 -C 2 H 5 (ethylbenzene). If there are two or more radicals, their position is indicated by the numbers of the carbon atoms in the ring to which they are attached. For disubstituted benzenes R-C 6 H 4 -R, another method of constructing names is also used, in which the position of the substituents is indicated before the trivial name of the compound with prefixes: ortho-(o-) - substituents of neighboring carbon atoms of the ring (1,2-); meta-(m-) - substituents through one carbon atom (1,3-); pair-(P-) - substituents on opposite sides of the ring (1,4-).
Types of isomerism (structural): 1) positions of substituents for di-, tri- and tetra-substituted benzenes (for example, o-, m- And P-xylenes); 2) a carbon skeleton in a side chain containing at least 3 carbon atoms; 3) substituents (R), starting with R=C 2 H 5 .
Methods for obtaining aromatic hydrocarbons1. C 6 H 12 > Pt, 300 °C> С 6 Н 6 + ЗН 2 (dehydrogenation of cycloalkanes)
2. n- C 6 H 14 > Cr2O3, 300°C> C 6 H 6 + 4H 2 (dehydrocyclization of alkanes)
3. ZS 2 H 2 > C, 600 °C> C 6 H 6 (cyclotrimerization of acetylene, Zelinsky reaction)
Chemical properties of aromatic hydrocarbonsBy chemical properties, arenas differ from saturated and unsaturated hydrocarbons. For arenes, the most characteristic reactions proceed with the preservation of the aromatic system, namely, the substitution reactions of hydrogen atoms associated with the cycle. Other reactions (addition, oxidation), in which delocalized C-C bonds of the benzene ring are involved and its aromaticity is disturbed, go with difficulty.
1. C 6 H 6 + Cl 2> AlCl 3> C 6 H 5 Cl + HCl (halogenation)
2. C 6 H 6 + HNO 3 > H2SO4> C 6 H 5 -NO 2 + H 2 O (nitration)
3. C 6 H 6 > H2SO4> C 6 H 5 -SO 3 H + H 2 O (sulfonation)
4. C 6 H 6 + RCl> AlCl 3> C 6 H 5 -R + HCl (alkylation)
5. (acylation)
6. C 6 H 6 + ZN 2> t, Ni> C 6 H 12 cyclohexane (hydrogen addition)
7. (1,2,3,4,5,6-hexachlorocyclohexane, addition of chlorine)
8. C 6 H 5 -CH 3 + [O]> C 6 H 5 -COOH boiling with a solution of KMnO 4 (oxidation of alkylbenzenes)
7. Halogenated hydrocarbons
halocarbons called derivatives of hydrocarbons in which one or more hydrogen atoms are replaced by halogen atoms.
Methods for producing halocarbons1. CH 2 \u003d CH 2 + HBr\u003e CH 3 -CH 2 Br (hydrohalogenation of unsaturated hydrocarbons)
CH?CH + HCl > CH 2 \u003d CHCl
2. CH 3 CH 2 OH + РCl 5 > CH 3 CH 2 Cl + POCl 3 + HCl (preparation from alcohols)
CH 3 CH 2 OH + HCl > CH 3 CH 2 Cl + H 2 O (in the presence of ZnCl 2, t°C)
3. a) CH 4 + Cl 2 >hv> CH 3 Cl + HCl (halogenation of hydrocarbons)
Chemical properties of halocarbons
Highest value for compounds of this class, they have substitution and elimination reactions.
1. CH 3 CH 2 Br + NaOH (aqueous solution) > CH 3 CH 2 OH + NaBr (formation of alcohols)
2. CH 3 CH 2 Br + NaCN > CH 3 CH 2 CN + NaBr (formation of nitriles)
3. CH 3 CH 2 Br + NH 3 > + Br - HBr- CH 3 CH 2 NH 2 (formation of amines)
4. CH 3 CH 2 Br + NaNO 2 > CH 3 CH 2 NO 2 + NaBr (formation of nitro compounds)
5. CH 3 Br + 2Na + CH 3 Br > CH 3 -CH 3 + 2NaBr (Wurtz reaction)
6. CH 3 Br + Mg > CH 3 MgBr (formation of organomagnesium compounds, Grignard reagent)
7. (dehydrohalogenation)
alcohols called derivatives of hydrocarbons, the molecules of which contain one or more hydroxyl groups (-OH) associated with saturated carbon atoms. The -OH group (hydroxyl, hydroxy group) is a functional group in the alcohol molecule. Systematic names are given by the name of the hydrocarbon with the addition of the suffix - ol and a number indicating the position of the hydroxy group. The numbering is carried out from the end of the chain closest to the OH group.
According to the number of hydroxyl groups, alcohols are divided into monohydric (one -OH group), polyhydric (two or more -OH groups). Monohydric alcohols: methanol CH 3 OH, ethanol C 2 H 5 OH; dihydric alcohol: ethylene glycol (ethanediol-1,2) HO-CH 2 -CH 2 -OH; trihydric alcohol: glycerol (propanetriol-1,2,3) HO-CH 2 -CH(OH)-CH 2 -OH. Depending on which carbon atom (primary, secondary or tertiary) the hydroxy group is associated with, primary alcohols R-CH 2 -OH, secondary R 2 CH-OH, tertiary R 3 C-OH are distinguished.
According to the structure of the radicals associated with the oxygen atom, alcohols are divided into saturated, or alkanols (CH 3 CH 2 -OH), unsaturated, or alkenols (CH 2 \u003d CH-CH 2 -OH), aromatic (C 6 H 5 CH 2 - OH).
Types of isomerism (structural isomerism): 1) isomerism of the position of the OH group (starting from C 3); 2) carbon skeleton (starting from C 4); 3) interclass isomerism with ethers (for example, ethyl alcohol CH 3 CH 2 OH and dimethyl ether CH 3 -O-CH 3). The consequence of the polarity of the O-H bond and the presence of lone pairs of electrons on the oxygen atom is the ability of alcohols to form hydrogen bonds.
