MINISTRY OF EDUCATION AND SCIENCE OF THE RUSSIAN FEDERATION

Federal State Budgetary Educational Institution

higher professional education

“Chuvash State Pedagogical University named after I.Ya. Yakovlev"

Faculty of Science Education

Department of Biology and Chemistry

COURSE WORK

by discipline

"CHEMISTRY OF ORGAN ELEMENT COMPOUNDS"

Topic: Reaction of dimethylphosphite.

Completed:

student Marsova Yu.V.

BiH profile

Checked by: professor

Department of Bioecology

Doctor of Chemical Sciences

Mitrasov Yu.N.

Cheboksary, 2015

Introduction

1. Preparation of esters from acid chlorides. Carbonates and esters of phosphorus acids

1.1 Synthesis of chlorocarbonates and carbonates

1.2 Esters of phosphorus acids

2. Application. Storage conditions and production.

3. Method for producing dimethylphosphite

Conclusion.

References.

Introduction

The processes of hydrolysis, hydration, dehydration, esterification and amidation are very important in the basic organic and petrochemical synthesis industry. Hydrolysis of fats, cellulose and carbohydrates has long produced soap, glycerin, ethanol and other valuable products. In the field of organic synthesis, the processes in question are used mainly for the production of C 2 -C 5 alcohols, phenols, ethers, -oxides, many unsaturated compounds, carboxylic acids and their derivatives (esters, anhydrides, nitriles, amides) and other compounds.

The listed substances have very important applications as intermediate products of organic synthesis (alcohols, acids and their derivatives, aldehydes, -oxides), monomers and starting materials for the synthesis of polymeric materials (phenol, esters of acrylic and methacrylic acids, melamine, chloroolefins), plasticizers and lubricants (esters), solvents (alcohols, ethers and esters, chloroolefins), pesticides (esters of carbamic and thiocarbamic acids). Very often, the reactions under consideration are an intermediate step in multi-stage syntheses of other target products.

The production of these substances is on a large scale. Thus, in the USA they synthesize 500 thousand tons of ethanol and isopropanol, 900 thousand tons of propylene oxide, 200 thousand tons of epichlorohydrin, over 4 million tons of esters, about 300 thousand tons of isocyanates.

1. Preparation of esters from acid chlorides. Carbonates and esters of phosphorus acids

Esters of carboxylic acids are very rarely obtained from acid chlorides, since the latter are expensive substances. In contrast, carbonic acid esters (carbonates) and phosphorus acid esters are synthesized mainly from acid chlorides, since the corresponding acids are not capable of esterification.

1.1 Synthesis of chlorocarbonates and carbonates

These esters are obtained from phosgene COCI 2, which is an acid chloride of carbonic acid (under normal conditions it is a gas that condenses into liquid at +8 0 C). The reaction proceeds by replacing chlorine atoms with an aloxy group in the absence of catalysts. In this case, both chlorine atoms are capable of being replaced, but the first of them quickly, and the second much more slowly. This allows, at a lower temperature and a molar ratio of reagents of 1: 1, to obtain in high yield esters of chlorocarbonic acid (chlorocarbonates), which, according to another classification, are also called chloroformates, i.e. esters of formic acid:

COCI 2 + ROH → CICOOR + HCI

In addition to the temperature and ratio of reagents, the high yield of chlorocarbonates is favored by the order in which the reagents are loaded: alcohol must be added to the excess phosgene. Thus, under periodic conditions, the synthesis of chlorocarbonates is carried out by cooling (to 0 0 C) and stirring, gradually adding the required amount of alcohol to the liquid phosgene. The product is purged from dissolved HCI and distilled, and the released HCI is purified from phosgene and disposed of as hydrochloric acid. Chlorocarbonates are of great practical importance for the production of pesticides - carbamic acid esters (carbamates) RNHCOOR.

Carbonic acid diesters (carbonates) are obtained from phosgene at 70 - 100 0 C and a slight excess of alcohol:

COCI 2 + 2ROH → CO(OR) 2 + 2HCI

A side reaction is the formation of a chloroalkane from alcohol and HCI. If its role is significant, then the resulting HCI can be bound with dry soda, calcium carbonate or a tertiary amine.

When preparing phenol ethers, which are less reactive than alcohols, a reaction is carried out with aqueous solutions of phenolates:

COCI 2 + 2ArONa → CO(OAr) 2 + 2NaCI

In this case, in order to avoid side hydrolysis of phosgene, the process is carried out with a sufficiently concentrated solution of the phenolate and in the presence of free phenol (to reduce the concentration of hydroxyl ions).

