On the question of the genetic relationship between organic compounds

Alice (in Wonderland to the Cheshire cat): - Tell me, where should I go from here? Alice (in Wonderland to the Cheshire cat): - Tell me, where should I go from here? Cheshire cat: - It depends on where you want to come? Cheshire cat: - It depends on where you want to come? 2

Synthesis strategy “I want to sing the praises of the creation of molecules – chemical synthesis… …I deeply believe that this is art. And at the same time, synthesis is logic.” Roald Hoffman ( Nobel Prize in Chemistry 1981 d) Selection of starting materials Construction of the carbon backbone of a molecule Introduction, removal or replacement of a functional group Protection of a group Stereoselectivity 5

CO + H 2 Ru, 1000 atm, C ThO 2, 600 atm, C Cr 2 O 3, 30 atm, C Fe, 2000 atm, C ZnO, Cr 2 O 3, 250 atm, C CH 3 OH 6

С n H 2n+2 Scheme of the formation of σ-bonds in a methane molecule Models of methane molecules: ball-and-stick (left) and scale (right) СH4СH4СH4СH4 Tetrahedral structure sp 3 -hybridization σ - bonds homolytic bond breaking X: Y homolytic bond breaking S R) substitution (S R) Combustion Dehydrogenation S - eng. substitution Prediction of reactivity 7

CH 3 Cl - METHYL CHLORIDE CH 4 METHANE C - SOOT C 2 H 2 - ACETYLENE CH 2 Cl 2 - DICHLOROMETHANE CHCl 3 - TRICHLOROMETHANE CCl 4 - TETRACHLOROMETHANE H 2 - HYDROGEN SYNTHESIS GAS CO + H 2 SYNTHESIS GAS CO + H 2 Cl 2, hγ Chlorination С pyrolysis Н 2 О, Ni, C О 2 conversion, Oxidation СH 3 OH – METHANOL HCHO – METHANAL solvents Benzene СHFCl 2 freon HCOOH - formic acid Synthetic gasoline SYNTHESIS BASED ON METHANE 8 СH 3 NO 2 – NITROMETHANE СCl 3 NO 2 chloropicrin CH 3 NH 2 methylamine HNO 3, C Nitration

C n H 2n Scheme of formation of σ-bonds with the participation of sp 2 -hybrid clouds of a carbon atom Scheme of formation of π-bonds with the participation of p-clouds of a carbon atom Model of an ethylene molecule Electrophilic addition reactions (A E) Polymerization Polymerization Oxidation OxidationCombustion 2 – hybridization of σ– and σ – and π – bonds Eb (C = C) = 611 kJ/mol Eb (C – C) = 348 kJ/mol A – English. addition – addition Prediction of reactivity 9

C 2 H 4 Ethylene Polymerization H 2 O, H + Hydration Cl 2 Chlorination Oxidation ETHYL ALCOHOL C 2 H 5 OH ETHYLNE ALCOHOL C 2 H 5 OH 4, H 2 O O 2, PdCl 2, CuCl 2 HDPE HDPE С MPa 80 0 С, 0.3 MPa, Al(C 2 H 5) 3, TiCl 4 SKD LDPE LDPE Butadiene-1,3 (divinyl) Acetic acid Dioxane Acetic acid 10

С n H 2n-2 Scheme of the formation of σ-bonds and π-bonds with the participation of sp-hybrid clouds of the carbon atom Models of the acetylene molecule electrophilic addition reactions (A E) oxidation oxidation di-, tri- and tetramerizations di-, tri- and tetramerizations combustion combustion reactions involving an "acidic" hydrogen atom Linear structure (180 0) (cylindrical distribution of electron density) sp - hybridization σ– and 2 σ - and 2π - bonds Prediction of reactivity 11

C2H2C2H2 HСl, Hg 2+ H 2 O, Hg 2+ Kucherov reaction С act, С trimerization SYNTHESIS BASED ON ACETYLENE ACETATE ALDEHYDE ACETIC aldehyde CuCl 2, HCl, NH 4 Cl ROH dimerization Acetic acid BENZENE SKD Divinyl Chloroprene SC Chloroprene VINYLACE ETHYLENE VINYL ETHER Polyvinyl ethersPolyvinyl chloride VINYL CHLORIDE HCN, СuCl, HCl, 80 0 C ACRYLONITRILE Fibers 12