Methods for obtaining alcohols1. CH 2 \u003d CH 2 + H 2 O / H +\u003e CH 3 -CH 2 OH (alkene hydration)
2. CH 3 -CHO + H 2> t, Ni> C 2 H 5 OH (reduction of aldehydes and ketones)
3. C 2 H 5 Br + NaOH (aq.) > C 2 H 5 OH + NaBr (hydrolysis of halogen derivatives)
ClCH 2 -CH 2 Cl + 2NaOH (aq.) > HOCH 2 -CH 2 OH + 2NaCl
4. CO + 2H 2> ZnO, CuO, 250 °C, 7 MPa> CH 3 OH (methanol production, industry)
5. C 6 H 12 O 6 > yeast> 2C 2 H 5 OH + 2CO 2 (monose fermentation)
6. 3CH 2 \u003d CH 2 + 2KMnO 4 + 4H 2 O\u003e 3CH 2 OH-CH 2 OH - ethylene glycol+ 2KOH + 2MnO 2 (oxidation under mild conditions)
7. a) CH 2 \u003d CH-CH 3 + O 2\u003e CH 2 \u003d CH-CHO + H 2 O
b) CH 2 \u003d CH-CHO + H 2\u003e CH 2 \u003d CH-CH 2 OH
c) CH 2 \u003d CH-CH 2 OH + H 2 O 2\u003e HOCH 2 -CH (OH) -CH 2 OH (obtaining glycerol)
Chemical properties of alcoholsThe chemical properties of alcohols are associated with the presence of the -OH group in their molecule. Alcohols are characterized by two types of reactions: cleavage C-O connections and O-N connections.
1. 2C 2 H 5 OH + 2Na > H 2 + 2C 2 H 5 ONa (formation of metal alcoholates Na, K, Mg, Al)
2. a) C 2 H 5 OH + NaOH? (does not work in aqueous solution)
b) CH 2 OH-CH 2 OH + 2NaOH> NaOCH 2 -CH 2 ONa + 2H 2 O
c) (qualitative reaction to polyhydric alcohols - the formation of a bright blue solution with copper hydroxide)
3. a) (formation of esters)
b) C 2 H 5 OH + H 2 SO 4 > C 2 H 5 -O-SO 3 H + H 2 O (in the cold)
4. a) C 2 H 5 OH + HBr> C 2 H 5 Br + H 2 O
b) C 2 H 5 OH + РCl 5 > C 2 H 5 Cl + POCl 3 + HCl
c) C 2 H 5 OH + SOCl 2 > C 2 H 5 Cl + SO 2 + HCl (replacement of the hydroxyl group by halogen)
5. C 2 H 5 OH + HOC 2 H 5 > H2SO4,<140 °C > C 2 H 5 -O-C 2 H 5 + H 2 O (intermolecular hydration)
6. C 2 H 5 OH> H2SO4, 170°C> CH 2 \u003d CH 2 + H 2 O (intramolecular hydration)
7. a) (dehydrogenation, oxidation of primary alcohols)
Phenols arene derivatives are called, in which one or more hydrogen atoms of the aromatic ring are replaced by hydroxyl groups. According to the number of hydroxyl groups in the aromatic ring, mono- and polyatomic (two- and three-atomic) phenols are distinguished. Trivial names are used for most phenols. Structural isomerism of phenols is associated with different positions of hydroxyl groups.
Methods for obtaining phenols
1. C 6 H 5 Cl + NaOH(p, 340°C) > C 6 H 5 OH + NaCl (alkaline hydrolysis of halocarbons)
2. (cumene method of obtaining)
3. C 6 H 5 SO 3 Na + NaOH (300–350°C) > C 6 H 5 OH + Na 2 SO 3 (alkaline melting of salts of aromatic sulfonic acids)
Chemical properties of phenolsPhenols in most bond reactions O-N more active alcohols, since this bond is more polar due to the shift of the electron density from the oxygen atom towards the benzene ring (participation of the unshared electron pair of the oxygen atom in the n-conjugation system). The acidity of phenols is much higher than that of alcohols.
For phenols, C-O bond cleavage reactions are not typical. The mutual influence of atoms in the phenol molecule is manifested not only in the behavior of the hydroxy group, but also in the greater reactivity of the benzene ring.
The hydroxyl group increases the electron density in the benzene ring, especially in ortho- And pair- positions (+ M effect of the OH group). For the detection of phenols, a qualitative reaction with iron(III) chloride is used. Monatomic phenols give a stable blue-violet color, which is associated with the formation of complex iron compounds.
1. 2C 6 H 5 OH + 2Na > 2C 6 H 5 ONa + H 2 (same as ethanol)
2. C 6 H 5 OH + NaOH > C 6 H 5 ONa + H 2 O (unlike ethanol)
C 6 H 5 ONa + H 2 O + CO 2 > C 6 H 5 OH + NaHCO 3 (phenol is a weaker acid than carbonic)
Phenols do not form esters in reactions with acids. For this, more reactive acid derivatives (anhydrides, acid chlorides) are used.
4. C 6 H 5 OH + CH 3 CH 2 OH> NaOH> C 6 H 5 OCH 2 CH 3 + NaBr (O-alkylation)
(interaction with bromine water, qualitative reaction)
6. (Nitration dilute HNO 3, nitration with conc. HNO 3 produces 2,4,6-trinitrophenol)
7. n C6H5OH+ n CH2O> n H 2 O + (-C 6 H 3 OH-CH 2 -) n(polycondensation, obtaining phenol-formaldehyde resins)
10. Aldehydes and ketones
Aldehydes are compounds in which the carbonyl group
connected to a hydrocarbon radical and a hydrogen atom, and ketones- carbonyl compounds with two hydrocarbon radicals.
The systematic names of aldehydes are built on the name of the corresponding hydrocarbon with the addition of a suffix –al. The chain numbering starts from the carbonyl carbon atom. Trivial names are derived from the trivial names of those acids into which aldehydes are converted during oxidation: H 2 C \u003d O - methanal (formaldehyde, formaldehyde); CH 3 CH=O - ethanal (acetic aldehyde). The systematic names of ketones of a simple structure are derived from the names of the radicals with the addition of the word "ketone". In a more general case, the name of a ketone is constructed from the name of the corresponding hydrocarbon and the suffix -He; chain numbering starts from the end of the chain closest to the carbonyl group. Examples: CH 3 -CO-CH 3 - dimethyl ketone (propanone, acetone). Aldehydes and ketones are characterized by structural isomerism. Isomerism of aldehydes: a) isomerism of the carbon skeleton, starting from C 4; b) interclass isomerism. Isomerism of ketones: a) carbon skeleton (with C 5); b) positions of the carbonyl group (with C 5); c) interclass isomerism.