Of the diesters of carbonic acid, the main interest is cyclic carbonates of glycols

They are valuable solvents and polycarbonates obtained from phosgene and an alkaline solution of some bisphenols, especially diphenylolpropane:

Dithiocarbonic acid esters (xathogenates) deserve attention. Salts of alkyl xanthogenates are obtained from alcoholic alkali and carbon disulfide (dithiocarbonic anhydride). Sodium isopropyl xanthate is used as an effective herbicide; these are also some xanthate disulfides obtained by the oxidation of alkyl anthogenates:

1.2 Esters of phosphorus acids

Phosphorus acid esters are obtained from phosphorus trichloride PCI 3, phosphorus chloroxide POCI 3 and phosphorus thiotrichloride PSCI 3. The reactivity of these acid chlorides towards alcohols and phenols varies in the series: PCI 3 > POCI 3 > PSCI 3, and, as in the case of phosgene, the replacement of each subsequent chlorine atom slows down more and more. This makes it possible to synthesize partial, complete and mixed (with different alcohols) esters.

Reactions of PCI 3 with alcohols occur very vigorously even at low temperatures with a large release of heat. The substitution is accompanied by the Arbuzov rearrangement, and dialkyl phosphite and alkyl chloride are formed:

PCI 3 + 3ROH → (RO) 2 HP=O + RCI + 2HCI

Most often, dimethyl phosphite HPO(OCH 3) 2 is obtained this way. Its synthesis is carried out (periodically or continuously) in a solution of liquid chloromethane at -24 0 C. The heat of the reaction is removed by evaporation of the solvent, part of which is taken for purification and the commercial product is released. The resulting hydrogen chloride is captured in the form of 20-30% hydrochloric acid. Dimethyl phosphite is purified in a film evaporator by vacuum distillation.

Dimethylphosphite is an intermediate product in the synthesis of other phosphorus-containing substances. Thus, the well-known insecticide chlorophos, which is a derivative of alkylphosphonic acid, is obtained from it. To do this, dimethylphosphite is condensed with chloral while cooling:

There is also a one-stage process that combines the synthesis of dimethyl phosphite from CH 3 OH and PCI 3 and the synthesis of chlorophos from dimethyl phosphite and chloral.

Reactions of POCI 3 with alcohols and phenols are important mainly for the synthesis of extractants (tributyl phosphate), plasticizers (tricresyl phosphate, etc.) and fire retardants.

The interaction of phosphorus chloroxide with alcohols occurs without catalysts and alkalis upon cooling, and only heating is required to replace the last chlorine atom:

POCI 3 + 3 ROH → PO(OR) 3 + 3HCI

To avoid by-product formation of alkyl chlorides

It is necessary to blow off the resulting HCI in a flow of inert gas.

Less reactive phenols react with phosphorus chloroxide when heated and in the presence of catalysts - anhydrous ZnCI 2 or CaCI 2:

POCI 3 + 3ArOH → PO(OAr) 3 + 3HCI

Hydrogen chloride is allowed to evaporate from the reaction mixture and is captured in the form of concentrated hydrochloric acid. In this way, tricresyl phosphate, a plasticizer for polymer materials, is produced on a large scale (periodically or continuously).

Reactions of PSCI 3 with alcohols and phenols are used exclusively for the synthesis of pesticides. The first chlorine atom is replaced by the action of alcohols at 20-30 0 C; to replace the second atom, an alcohol solution of alkali is required; for the third, interaction with an alcoholate or phenolate is required. In the synthesis of most pesticides of this series, the first step is the preparation of dialkyl chlorothiophosphates with the same or different alkyl groups (usually methyl and ethyl):

The pesticides metaphos and thiophos are then obtained respectively from dimethyl and diethyl chlorothiophosphates and sodium p-nitrophenolate:

(RO) 2 PSCI + NaOC 6 H 4 NO 2 + NaCI

The best results are obtained when the reaction is carried out in acetone or methyl ethyl ketone, when both reagents are well homogenized. However, the process can also be carried out with an aqueous solution of nitrophenolate by adding dialkyl chlorothiophosphate to it at 50 - 100 0 C. To avoid side hydrolysis reactions, it is necessary to adjust the pH of the medium so that there is an excess of free phenol.