13

Scheme of the formation of π-bonds in the benzene molecule Delocalization of electron density in the benzene molecule Scheme of the formation of σ-bonds in the benzene molecule with the participation of sp 2 - hybrid orbitals of carbon atoms С n H 2n-6 Prediction of reactivity Planar sp 2 molecule - hybridization of σ– and σ – and π – bonds Aromatic structure Electrophilic substitution reactions (S E) Radical addition reactions (А R) Radical addition reactions (А R) Combustion 14 M. Faraday (1791–1867) English physicist and a chemist. Founder of electrochemistry. Discovered benzene; first received in a liquid state chlorine, hydrogen sulfide, ammonia, nitrogen oxide (IV).

BENZENE H 2 /Pt, C hydrogenation SYNTHESIS BASED ON BENZENE NITROBENZENE NITROBENZENE Сl 2, FeCl 3 chlorination of HNO 3, H 2 SO 4 (conc) nitration of CH 3 Cl, AlCl 3 alkylation CHLOROBENZENE Aniline TOLUENE TOLUENE Benzoic acid 2,4,6- trinitrotoluene STYRENE STYRENE Polystyrene 1. CH 3 CH 2 Cl, AlCl 3 Alkylation 2. – H 2, Ni dehydrogenation CH 2 =CH-CH 3, AlCl 3 alkylation CHLORANE HEXACHLORANE 15

SYNTHESIS BASED ON METHANOL CH 3 OH VINYL METHYL ETHER VINYL METHYL ETHER DIMETHYLANILINE C 6 H 5 N(CH 3) 2 DIMETHYLANILINE C 6 H 5 N(CH 3) 2 3 METHYLAMINE CH 3 NH 2 METHYLAMINE CH 3 NH 2 VINYL ACETATE METHYL CHLORIDE CH 3 Cl METHYL CHLORIDE CH 3 Cl FORMALDEHYDE CuO, t HCl NH 3 METHYLTHIOL CH 3 SH METHYLTHIOL CH 3 SH H 2 S, t C 6 H 5 NH 2 + CO 1 6H +, t

SYNTHESIS BASED ON FORMALDEHYDE METHANOL CH 3 OH METHANOL CH 3 OH HEXMETHYLENTETRAMINE) FORMIC ACID FORMIC ACID Hexogen [O] [H] 1861 A.M. Butlerov 18

CxHyOzCxHyOz genetic connection oxygen-containing organic compounds ALDEHYDES ALDEHYDES CARBOXIC ACIDS CARBOXIC ACIDS KETONES KETONES ESTERS ETHERS ETHERS ALCOHOLS hydrolysis dehydration hydrogenation oxidation, dehydrogenation esterification esterification oxidation H+, t

C n H 2n+2 C n H 2n Cycloalkanes Alkenes C n H 2n-2 AlkynesAlkadienes C n H 2n-6 Arenes, benzene

C n H 2n+2 C n H 2n CycloalkanesAlkenes C n H 2n-2 AlkynesAlkadienes Primary Secondary Tertiary C n H 2n-6 Arenes, benzene 12 C n H 2n Cycloalkanes Alkenes C n H 2n-2 AlkynesAlkadienes α 23

C n H 2n+2 C n H 2n CycloalkanesAlkenes C n H 2n-2 AlkynesAlkadienes Primary Secondary Tertiary C n H 2n-6 Arenes, benzene 12 C n H 2n Cycloalkanes Alkenes C n H 2n-2 AlkynesAlkadienes

C n H 2n+2 C n H 2n CycloalkanesAlkenes C n H 2n-2 AlkynesAlkadienes Primary Secondary Tertiary C n H 2n-6 Arenes, benzene Polyethylene Polypropylene 12 C n H 2n Cycloalkanes Alkenes C n H 2n-2 AlkynesAlkadienes Rubber Catalyst Ziegler - Natta (1963) 25

C n H 2n+2 C n H 2n CycloalkanesAlkenes C n H 2n-2 AlkynesAlkadienes Primary Secondary Tertiary C n H 2n-6 Arenes, benzene Polyethylene Polypropylene Rubbers Fats Phenolformaldehyde resins 12 C n H 2n Cycloalkanes Alkenes C n H 2n- 2 AlkynesAlkadienes