The carbon and oxygen atoms in the carbonyl group are in the state sp2- hybridization. The C=O bond is highly polar. The electrons of the C=O multiple bond are shifted to the electronegative oxygen atom, which leads to the appearance of a partial negative charge on it, and the carbonyl carbon atom acquires a partial positive charge.
Methods for obtaining aldehydes and ketones1. a) (dehydrogenation, oxidation of primary alcohols)
b) (dehydrogenation, oxidation of secondary alcohols)
2. a) CH 3 CH 2 CHCl 2 + 2NaOH> in water> CH 3 CH 2 CHO + 2NaCl + H 2 O (hydrolysis of dihalogen derivatives)
b) CH 3 СCl 2 CH 3 + 2NaOH> in water> CH 3 COCH 3 + 2NaCl + H 2 O
3. (hydration of alkynes, Kucherov reaction)
4. (oxidation of ethylene to ethanal)
(methane oxidation to formaldehyde)
CH 4 + O 2 > 400-600°C NO> H 2 C \u003d O + H 2 O
Chemical properties of aldehydes and ketonesFor carbonyl compounds, reactions of various types are characteristic: a) addition to the carbonyl group; b) reduction and oxidation; c) condensation; e) polymerization.
1. (addition of hydrocyanic acid, formation of hydroxynitriles)
2. (addition of sodium hydrosulphate)
3. (recovery)
4. (formation of hemiacetals and acetals)
5. (interaction with hydroxolamine, formation of acetaldehyde oxime)
6. (formation of dihalogen derivatives)
7. (?-halogenation in the presence of OH?)
8. (albdol condensation)
9. R-CH \u003d O + Ag 2 O> NH3> R-COOH + 2Agv (oxidation, silver mirror reaction)
R-CH \u003d O + 2Cu (OH) 2\u003e R-COOH + Cu 2 Ov, + 2H 2 O (red precipitate, oxidation)
10. (ketone oxidation, severe conditions)
11. n CH 2 \u003d O\u003e (-CH2-O-) n paraforms n= 8-12 (polymerization)
11. Carboxylic acids and their derivatives
carboxylic acids called organic compounds containing one or more carboxyl groups -COOH associated with a hydrocarbon radical. According to the number of carboxyl groups, acids are divided into: monobasic (monocarboxylic) CH 3 COOH (acetic), polybasic (dicarboxylic, tricarboxylic, etc.). According to the nature of the hydrocarbon radical, acids are distinguished: limiting (for example, CH 3 CH 2 CH 2 COOH); unsaturated (CH 2 \u003d CH (-COOH); aromatic (C 6 H 5 COOH).
The systematic names of acids are given by the name of the corresponding hydrocarbon with the addition of the suffix –new and the words "acid": HCOOH - methane (formic) acid, CH 3 COOH - ethanoic (acetic) acid. For carboxylic acids, the characteristic structural isomerism is: a) skeletal isomerism in the hydrocarbon radical (starting from C 4); b) interclass isomerism, starting from C 2 . Possible cis-trans isomerism in the case of unsaturated carboxylic acids. electron density? - bonds in the carbonyl group are shifted towards the oxygen atom. As a result, carbonyl carbon has a lack of electron density, and it attracts lone pairs of the oxygen atom of the hydroxyl group, as a result of which the electron density of the O-H bond shifts towards the oxygen atom, hydrogen becomes mobile and acquires the ability to split off in the form of a proton.
In an aqueous solution, carboxylic acids dissociate into ions:
R-COOH - R-COO? + H +
Solubility in water and high boiling points of acids are due to the formation of intermolecular hydrogen bonds.
Methods for obtaining carboxylic acids1. CH 3 -CCl 3 + 3NaOH > CH 3 -COOH + 3NaCl + H 2 O (hydrolysis of trihalogen derivatives)
2. R-CHO + [O] > R-COOH (oxidation of aldehydes and ketones)
3. CH 3 -CH \u003d CH 2 + CO + H 2 O / H + > Ni, p, t> CH 3 -CH 2 -CH 2 -COOH (oxosynthesis)
4. CH 3 C?N + 2H 2 O / H + > CH 3 COOH + NH 4 (hydrolysis of nitriles)
5. CO + NaOH > HCOONa; 2HCOONa + H 2 SO 4 > 2HCOOH + Na 2 SO 4 (obtaining HCOOH)
Chemical properties of carboxylic acids and their derivativesCarboxylic acids are highly reactive and react with various substances, forming a variety of compounds, among which great importance have functional derivatives: esters, amides, nitriles, salts, anhydrides, halo-anhydrides.
1. a) 2CH 3 COOH + Fe > (CH 3 COO) 2 Fe + H 2 (formation of salts)
b) 2CH 3 COOH + MgO > (CH 3 COO) 2 Mg + H 2 O
c) CH 3 COOH + KOH > CH 3 COOK + H 2 O
d) CH 3 COOH + NaHCO 3 > CH 3 COONa + CO 2 + H 2 O
CH 3 COONa + H 2 O - CH 3 COOH + NaOH (salts of carboxylic acids are hydrolyzed)
2. (formation of nested esters)
(saponification of nested ether)
3. (obtaining acid chlorides)
4. (water decomposition)
5. CH 3 -COOH + Cl 2> hv> Cl-CH 2 -COOH + HCl (halogenation in?-position)
6. HO-CH \u003d O + Ag 2 O> NH3> 2Ag + H 2 CO 3 (H 2 O + CO 2) (HCOOH features)
HCOOH > t> CO + H 2 O
Fats- esters of glycerol and higher monohydric carboxylic acids. The common name for these compounds is triglycerides. The composition of natural triglycerides includes residues of saturated acids (palmitic C 15 H 31 COOH, stearic C 17 H 35 COOH) and unsaturated acids (oleic C 17 H 33 COOH, linoleic C 17 H 31 COOH). Fats consist mainly of triglycerides of saturated acids. Vegetable fats - oils (sunflower, soybean) - liquids. The composition of triglycerides of oils includes residues of unsaturated acids.