In a similar way, the insecticide methyl mercaptoforce is obtained from dimethyl chlorothiophosphate and -oxydiethyl sulfide, which is partially isomerized into a thiol derivative and is a mixture of two substances:

There are many other pesticides of this class that are used in the national economy of the country.

2. Application, storage conditions and production.

Dimethylphosphite is used to produce fire retardants, chlorophos, dichlorvos, nitorphos, in the production of pesticides, in the pharmaceutical industry, in the production of organophosphorus preparations, including pyrovotex and insecticides.

Chlorophos, also known as dilox, tkuvon, ricifon, is an insecticide. It is used to treat cattle affected by the cutaneous botfly; it is also widely used in the fight against bedbugs, ticks, thrips, and pests in the plant growing industry; it is easily soluble in water and practically safe for warm-blooded creatures.

Storage conditions.

Dimethylphosphite is stored in covered containers made of corrosion-resistant steel, aluminum alloys, or plastic containers. The storage location must be protected from sunlight at a temperature not exceeding 21 C using an inert gas that reduces reactivity

The guaranteed shelf life is six months at a temperature of 5 C, and three months at a temperature of 20 C.

Production of dimethylphosphite.

Dimethyl phosphite is synthesized by condensation of chlorane and dimethyl phosphate.

Certification information.

Dimethyl phosphite received a state registration certificate in the RPOHVB.

Package.

Dimethylphosphite is poured into containers (railway tanks, stainless steel containers, two-hundred-liter stainless steel barrels, plastic containers, plastic cubes, plastic containers), or into containers provided by the consumer.

Transportation.

Transportation is carried out by all types of transport except water and air. For rail transportation, stainless steel tanks are used. For road transport, containers of smaller tonnage (cubes, containers, barrels) are used.

RUSSIAN FEDERATION FEDERAL SERVICE ON INTELLECTUAL PROPERTY, PATENTS AND TRADEMARKS (51) IPC 7 C07F9/142 (12) DESCRIPTION OF THE INVENTION TO THE PATENT Status: as of January 18, 2011 – may cease to be valid

3. Method for producing dimethyl phosphite.

The invention relates to the field of technology of organic compounds, namely to an improved method for producing dimethyl phosphite. A method for producing dimethyl phosphite is described, including the interaction of phosphorus trichloride with methanol in an environment of evaporating methyl chloride, under reduced pressure, stripping of volatile components and subsequent purification of the resulting product by vacuum distillation, while the process is carried out at a molar ratio of methanol to phosphorus trichloride of 3.02-3.3 :1, with their volume ratio respectively 1.43-1.53:1 and a residual pressure of 0.02-0.04 MPa. The technical result is an increase in the manufacturability and safety of the process. 1 salary files, 1 table.

The invention relates to the chemistry of organophosphorus compounds, namely to the production of dimethyl phosphite, used as an intermediate product in organic chemistry in the production of insecticides, herbicides, fire retardants, etc.

The classical method of obtaining lower dialkyl phosphites by the interaction of phosphorus trichloride and alcohol with a molar ratio of reagents of 1:3, the process is carried out by gradually adding phosphorus trichloride to the alcohol, in a solvent environment and while cooling the reaction mixture. Cooling is carried out using a solvent with a low boiling point, which, evaporating during the reaction, removes the generated heat. Hydrogen chloride and alkyl halide remaining in the mixture are removed by passing a current of dry gas, traces of hydrogen chloride are neutralized with ammonia, and the target product is purified by distillation under reduced pressure (D. Purdela, R. Valceanu. Chemistry of organic phosphorus compounds, M.: Khimiya, 1972 , p.183).

In the reaction of phosphorus trichloride with methanol, the rate and heat of reaction are relatively high, a second phase and a liquid-gas system appear. When in contact with hydrogen chloride under low temperature conditions, dimethyl phosphite decomposes to form monomethyl phosphite and subsequently phosphorous acid (at an increased content of hydrogen chloride in the reaction mass). With a lack of methanol, unstable chlorine-containing quasi-phosphonium compounds are formed, prone to decomposition with the release of large amounts of energy (explosive). The presence of these impurities both during synthesis and in the isolated raw dimethylphosphite reduces the safety of the technological process and complicates further purification of the product by distillation. Many conditions must be met for a safe and at the same time technologically advanced process.