C n H 2n+2 C n H 2n CycloalkanesAlkenes C n H 2n-2 AlkynesAlkadienes Primary Secondary Tertiary C n H 2n-6 Arenes, benzene Polyethylene Polypropylene Rubbers Fats Synthetic dyes Phenol formaldehyde resins 12 C n H 2n Cycloalkanes Alkenes C n H 2n-2 AlkynesAlkadienes

Application of aniline ANILIN N.N. Zinin (1812 - 1880) Medicinal substances Dyes Explosives Streptocide NorsulfazolFtalazol Obtaining aniline - Zinin reaction Tetryl Aniline yellow Nitrobenzene p-Aminobenzoic acid (PABA) Sulfanilic acid indigo Paracetamol 28

C n H 2n+2 C n H 2n Cycloalkanes Alkenes C n H 2n-2 Alkynes Alkadienes Primary Secondary Tertiary C n H 2n-6 Arenes, benzene Polyethylene Polypropylene Rubber Fats Synthetic dyes Phenol-formaldehyde resins Proteins 12 C n H 2n Cycloalkanes Alkenes C n H 2n-2 Alkynes Alkadienes

There is a genetic relationship between different classes of organic substances, which makes it possible to synthesize the desired compounds based on the chosen scheme of transformations. In turn, the simplest organic substances can be obtained from inorganic substances. As an example, consider the practical implementation of reactions according to the following scheme:

acetic acid aminoacetic acid.

1) From carbon (graphite), methane can be obtained by direct synthesis:

or in two stages - through aluminum carbide:

3C + 4Al t Al4 C3

Al4 C3 + 12H2 OCH4 + Al(OH)3 .

2) Ethylene from methane can be obtained different ways in several stages, for example, it is possible to carry out the Wurtz synthesis followed by the dehydrogenation of ethane:

or carry out thermal cracking of methane and partial hydrogenation of the resulting acetylene:

CHCH + H2 Ni CH2 CH2 .

3) Ethyl alcohol is obtained by hydration of ethylene in the presence of an inorganic acid:

CH2 CH2 + H2 OH + , t CH3 CH2 OH.

4) Acetic aldehyde (ethanal) can be obtained by dehydrogenation of ethanol on a copper catalyst, or by oxidation of alcohol with copper (II) oxide:

5) Acetic aldehyde is easily oxidized to acetic acid, for example, by the "silver mirror" reaction, or by interaction with an acidified solution of KMnO4 or K2 Cr2 O7 when heated. Schematically, this can be shown by the following equation (try to write complete reaction equations):

6) The synthesis of aminoacetic acid is carried out through an intermediate stage for the production of chloroacetic acid:

CH3 CO OH + Cl2 P (red) ClCH2 CO OH + HCl

Please note that halogen derivatives of organic compounds, due to their high reactivity, are often used in organic synthesis as starting and intermediate substances.

The structure of molecules of organic compounds allows us to conclude that chemical properties substances and the close relationship between them. Compounds of other classes are obtained from substances of one class by successive transformations. Moreover, all organic substances can be represented as derivatives of the simplest compounds - hydrocarbons. The genetic relationship of organic compounds can be represented as a diagram:

C 2 H 6 → C 2 H 5 Br → C 2 H 5 OH → CH 3 -SON → CH 3 COOH →

CH 3 COOS 3 H 7 ; and etc.

According to the scheme, it is necessary to draw up equations for the chemical transformations of one substance into another. They confirm the interconnection of all organic compounds, the complication of the composition of matter, the development of the nature of substances from simple to complex.

The composition of organic substances most often includes a small number of chemical elements: hydrogen, carbon, oxygen, nitrogen, sulfur, chlorine and other halogens. The organic substance methane can be synthesized from two simple inorganic substances, carbon and hydrogen.

C + 2H 2 = CH 4 + Q

This is one example of the fact that between all substances of nature - inorganic and organic - there is a unity and genetic connection, which are manifested in the mutual transformations of substances.

Part 2. Complete the practical task.

The task is experimental.

Prove that potatoes contain starch.

To prove the presence of starch in potatoes, a drop of iodine solution should be applied to a potato slice. The cut potato will turn blue-violet. The reaction with iodine solution is a qualitative reaction for starch.