Fats as esters are characterized by a reversible hydrolysis reaction catalyzed by mineral acids. With the participation of alkalis, the hydrolysis of fats occurs irreversibly. The products in this case are soaps - salts of higher carboxylic acids and alkali metals. Sodium salts are solid soaps, potassium salts are liquid. The reaction of alkaline hydrolysis of fats is also called saponification.
Amines- organic derivatives of ammonia, in the molecule of which one, two or three hydrogen atoms are replaced by hydrocarbon radicals. Depending on the number of hydrocarbon radicals, primary RNH 2 , secondary R 2 NH, tertiary R 3 N amines are distinguished. According to the nature of the hydrocarbon radical, amines are divided into aliphatic (fatty), aromatic and mixed (or fatty-aromatic). The names of amines in most cases are formed from the names of hydrocarbon radicals and the suffix -amine. For example, CH 3 NH 2 is methylamine; CH 3 -CH 2 -NH 2 - ethylamine. If the amine contains various radicals, then they are listed in alphabetical order: CH 3 -CH 2 -NH-CH 3 - methylethylamine.
The isomerism of amines is determined by the number and structure of radicals, as well as the position of the amino group. N-H connection is polar, so primary and secondary amines form intermolecular hydrogen bonds. Tertiary amines do not form associated hydrogen bonds. Amines are capable of forming hydrogen bonds with water. Therefore, lower amines are highly soluble in water. With an increase in the number and size of hydrocarbon radicals, the solubility of amines in water decreases.
Methods for obtaining amines1. R-NO 2 + 6 [H] > R-NH 2 + 2H 2 O (reduction of nitro compounds)
2. NH 3 + CH 3 I > I? > NH3> CH 3 NH 2 + NH 4 I (ammonia alkylation)
3. a) C 6 H 5 -NO 2 + 3 (NH 4) 2 S> C 6 H 5 -NH 2 + 3S + 6NH 3 + 2H 2 O (Zinin reaction)
b) C 6 H 5 -NO 2 + 3Fe + 6HCl> C 6 H 5 -NH 2 + 3FeCl 2 + 2H 2 O (reduction of nitro compounds)
c) C 6 H 5 -NO 2 + ZN 2> catalyst, t> C 6 H 5 -NH 2 + 2H 2 O
4. R-C?N + 4[H]> RCH 2 NH 2 (reduction of nitriles)
5. ROH + NH 3 > Al 2 O 3 ,350 °C> RNH 2 + 2H 2 O (obtaining lower alkylamines C 2 -C 4)
Chemical properties of aminesAmines have a structure similar to ammonia and exhibit similar properties. In both ammonia and amines, the nitrogen atom has a lone pair of electrons. Amines are characterized by pronounced basic properties. Aqueous solutions of aliphatic amines exhibit an alkaline reaction. Aliphatic amines are stronger bases than ammonia. Aromatic amines are weaker bases than ammonia, since the unshared electron pair of the nitrogen atom is shifted towards the benzene ring, conjugating with its ?-electrons.
The basicity of amines is influenced by various factors: the electronic effects of hydrocarbon radicals, the spatial shielding of the nitrogen atom by radicals, and the ability of the resulting ions to stabilize due to solvation in a solvent medium. As a result of the donor effect of alkyl groups, the basicity of aliphatic amines in the gas phase (without solvent) increases in the series: primary< вторичные < третичные. Основность ароматических аминов зависит также от характера заместителей в бензольном кольце. Электроноакцепторные заместители (-F, -Cl, -NO 2 и т. п.) уменьшают основные свойства ариламина по сравнению с анилином, а электронодонорные (алкил R-, -OCH 3 , -N(CH 3) 2 и др.), напротив, увеличивают.
1. CH 3 -NH 2 + H 2 O> OH (interaction with water)
2. (CH 3) 2 NH + HCl > [(CH 3) 2 NH 2] Cl dimethylammonium chloride (reaction with acids)
[(CH 3) 2 NH 2] Cl + NaOH > (CH 3) 2 NH + NaCl + H 2 O (reaction of amine salts with alkalis)
(acylation, does not work with tertiary amines)
4. R-NH 2 + CH 3 I> I? > NH3> CH 3 NHR + NH 4 I (alkylation)
5. Interaction with nitrous acid: the structure of the reaction products with nitrous acid depends on the nature of the amine. Therefore, this reaction is used to distinguish between primary, secondary and tertiary amines.
a) R-NH 2 + HNO 2 > R-OH + N 2 + H 2 O (primary fatty amines)
b) C 6 H 5 -NH 2 + NaNO 2 + HCl> [C 6 H 5 -N? N] + Cl? – diazonium salt (primary aromatic amines)
c) R 2 NH + H-O-N \u003d O\u003e R 2 N-N \u003d O (N-nitrosamine) + H 2 O (secondary fatty and aromatic amines)
d) R 3 N + H-O-N \u003d O\u003e no reaction at low temperature (tertiary fatty amines)
(tertiary aromatic amines)
properties of aniline. Aniline is characterized by reactions both at the amino group and at the benzene ring. The benzene ring weakens the basic properties of the amino group compared to aliphatic amines and ammonia, but under the influence of the amino group, the benzene ring becomes more active in substitution reactions compared to benzene.
C 6 H 5 -NH 2 + HCl > Cl \u003d C 6 H 5 NH 2 HCl
C 6 H 5 NH 2 HCl + NaOH > C 6 H 5 NH 2 + NaCl + H 2 O
C 6 H 5 NH 2 + CH3I > t> +I?