There is a known method for producing dialkyl phosphites by reacting phosphorus trichloride with a lower aliphatic alcohol in an organic solvent and removing the resulting hydrogen chloride, in which, in order to simplify the technology, the process of obtaining dimethyl phosphite is carried out in a preheated column at a temperature in the reaction zone of 45-110 ° C (Patent SU No. 910123, class C 07 F 9/142, published 02.28.82). The method uses the resulting boiling point gradient in a series of reagents: alcohol, phosphorus trichloride, solvent, resulting products and by-products of the reaction (alkyl chlorides and hydrogen chloride). Using this method, a product is obtained containing 96 wt.% dimethylphosphite and up to 0.6 wt.% monomethylphosphite.

The closest in technical essence and achieved result is the method for producing lower dialkyl phosphites, which consists in the fact that a mixture of phosphorus trichloride and methanol and a low-boiling solvent, for example methyl chloride, at a temperature from minus 30°C to plus 10°C under pressure is fed into the reaction a column where the solvent evaporates, entraining the resulting hydrogen chloride. Dimethyl phosphite, collected at the bottom of the column, is sent to the second column with reduced pressure to remove the remaining hydrogen chloride and solvent dissolved in it (stripping), and then the dimethyl phosphite is purified by distillation under vacuum (US No. 2631161, class 260-461, 1953) .

The invention solves the problem of increasing the manufacturability and safety of the process by optimizing the composition of the reaction mass and the resulting raw dimethylphosphite for further purification by vacuum distillation, in particular reducing the amount of impurities in the reaction mass and raw dimethylphosphite: monomethylphosphite, phosphorous acid, as well as unidentifiable impurities.

This problem is solved by the fact that in the known method for producing dimethyl phosphite by reacting phosphorus trichloride with methanol in an environment of evaporating methyl chloride under reduced pressure, stripping of volatile components and subsequent purification of the resulting product by vacuum distillation, according to the invention, the interaction is carried out at a molar ratio of methanol to phosphorus trichloride of 3.02 -3.3:1, with their volume ratio of 1.43-1.53:1, respectively, and a residual pressure of 0.02-0.04 mPa. In addition, the interaction is carried out preferentially at a temperature of 0-30°C.

The synthesis of dimethyl phosphite according to the proposed method is carried out in a reactor, which is a vertical cylindrical hollow apparatus with a conical bottom, made of corrosion-resistant steel, equipped with a distributor for supplying methyl chloride, built into the bottom of the reactor, and two siphons for supplying phosphorus trichloride and methanol, mounted diametrically into the conical part of the reactor. The content of methyl chloride in the reaction mass is constant and maintained at the level of 4.8-5.2 wt.%.

The synthesis temperature of 0-30°C in the reactor is maintained automatically due to the evaporation of liquid methyl chloride supplied to the reaction zone, and the necessary vacuum in the reactor is maintained by a vacuum pump to remove highly volatile substances from the reaction zone - hydrogen chloride, methyl chloride and excess methanol. Raw dimethyl phosphite, not completely freed from volatile products, from the reactor enters a stripping column through a water seal to completely remove residual volatile products, and then the dimethyl phosphite is purified by distillation under vacuum.

The use of the proposed method makes it possible to obtain raw dimethyl phosphite of a stably constant composition with a reduced content of undesirable impurities, which, in turn, makes it possible to isolate the target product of higher quality and increase the safety of the process.

Reducing the molar ratio of methanol to phosphorus trichloride below 3.02, the volume ratio of methanol to phosphorus trichloride below 1.43 and the residual pressure below 0.02 MPa, in addition to increasing the content of the reaction mass and dimethylphosphite-raw monomethylphosphite and phosphorous acid, leads to the production of intermediate products methyl dichlorophosphite and dimethyl chlorophosphite, which are very reactive compounds capable of causing an explosion, and increasing the molar ratio of methanol to phosphorus trichloride above 3.3:1, the volume ratio of methanol to phosphorus trichloride above 1.53 and the residual pressure above 0.04 mPa leads to an increase the content of unidentifiable impurities in the target product and a decrease in yield.

The process is carried out at a molar ratio of the components of methanol to phosphorus trichloride of 3.24:1 and at a volume ratio of the components of 1.50:1.

The continuous volumetric flow rate of reagents and methyl chloride (coolant) is:

Phosphorus trichloride – 0.3-0.8 m 3 /h;

Methanol - 0.4-1.2 m 3 / h;

Methyl chloride – 0.5-2.5 m 3 /h.