E T A L O N

to option 25

Number of options(packages) of tasks for examinees:

Option number 25 from 25 options

Job completion time:

Option number 25 45 min.

Conditions for completing tasks

Labor protection requirements: teacher (expert) supervising the execution of tasks(safety briefing when working with reagents)

Equipment: paper, ballpoint pen, laboratory equipment

Literature for examinees reference, methodical and tables

1. Familiarize yourself with the test items, assessed skills, knowledge and assessment indicators .

Option #25 of 25

Part 1. Answer the theoretical questions:

1. Aluminum. Amphoteric aluminum. Aluminum oxides and hydroxides.

2. Proteins are natural polymers. The structure and structure of proteins. Qualitative reactions and application.

Part 2. Complete the practical task

3. The problem is experimental.

How to experimentally obtain oxygen in the laboratory, prove its presence.

Option 25 out of 25.

In the school course of organic chemistry, the study of the genetic relationship between substances plays a significant role. Indeed, the course is based on the idea of ​​the development of substances as steps in the organization of matter. This idea is also implemented in the content of the course, where the material is arranged in order of complexity from the simplest hydrocarbons to proteins.

The transition from one class of organic substances to another is closely related to the fundamental concepts of chemistry -- chemical element, chemical reaction, homology, isomerism, variety of substances and their classification. For example, in the genetic chain of transformations of methane - acetylene - acetic aldehyde, similar - the preservation of the element carbon in all substances - and different - forms of the existence of this element can be traced. chemical reactions specify the theoretical provisions of the course, and many of them are important in practical terms. Therefore, often genetic transitions between substances are considered not only with the help of reaction equations, but are carried out and, in practice, that is, the theory is connected with practice. Therefore, knowledge about the genetic relationship between substances is also necessary for the polytechnic education of students. When studying the genetic relationship between substances, the unity of nature, the interconnection of its phenomena, is revealed to students. So, inorganic compounds can also be included in the process of transformation of organic substances. This example reflects the intra-subject connection of the chemistry course. In addition, the chain of these transitions is part of a more general one - the phenomenon of the circulation of substances in nature. Therefore, each reaction studied in the course of chemistry acts as a separate link in the entire chain of transformations. In this case, it turns out not only the method of obtaining the product, but also the conditions for the reaction (the use of information from physics and mathematics), the location of raw materials and factories (connection with geography), etc. There is also a problem - to foresee further fate obtained substances and their decay products, their influence on surrounding a person Wednesday. Thus, a number of information from other school subjects is applied and generalized in the material on genetic transitions.

The role of knowledge about the genetic connection between substances is also great in the formation of the dialectical-materialistic worldview of students. Revealing how the simplest hydrocarbons and other organic compounds were formed from inorganic substances, how the complication of their composition and structure led to the formation of proteins that initiated life, we thereby reinforce the materialistic theory of the origin of life on Earth with examples. The laws of dialectics, which students learn in the lessons of social science, are used in the study of genetic transitions. So, the question of the genetic relationship between substances at integrated approach does not appear to him as a separate one, but is integral part common in the education and upbringing of students.

An analysis of students' answers in lessons and exams shows that the question of the genetic relationship between substances causes difficulties. This is explained by the fact that the study of the question of genetic connection, although carried out throughout the entire course of chemistry, is carried out fragmentarily, unsystematically, without isolating the main direction.

In the diagram, the generalized formula corresponds to several groups of substances of the same composition, but of different structures. For example, the formula SpNgp+gO combines isomeric limit monohydric alcohols and ethers, respectively, having their own general formulas.

The straight lines in the general diagram show the main relationships between groups and classes of organic compounds. So, with the help of general formulas, transitions between groups of hydrocarbons are depicted. However, the abundance of lines in the diagram would make it difficult to perceive the main one, and therefore a number of transitions to, it is not shown. The general scheme also allows you to understand the genetic transitions between inorganic and organic substances (the synthesis of hydrocarbons from simple substances and their thermal decomposition), to give a general idea of ​​the cycle of substances using the example of carbon to other elements. You can detail the general scheme using tables of isomeric homologous series of substances, as well as when performing exercise. 16 and 17 (p. 114

Next, we summarize information about intergroup isomers. We note that these include monohydric alcohols and ethers, aldehydes and ketones, phenols and aromatic alcohols, carboxylic acids And esters. The composition of these isomers, as well as singly presented substances in the course (ethylene glycol and unsaturated acids), can be expressed by general formulas. When analyzing such formulas, we identify signs of the complication of substances, determine the place of each group in the genetic chain and reflect this in the general scheme. We carry out its concretization in the lesson and at home when performing ex. 27, 28, 29, 30, 33, 37 (pp. 140-141).