14. Amino acids
Amino acids called hetero-functional compounds, the molecules of which contain both an amino group and a carboxyl group. Depending on the mutual arrangement of the amino- and carboxyl groups, amino acids are divided into ?-, ?-, ?-, etc. According to IUPAC, for the name of amino acids, the NH 2 group is called the prefix amino-, indicating the number of the carbon atom to which it is bonded, followed by the name of the corresponding acid.
2-aminopropanoic acid (?-aminopropanoic, ?-alanine) 
3-aminopropanoic acid (?-aminopropanoic, ?-alanine) 
6-aminohexanoic acid (?-aminocaproic) By the nature of the hydrocarbon radical, aliphatic (fatty) and aromatic amino acids are distinguished. The isomerism of amino acids depends on the structure of the carbon skeleton, the position of the amino group in relation to the carboxyl group. Amino acids are also characterized by optical isomerism.
Methods for obtaining amino acids1. (ammonolysis of halogen acids)
2. CH 2 \u003d CH-COOH + NH 3 > H 2 N-CH 2 -CH 2 -COOH (ammonia addition to ?, ?-unsaturated acids)
(action of HCN and NH 3 on aldehydes or ketones)
4. Hydrolysis of proteins under the influence of enzymes, acids or alkalis.
5. Microbiological synthesis.
Chemical properties of amino acidsAmino acids exhibit the properties of bases due to the amino group and the properties of acids due to the carboxyl group, that is, they are amphoteric compounds. In the crystalline state and in an environment close to neutral, amino acids exist in the form of an internal salt - a dipolar ion, also called the zwitterion H 3 N + -CH 2 -COO?.
1. H 2 N-CH 2 -COOH + HCl> Cl? (formation of salts at the amino group)
2. H 2 N-CH 2 -COOH + NaOH> H 2 N-CH 2 -COO? Na + + H 2 O (formation of salts)
(ester formation)
(acylation)
5. + NH 3 -CH 2 -COO? + 3CH 3 I > -HI> (CH 3) 3 N + -CH 2 -COO? – aminoacetic acid betaine
(alkylation)
(interaction with nitrous acid)
7. n H 2 N-(CH 2) 5 -COOH> (-HN-(CH 2) 5 -CO-) n+ n H 2 O (obtaining capron)
15. Carbohydrates. Monosaccharides. Oligosaccharides. Polysaccharides
Carbohydrates(sugar) - organic compounds having a similar structure and properties, the composition of most of which is reflected by the formula С x (Н 2 O) y, where x, y? 3.
Classification:
Monosaccharides are not hydrolyzed to form simpler carbohydrates. Oligo- and polysaccharides are cleaved by acid hydrolysis to monosaccharides. Well-known representatives: glucose (grape sugar) C 6 H 12 O 6, sucrose (cane, beet sugar) C 12 H 22 O 11, starch and cellulose [C 6 H 10 O 5] n.
How to get1. mCO 2 + nH 2 O > hv, chlorophyll> C m (H 2 O) n (carbohydrates) + mO 2 (obtained by photosynthesis)
carbohydrates: C 6 H 12 O 6 + 6O 2 > 6CO 2 + 6H 2 O + 2920 kJ
(metabolism: glucose is oxidized with the release of a large amount of energy in a living organism during metabolism)
2. 6nCO 2 + 5nH 2 O > hv, chlorophyll> (C 6 H 10 O 5) n + 6nO 2 (obtaining starch or cellulose)
Chemical propertiesMonosaccharides. All monoses in the crystalline state have a cyclic structure (?- or?-). When dissolved in water, the cyclic hemiacetal is destroyed, turning into a linear (oxo-) form.
The chemical properties of monosaccharides are due to the presence of three types of functional groups in the molecule (carbonyl, alcohol hydroxyls, and glycosidic (hemiacetal) hydroxyl).
1. C 5 H 11 O 5 -CHO (glucose) + Ag 2 O > NH 3 > CH 2 OH- (CHOH) 4 -COOH (gluconic acid) + 2Ag (oxidation)
2. C 5 H 11 O 5 -CHO (glucose) + [H]> CH 2 OH-(CHOH) 4 -CH 2 OH (sorbitol) (reduction)
(monoalkylation)
(polyalkylation)
5. The most important property of monosaccharides is their enzymatic fermentation, i.e., the breakdown of molecules into fragments under the action of various enzymes. Fermentation is mainly carried out by hexoses in the presence of enzymes secreted by yeasts, bacteria or molds. Depending on the nature of the active enzyme, reactions of the following types are distinguished:
a) C 6 H 12 O 6 > 2C 2 H 5 OH + 2CO 2 (alcoholic fermentation);
b) C 6 H 12 O 6 > 2CH 3 -CH (OH) -COOH (lactic acid fermentation);
c) C 6 H 12 O 6 > C 3 H 7 COOH + 2CO 2 + 2H 2 O (butyric fermentation);
d) C 6 H 12 O 6 + O 2 > HOOC-CH 2 -C (OH) (COOH) -CH 2 -COOH + 2H 2 O (citric acid fermentation);
e) 2C 6 H 12 O 6 > C 4 H 9 OH + CH 3 -CO-CH 3 + 5CO 2 + 4H 2 (acetone-butanol fermentation).
Disaccharides. Disaccharides are carbohydrates whose molecules consist of two monosaccharide residues connected to each other by the interaction of hydroxyl groups (two hemiacetal or one hemiacetal and one alcohol). The absence or presence of glycosidic (hemiacetal) hydroxyl affects the properties of disaccharides. Bioses are divided into two groups: regenerating And non-restoring. Reducing bioses are able to exhibit the properties of reducing agents and, when interacting with an ammonia solution of silver, oxidize to the corresponding acids, contain glycosidic hydroxyl in their structure, the relationship between monoses is glycoside-glycose. Education scheme regenerating bios on the example of maltose:
Disaccharides are characterized by a hydrolysis reaction, as a result of which two molecules of monosaccharides are formed:
An example of the most common disaccharides in nature is sucrose (beet or cane sugar). The sucrose molecule consists of β-D-glucopyranose and β-D-fructofuranose residues connected to each other through the interaction of hemiacetal (glycosidic) hydroxyls. Bioses of this type do not show reducing properties, since they do not contain glycosidic hydroxyl in their structure, the relationship between monoses is glycoside-glycosidic. These disaccharides are called non-restoring, i.e. not able to oxidize.