Dimethyl phosphite - raw material from the synthesis reactor through a water seal continuously enters the stripping column to completely separate the remaining volatile products. The stripping column consists of a cylindrical, packed part filled with Raschig rings and a hollow cubic part, made in the form of a cone and equipped with a jacket for heating with steam. Stripping of highly volatile products is carried out in continuous film mode at a column bottom temperature of 70-90°C and a residual pressure of 0.093 mPa.

Volatile components (methyl chloride, hydrogen chloride, methanol) are condensed in the heat exchanger and returned to the reactor, and raw dimethyl phosphite, freed from volatile components, is continuously fed for distillation into two successively located rotary film evaporators (RFI).

The process was carried out in the following mode:

The volumetric consumption of raw dimethyl phosphite for feeding RPI is no more than 0.6 m 3 ;

Temperature in the vapor phase no more than 90°C;

Residual pressure not less than 0.093 MPa.

The target product thus obtained contains 99.35% dimethylphosphite.

Examples 2-10. The process was carried out similarly to example 1, changing the molar and volume ratio of the reagents, temperature and pressure.

The results are presented in the table.

	Molar ratio M:TP	Volume ratio M:TP	Reaction temperature mass	Residual pressure, mPa			Yield in synthesis in terms of TF
Notes: M – methanol; TP – phosphorus trichloride; DMF – dimethyl phosphite; MMF – monomethylphosphite; FA – phosphorous acid.

Conclusion:

Widely used in production and in everyday life organophosphorus

compounds (chlorophos, thiophos, karbofos, etc.) caused an increased

frequency of poisoning by them.

Modern views on the principles of treatment of FOS poisoning

based on evidence-based medicine (EBM). Choice of funds

relief of the main syndromes from the standpoint of EBM should be based on

ideas about the mechanism and pathogenesis of intoxication (the principle

validity) and modern information from the pharmacopoeia (principle of effectiveness). Fundamental importance should be given to antidote

therapy. Since the leading pathological processes occur in

synapses, then antidote therapy is aimed at normalizing the conduction

nerve impulses in them.

Poisoning prevention measures play an important role

organophosphorus compounds.

References:

1. Gabrielyan O. S., Ostroumov I. G. Chemistry. M., Bustard, 2008;

2. Chichibabin A.E. Basic principles of organic chemistry. M., Goskhimizdat, 1963. – 922 pp.;

3. Lebedev N. N. Chemistry and technology of basic organic and petrochemical synthesis. M., Chemistry. 1988. – 592 pp.;

4. Paushkin Ya. M., Adelson S. V., Vishnyakova T. P. Technology of petrochemical synthesis. M., 1973. – 448 pp.;

5. Yukelson I. I. Technology of basic organic synthesis. M., "Chemistry", 1968.

Abstract on the topic:

Organoelement compounds

Completed by: FNBMT student

2 courses 241 groups

Lazavoy A.

The chemistry of organoelement compounds arose and is developing at the junction of org. and non-org. chemistry and connects these two areas of chemistry. Organoelement compounds are extremely rare in nature; Most of them are synthesized in the laboratory. conditions.

Organoelement compounds contain a carbon-element chemical bond. Organoelement compounds, as a rule, do not include organic compounds with simple or multiple bonds C--N, C-O, C-S and C-Hal. The reactivity of organoelement compounds is determined primarily by the nature of the carbon-element bond, its strength, polarity, etc. Organoelement compounds are usually divided into organoboron, organosilicon and organometallic compounds. The main group of organoelement compounds is organometallic compounds. A special place among them is occupied by p-complexes of transition metals with unsaturated organic ligands. Such compounds contain delocalized metal-ligand covalent bonds, the formation of which involves fully or partially filled d-orbitals of the metal. Organoelement compounds of other elements, including most organoelement compounds of non-transition metals as well as some transition metal compounds, typically have carbon-element s-bonds of varying polarities.

Rice. 1 Ferrocene is an example of an organoelement compound.

Organometallic compounds

Organometallic compounds contain a metal-carbon (M--C) bond in the molecule. Cyanides, carbides, and in some cases metal carbonyls, also containing an M--C bond, are considered inorganic compounds. Organometallic compounds sometimes include organic compounds of B, Si, As and some other non-metals.