We pose the problem for students about the possibility of further continuation of the general scheme based on the complication of the composition and structure of matter. For these purposes, we pay attention to the composition of fats: the molecule contains six oxygen atoms, based on the formulas of hexatomic alcohol (p. 154), glucose and its isomers (p. 152--156), students derive their general formulas. We also carry out a higher form of work, when the students themselves draw up schemes of the genetic connection between substances and specify them. When analyzing the general scheme, we strive for students to note relative nature the relationships between substances reflected in it. We also ask students to show that general scheme can be continued, since the path of knowledge does not end with what has been studied.

The material world in which we live and of which we are a tiny part is one and at the same time infinitely diverse. Unity and Diversity chemical substances of this world is most clearly manifested in the genetic connection of substances, which is reflected in the so-called genetic series. Let's single out the most characteristics these rows:

1. All substances of this series must be formed by one chemical element. For example, a series written with the following forms st:

2. Substances formed by the same element must belong to different classes, i.e., reflect different forms of its existence.

3. Substances that form the genetic series of one element must be connected by mutual transformations. On this basis, one can distinguish between complete and incomplete genetic series.

For example, the above genetic series of bromine will be incomplete, incomplete. And here is the next row:

can already be considered as complete: it begins with the simple substance bromine and ends with it.

Summarizing the above, we can give the following definition of the genetic series:

The genetic connection is a more general concept than the genetic series, which is, albeit a vivid, but particular manifestation of this connection, which is realized in any mutual transformations of substances. Then, obviously, the first series of substances given in the text of the paragraph also fits this definition.

To characterize the genetic relationship of inorganic substances, we will consider three types of genetic series: the genetic series of the metal element, the genetic series of the non-metal element, the genetic series of the metal element, which corresponds to amphoteric oxide and hydroxide.

I. Genetic range of the metal element. The metal series is the richest in substances, in which different degrees of oxidation are manifested. As an example, consider the genetic series of iron with oxidation states +2 and +3:

Recall that for the oxidation of iron to iron (II) chloride, you need to take a weaker oxidizing agent than to obtain iron (III) chloride:

II. The genetic series of the non-metal element. Similarly to the metal series, the non-metal series with different oxidation states is richer in bonds, for example, the genetic series of sulfur with oxidation states +4 and +6:

Difficulty can cause only the last transition. If you perform tasks of this type, then follow the rule: in order to obtain a simple substance from an oxidized compound of an element, you need to take its most reduced compound for this purpose, for example, the volatile hydrogen compound of a non-metal. In our example:

By this reaction, sulfur is formed from volcanic gases in nature.

Similarly for chlorine:

III. The genetic series of the metal element, to which the amphoteric oxide and hydroxide correspond, is very rich in bonds, since they exhibit, depending on the conditions, either the properties of an acid or the properties of a base. For example, consider the genetic series of aluminum:

In organic chemistry, one should also distinguish between more general concept- "genetic connection" and a more particular concept - "genetic series". If the basis of the genetic series in inorganic chemistry are substances formed by one chemical element, then the basis of the genetic series in organic chemistry (the chemistry of carbon compounds) is made up of substances with the same number of carbon atoms in the molecule. Consider the genetic series of organic substances, in which we include the largest number of classes of compounds:

Each number corresponds to a specific reaction equation:

The last transition does not fit the definition of the genetic series - a product is formed with not two, but with many carbon atoms, but with its help, genetic bonds are most diversely represented. And finally, we will give examples of the genetic connection between the classes of organic and inorganic compounds, which prove the unity of the world of substances, where there is no division into organic and inorganic substances. For example, consider the scheme for obtaining aniline - an organic substance from limestone - an inorganic compound:

Let us take the opportunity to repeat the names of the reactions corresponding to the proposed transitions:

Questions and tasks to § 23