The scheme of formation of sucrose:
Sucrose inversion. Acid hydrolysis of (+) sucrose or the action of invertase produces equal amounts of D (+) glucose and D (-) fructose. Hydrolysis is accompanied by a change in the sign of the specific rotation angle [?] from positive to negative; therefore, the process is called inversion, and the mixture of D(+)glucose and D(-)fructose is called invert sugar.
Polysaccharides (polioses). Polysaccharides are natural high-molecular carbohydrates, the macromolecules of which consist of monosaccharide residues. Main representatives: starch And cellulose, which are built from residues of one monosaccharide - D-glucose. Starch and cellulose have the same molecular formula: (C 6 H 10 O 5) n, but different properties. This is due to the peculiarities of their spatial structure. Starch is made up of ?-D-glucose residues, while cellulose is made up of ?-D-glucose. Starch- a reserve polysaccharide of plants, accumulates in the form of grains in the cells of seeds, bulbs, leaves, stems, is a white amorphous substance insoluble in cold water. Starch - mixture amylose And amylopectin, which are built from residues? -D-glucopyranose.
amylose– linear polysaccharide, the relationship between the residues of D-glucose 1?-4. The chain shape is helical, one turn of the helix contains 6 D-glucose residues. The content of amylose in starch is 15–25%.
amylose 
amylopectin Amylopectin– branched polysaccharide, bonds between D-glucose residues – 1?-4 and 1?-6. The content of amylopectin in starch is 75–85%.
1. Formation of ethers and esters (similar to bioses).
2. Qualitative reaction - staining with the addition of iodine: for amylose - in blue, for amylopectin - in red.
3. Acid hydrolysis of starch: starch > dextrins > maltose > α-D-glucose.
Cellulose. Structural polysaccharide of plants, built from residues of β-D-glucopyranose, the nature of the compound is 1β-4. The content of cellulose, for example, in cotton is 90-99%, in hardwoods - 40-50%. This biopolymer has high mechanical strength and acts as a supporting material for plants, forming the walls of plant cells.
Characterization of chemical properties1. Acid hydrolysis (saccharification): cellulose > cellobiose > α-D-glucose.
2. Formation of esters
Acetate fibers are made from solutions of cellulose acetate in acetone.
Nitrocellulose is explosive and forms the basis of smokeless powder. Pyroxylin - a mixture of di- and trinitrates of cellulose - is used for the manufacture of celluloid, collodion, photographic films, varnishes.
M.: 20 0 7. - 1 10 s.
This manual contains in a visual form a course of organic chemistry, studied in grades 10-11 of a comprehensive school. The manual can be used when studying, summarizing and repeating educational material, and can also be useful in organizing systematic repetition in preparation for final or entrance exams.
Format: djvu/zip
Size: 1.5 MB
Download: ifolder.ru
Content
I. Theory of the chemical structure of organic compounds
1 The emergence of organic chemistry as a science (1807 J. Berzelius) 3
2. Organic and inorganic substances. Composition and some properties of organic substances 4
3. Pre-structural theories 5
4. Connection between the concepts of the theory of chemical structure 6
5. Prerequisites for the emergence of the theory of the chemical structure of organic substances 7
6. Theory of chemical structure. Basic provisions (1,2) 8
7. Theory of chemical structure. Basic provisions (3.4) 9
8. Theory of chemical structure. Key points (5) 10
9. Algorithm for searching for possible isomers of alkanes (isomerism of the carbon skeleton) 11
10. Classification of chemical compounds typical of organic compounds (according to the type of chemical transformations) 12
11. Classification of chemical compounds typical of organic compounds (according to the type of bond breaking) 13
12. Classification of hydrocarbons 14
II. Limit hydrocarbons
1. Methane. physical properties. Molecule structure 15
2. Sp3 hybridization 16
3. Alkanes 17
4. Isomers and homologues 18
5. Alkanes (unbranched structure) and alkyls 19
6. Nomenclature (rational) 20
7. Nomenclature (systematic) 21
8. Determination of the qualitative composition of organic compounds 22
9. Chemical properties of alkanes 23
10. Obtaining alkanes 24
11. Use of alkanes 25
12. Cycloalkanes (cycloparaffins, naphthenes) 26
III. Unsaturated hydrocarbons
1. Ethylene (ethene). The structure of the molecule. sp2 - hybridization 27
2. Alkenes (olefins, ethylene hydrocarbons) 28
3. Properties of alkenes 29
4. Properties of alkenes 30
5. Use of alkenes 31
6. Obtaining alkenes 32
7. Diene hydrocarbons (alkadienes) 33
8. Chemical properties of alkadienes (with conjugated bonds) Preparation 34
9. general characteristics rubbers. Their structure and properties 35
10. Acetylene (ethyne). Molecule structure sp-hybritization 36
11. Comparison of the structure of the solecule of ethane, ethylene and acetylene. Comparison of o and ts connections 37
12. Alkynes (acetylenic hydrocarbons) 38
13. Chemical properties of alkynes 39
14. Chemical properties of alkynes 40
15. Application of acetylene 41
16. Obtaining acetylene and its homologues 42
IV. aromatic hydrocarbons
1. Benzene. physical properties. Formula Kekule 43
2. Electronic structure of benzene 44
3. Chemical properties of benzene 45
4. Chemical properties of benzene 46
5. Arenes (Aromatic hydrocarbons. Alkylbenzenes) 47
6. Toluene. Chemical properties. Mutual influence of atoms in a toluene molecule 48
7. Orientation rules in the benzene ring..49
8. The use of benzene. Getting arenas 50
9. Styrene. Naphthalene. Anthracene 51
10. Genetic relationship between groups of hydrocarbons 52
11. General information about hydrocarbon groups 53
12. General information about hydrocarbon groups 54
V. Alcohols and phenols
1. Limit monohydric alcohols 55
2. Chemical properties of alcohols 56
3. Ethanol (Ethyl alcohol) 57
4. Application of saturated monohydric alcohols 58
5. Methods for obtaining alcohols 59
6. Limit polyhydric alcohols 60
7. Ethers 61
8. Phenols 62
9. Chemical properties of phenol (by hydroxo group) 63
10. Chemical properties of phenol (on the benzene ring) 64
VI. Aldehydes and carboxylic acids
1. Aldehydes. Structure. Nomenclature. Isomerism 65
2. Formaldehyde. Receipt. Properties 66
3. Properties of aldehydes 67
4. Properties of aldehydes 60
5. Ketones G9
6. Preparation of aldehydes and ketones 70
7. Carboxylic acids. Homologous series 71