The first organometallic compound (Zeise's salt K?pO) was obtained by W. Zeise in 1827. Subsequently, the work of R. Bunsen, who isolated the organic compound As (1839), and E. Frankland, who obtained diethylzinc (1849), laid the foundation for the chemistry of organometallic compounds. From ser. 19th century to midday 20th century The chemistry of non-transition metal compounds developed predominantly. The main achievement of this period was the synthesis and widespread use of organomagnesium compounds (Grignard reagents). In the 50s 20th century There was a sharp rise in the chemistry of organometallic compounds, especially transition metals. The discovery and establishment of the structure of ferrocene (1951) was followed by the synthesis and isolation of many related organometallic complexes. This was facilitated by the development and implementation of physical research methods, as well as the successful use of organometallic compounds in practice.

Based on the nature of the metal-carbon bond, organometallic compounds are divided into several types:

Compounds with M--C s-bonds in which the organic group is bonded to the metal by a two-electron, two-center covalent bond (in some cases with a noticeably polar character). Most non-transition metals form such compounds. Transition metal compounds of this type are stable only in the presence of p-ligands (CO, cyclopentadienyl, etc.) in the molecule.

Organometallic compounds with ionic bonds M--C. Such compounds are essentially metal salts of carbanions. Characteristic of alkali and alkaline earth metals (with the exception of Li and Mg), for example Na+(C5H5)-, K+(C-=CR), etc. 3) Electron-deficient compounds with bridging two-electron multicenter bonds M--C--M. These include compounds of Li, Mg, Be, Al.

p-Complexes of metal compounds containing p-linked organic ligands (alkenes, alkynes, aromatic compounds, etc.). Organometallic compounds of this type are characteristic of transition metals. Only a few examples are known for non-transition metals.

Complete organometallic compounds are known, in which the metal atom is bonded only to C atoms, and mixed ones, which also contain a metal-heteroatom bond.

The names of organometallic compounds are made up of the names of organic radicals, the metal and other groups attached to the metal, for example, tetraethyl lead [Pb(C2H5)4], dibutyltin dichloride. In the case of p-complexes, the prefix h is used for the C atoms involved in binding to the metal; the names of the bridging ligands are preceded by the prefix m, for example, tetracarbonyl (h-cyclopentadienyl) vanadium, dicarbonylmethyl (h-cyclopentadienyl) iron.

Application

Organometallic compounds have a wide range of applications in organic chemistry. Organolithium and organomagnesium compounds can be used as strong bases or as reagents for nucleophilic alkylation or arylation.

Another area of ​​application of MOS is catalysis. Thus, the Ziegler-Natta catalyst used in industry for the production of polyethylene includes MOS (C2H5)3Al.

Organoboron compounds

Organoboron compounds contain a B atom bonded to an organic residue. Includes: organoborane RnBX3-n (n = 1-3); neutral complexes RnX3-nB*L (u = 1-3); organoborates M (n = 1-4); boronium salts Y, where X-H, Hal, OH, OR", SeR", Np, NR2, NHNHR", SO4, etc., M - metal cation, NH4 or others, L - ether, amine, sulfide , phosphine, etc., Y - anion. Organoboron compounds also include compounds containing B in the cycle (boracyclanes), intracomplex compounds and organocarboranes [for example, R2B-BR2, R2BNHNHBR2, C6H4(BR2)2] and polyboranes. compounds. In all these substances, the coordination number of boron is 3 or 4. The most studied are alkyl-, cycloalkyl-, aryl-, alkenyl- and allylboranes, as well as boracyclanes.

In terms of chemical properties, organoboron compounds differ from organic compounds of Li, Mg, Al and other metals. Thus, alkyl and arylboranes do not react with CO2, organic halides, epoxides, carboxylic acid derivatives, etc. Trialkylboranes, tricycloalkylboranes and aliphatic boracyclanes do not break down with water, alcohols, amines, ketones and esters, solutions of inorganic acids and alkalis up to 100-130°C. This allows many reactions of organoboron compounds to be carried out in aqueous and alcoholic solutions. However, in the hydrides (R2BH)2 and (RBp)2, the B--H bonds are easily cleaved by water and alcohols.