8. Some saturated monobasic acids 72
9. Carboxylic acids. Properties 73
10. Chemical properties of saturated monobasic carboxylic acids 74
11. Chemical properties of saturated monobasic carboxylic acids 15
12. Obtaining carboxylic acids 76
13.0 separate representatives of carboxylic acids. Classification 77
14. Separate representatives of carboxylic acids 78
VII. Complex ethers. Fats
1. Esters 79
2. Chemical properties of esters 80
3. Fats. Classification. Getting 81
4. Chemical properties of fats 82
5. Soaps 83
6. Synthetic detergents (CMC) 84
VIII. hydrocarbons
1. Carbohydrates. Compound. Classification 85
2. Glucose. Structure. Fructose 86
3. Glucose. Chemical properties 87
4. Glucose. Special properties. Application 88
5. Sucrose. Structure. Properties 89
6. Polysaccharides (CeH-mOsJn. Natural polymers 90
7. Starch and cellulose. Chemical properties 91
IX. Amines. Amino acids. Squirrels
1. Amines. Compound. Nomenclature. Isomerism 92
2. Amines. Chemical properties 93
3. Aniline. Structure. Properties 94
4. Amino acids. Nomenclature. Isomerism 95
5. Amino acids. Properties 96
6. Some amino acids of proteins 97
7. Obtaining and using amino acids 98
8. Proteins. Compound. Building 99
9. Protein structures 100
10. Chemical properties of proteins 101
11. Isomerism of classes of compounds 102
12. Genetic connection of organic substances 103
X Application
1. Qualitative reactions of organic compounds 104
2. Qualitative reactions of organic compounds 105
3. Periodic system of chemical elements 106
4. Symbols 107
State budgetary educational institution higher professional education
"Pyatigorsk State Pharmaceutical Academy"
Ministry of Health and Social Development of the Russian Federation
ORGANIC CHEMISTRY
SCHEMES AND DRAWINGS
Textbook for 2nd year students (3, 4 semesters)
(full-time education) for students of 2 and 3 courses (correspondence education)
in discipline C2.B.7 - "Organic Chemistry"
Pyatigorsk, 2011
UDC. 547(076)
Printed by decision of the CMS of the Pyatigorsk State Pharmaceutical Academy. Minutes No. 7 dated April 2, 2003
General edition: Head. Department, Professor Oganesyan E.T.
But on the basis of the current program in organic chemistry for pharmaceutical universities, a manual has been created that allows in a concise and accessible form to obtain information about the structure, methods of preparation and reactivity of the most important classes of organic compounds.
Reviewers: Professor Kompantsev V.A., Associate Professor Saushkina A.S.
Editorial Council:
Belikov V.G. (responsible editor) – prof. Ph.D.; Vergeichik E.N. (deputy editor) - prof., Ph.D.; Pogorelov V.I. (deputy editor) - prof., Ph.D.; Muravieva D.A. – Prof., Ph.D.; Gaevy M.D. – Prof., MD; Gatsan V.V. – Prof., Ph.D.
Karpova V.V.; Bratashova T.M. (responsible secretary)
1.1 Classification and main varieties of nomenclature
1.3 Substitutive nomenclature of functional derivatives
2.2 sp 3 -Hybridization. The structure of alkanes. Forecasting
2.3 Structure of cycloalkanes. reactionary forecasting
2.4 sp 2 -Hybridization. The structure of ethylene. Forecasting
2.5 The structure of butadiene-1,3. The concept of conjugation. Influence
2.7 sp hybridization. The structure of acetylene and the reaction
ability of alkynes .............................................................. ............................................... |
|||
Electronic structure of heterocyclic compounds. |
|||
Prediction of reactivity based on structure analysis .............................. |
|||
Features of the structure of the sp2 -hybrid nitrogen atom .............................................. |
|||
Electronic structure of pyridine ............................................................... .................... |
|||
Electronic structure of pyrrole ............................................................... ...................... |
|||
Electronic structure of pyrazole .............................................................. .................... |
|||
Isomerism of organic compounds ............................................................... ......................... |
|||
Types of isomerism .................................................. ................................................ |
|||
Properties of chiral compounds ............................................................... ................... |
|||
Rules for working with Fisher's projection formulas............................................... |
|||
Stereochemical nomenclature .................................................................. ............................... |
|||
D-, L-notation system .............................................. ................................. |
|||
R-,S-notation system .............................................. ................................. |
|||
Classification and mechanisms of organic reactions .............................................. |
|||
Classification of reactions .................................................................. ................................. |
|||
Mechanism of radical substitution reactions (SR) .............................................. |
|||
Mechanism of electrophilic substitution reactions (SE) .................................................. |
|||
The reaction mechanism of nucleophilic substitution (SN) at |
|||
sp3 -hybrid carbon atom .............................................. ................................. |
|||
Mechanism of electrophilic addition reactions (AdE ) .................................. |
|||
Mechanism of nucleophilic addition reactions (AdN) .............................................. |
|||
Reactivity and methods for obtaining organic substances in |
|||
diagrams ................................................. ................................................. ......................... |
|||
FOREWORD
The study of organic chemistry in pharmaceutical higher educational institutions sets as its most important goal the formation of a methodical approach for students to study the relationship between the structure of molecules and their properties.
The abundance of theoretical material creates the prerequisites for achieving this goal, however, students often experience an urgent need for such a source of information that would allow them to quickly and easily answer many questions related to the study of methods for obtaining and reactivity of organic compounds.
The present tutorial it is designed to help students in a concise and accessible form to obtain information,
concerning the structure and properties of the most important classes of organic compounds.
1. BASES OF CLASSIFICATION AND NOMENCLATURE OF ORGANIC COMPOUNDS
1.1 Classification and main varieties of the nomenclature of organic compounds
Organic chemistry is the chemistry of hydrocarbons and their derivatives. Several million organic compounds are now known. To study such a huge number of substances, they are divided into smaller groups - classes, within which the compounds have similarities in structure, and hence in chemical properties.
Organic substances can be classified according to various criteria: I - according to the structure of the carbon chain, they can be a) acyclic (carbon-
ice chains do not have cycles); b) cyclic (carbon chains are closed in cycles);
II - according to the nature of carbon-carbon bonds, substances are divided into a) limiting (in molecules there are only single carbon-carbon bonds); b) unsaturated (molecules have double or triple carbon-carbon bonds); c) aromatic (cyclic compounds with a special type of bond (see.
III - according to the presence of functional groups, the substances are assigned to different classes (the most important ones are presented in Table 1).
Nomenclature is a set of rules that allow you to give a name to each chemical compound. The replacement nomenclature is of the greatest importance; for derivatives of hydrocarbons, in addition to the substitutional one, the radical-functional nomenclature is often used. For some compounds, trivial (historically established) names are used.
1.2 Substitutive hydrocarbon nomenclature
Hydrocarbons are substances whose molecules consist only of carbon and hydrogen atoms.
To give a name to an acyclic hydrocarbon according to substitutional nomenclature, one must:
1 . Select the parent structure using the following order:
1) the maximum number of multiple (double, triple) bonds;
2) maximum chain length;
3) the maximum number of substituents (radicals).
2* . Number the parent structure so that the smallest values (locants) get:
1) multiple bonds;
2) hydrocarbon substituents.
Each subsequent item is valid in the absence of the previous one, or if the previous one did not give an unambiguous answer.
3 . Name all radicals (see Table 2)
4. Compose a name according to the following scheme:
Console |
Ending |
||||||||||||||||||||||||||||||||||||||
Hydrocarbon |
An - alkanes |
||||||||||||||||||||||||||||||||||||||
deputies |
hydrocarbon |
En - alkenes |
indicating |
||||||||||||||||||||||||||||||||||||
alphabetically |
chain (ancestor- |
Yn - alkynes |
provisions |
||||||||||||||||||||||||||||||||||||
structure) |
Diene - alkadienes |
multiple bonds |
|||||||||||||||||||||||||||||||||||||
For example: |
|||||||||||||||||||||||||||||||||||||||
3-ethylhexane |
|||||||||||||||||||||||||||||||||||||||
C2 H5 |
|||||||||||||||||||||||||||||||||||||||
3-methyl-3-ethylpentene-1 |
|||||||||||||||||||||||||||||||||||||||
CH3 2 |
|||||||||||||||||||||||||||||||||||||||
(CH2) |
|||||||||||||||||||||||||||||||||||||||
C3 H7 CH3 |
|||||||||||||||||||||||||||||||||||||||
3,3,4-trimethyl-4-propylnonin-1 |
|||||||||||||||||||||||||||||||||||||||
2-isopropylbutadiene-1,3 or 2-(1-methylethyl)butadiene-1,3 |
|||||||||||||||||||||||||||||||||||||||
Table 1 |
|||||||||||||||||||||||||||||||||||||||
table 2 |
|||||||
Names of some hydrocarbon substituents |
|||||||
Titles |
|||||||
trivial |
systematic |
||||||
permissible |
|||||||
CH3- |
|||||||
(CH-) |
|||||||
isopropyl |
1-methylethyl |
||||||
CH3-CH2-CH2-CH2- |
|||||||
CH CH2 |
isobutyl |
2-methylpropyl |
|||||
sec-butyl |
1-methylpropyl |
||||||
tert-butyl |
1,1-dimethylethyl |
||||||
II Alkenyls |
|||||||
CH2- |
propen-2-yl |
||||||
III alkynyls |
|||||||
not used |
|||||||
CH2 - |
not used |
propyn-2-yl |
|||||
(C6 H5-) |
|||||||
2-methylphenyl |
|||||||
phenylmethyl |
|||||||
2-phenylethenyl |
|||||||
For cyclic hydrocarbons, either the cycle or the acyclic hydrocarbon chain associated with the cycle is chosen as the parent structure. The numbering of the cycle in the case of the presence of substituents is carried out from one substituent to another so that the locants receive the smallest value.
CH2-CH2-CH3 |
CH C2 H5 |
|||||||||||||
sec-butylbenzene |
||||||||||||||
1-methyl-2-propylcyclopentane |
||||||||||||||
For some cyclic hydrocarbons, IUPAC rules allow the following trivial names:
CCH3 |
|||||||||
ortho-xylene |
meta-xylene |
||||||||
para-xylene |
|||||||||
naphthalene |
|||||||||
anthracene |
|||||||||
phenanthrene |
|||||||||
H3 C C CH3 |
|||||||||
1.3 Substitutive nomenclature for functional derivatives of hydrocarbons
Functional groups (F.G.) - groups of non-carbon atoms |
||||||
nature, replacing hydrogen atoms in the hydrocarbon chain and |
||||||
defining properties (function) of compounds. |
||||||
The most important functional groups are: |
||||||
Table 3 |
||||||
Name |
Name |
Name |
||||
hydroxy- |
||||||
SO3H |
||||||
carbonyl- |
||||||
alkylthio- |
||||||
carboxyl- |
||||||
carbamoyl- |
||||||
carbonyl- |
||||||
According to the nature and quantity of PG, organic compounds are divided into the following |
||||||
common groups: |
||||||
Functional derivatives of hydrocarbons
Monofunctional |
Polyfunctional |
Heterofunctional |
|||||||||||||||||||||
identical F.G.) |
|||||||||||||||||||||||
To give a name to the functional derivatives of hydrocarbons, it is necessary: 1. Choose the parent structure - a hydrocarbon chain linked:
1) with a functional group (for monofunctional compounds);
2) with a large number of functional groups (for polyfunctional compounds);