Application

Organoboron compounds are also used to obtain borohydrides and carboranes; as additives to motor and jet fuels, lubricating oils and dyes; as catalysts and cocatalysts for the polymerization of unsaturated compounds in the oxidation of hydrocarbons; antioxidants, bactericides, fungicides; reagents in chemistry analysis, for example calignost NaB(C6H5)4 and cesignost Na[(C6H5)3ВСК] - for the determination and isolation of K+, Rb+, Cs+, NH4+, amines and antibiotics; flavognost (C6H5)2BOCH2CH2NH2 - for the determination, identification and characterization of flavones and isolation of antibiotics. Some organoboron compounds are used in medicine, in particular for neutron therapy of cancer tumors.

Organosilicon compounds

Organosilicon compounds contain the Si-C bond. Sometimes all organic substances containing Si, for example, silicon esters, are classified as organosilicon compounds.

Organosilicon compounds are divided into “monomers”, containing one or more Si atoms, which are discussed in this article, and organosilicon polymers. The following groups of organosilicon compounds are the most studied: organohalipsilanes RnSiHal4-n (n=1-3) and RnSiHmHal4-n-m (n and m = 1.2; m+n=2.3); alkoxysilanes and aroxysilanes Si(OR)4, R"nSi(OR)4-n; organohydrosilanes RnSiH4-n; organoaminosilanes RnSi(NR"2)4-n; organosilanols RnSi(OH)4-nI; organoacyloxysilanes RnSi(OCOR")4-n (n=1-3); silatranes, etc.; compounds with several Si atoms - organosiloxanes with Si--O--Si bonds, organosilazanes with Si--N--Si bonds, organosilatins (Si--S--Si), polyorganosilanes (Si--Si), etc.

According to IUPAC nomenclature, compounds with one Si atom are considered to be derivatives of the silane SiH4, pointing to ours. all substituents associated with the Si atom, except for H atoms, for example. (Cp)2SillCl-dimethylchlorosilane, CF3CpCpSiCl3-3,3,3-trifluoropropyltrichlorosilane. Often the name is taken as a basis. org. connection, adding the name. a corresponding silicon-containing substituent, e.g. Cl2(Cp)SiCpSi(Cp)Cl2-bis-(methyldichlorosilyl) methane.

Application

The main application of monomeric organosilicon compounds is the synthesis of organosilicon polymers. Mono- and difunctional organosilicon compounds are used in the production of organosilicon liquids; difunctional - when producing organosilicon rubbers; di-, tri-, tetra- and polyfunctional - in the production of resins and varnishes. Organosilicon compounds are also used as water repellents, anti-adhesives, finishing agents for fiberglass, textile and building materials, plastic fillers, for modifying the surfaces of sorbents and other materials; obtaining coatings for microelectronic devices, special ceramics; as feedstock in the synthesis of catalysts for the polymerization of olefins, pesticides, medicines, etc., as cross-linking and modifying agents for various polymers, as coolants (up to 400 ° C); tetramethylsilane is a reference substance in NMR spectroscopy. The toxic effect of organosilicon compounds varies widely (LD50 from 0.1 to 5000 mg/kg and above). Thus, the maximum permissible concentration for triethoxylane is 1 mg/m3, tetraethoxysilane is 20 mg/m3, and phenyltriethoxysilane does not cause acute poisoning. The presence of amino groups in organic substituents of organosilicon compounds increases the general toxicity and irritant effect, for example. LD50 (mice, oral) for diethylaminomethyl- and (3-aminopropyl) triethoxysilane 7500 and 250 mg/kg, respectively. For the latter, the MPC is 2.5 mg/m3. 1-arylsilatranes are particularly toxic (LD50 0.1-1 mg/kg). World production of organosilicon compounds (without tetraethoxysilane and ethyl silicates) in 1983 amounted to 300 thousand tons and, according to forecasts, by 2000 it will exceed 800 thousand tons.

organometal compound organoboron silicone

Literature used

Methods of organoelement chemistry, under the general direction. ed. A.N. Nesmeyanova and K.A. Kocheshkova, M., 1963-1978;

Cotton F., Wilkinson J., Fundamentals of Inorganic Chemistry, trans. from English, M., 1979, p. 550-636;

General organic chemistry, trans. from English, vol. 7, M., 1984;

Organometallic chemistry of transition metals. Fundamentals and Applications, trans. from English, parts 1-2, M., 1989;

Comprehensive organometallic chemistry, ed. by G. Wilkinson, v. 1-9. Oxf., 1982.

Mikhailov B. M., Bubnov Yu. N., Organoboron compounds in organic synthesis, M., 1977;

Pelter A., ​​Smith K., in the book: General organic chemistry, trans. from English, vol. 6, part 14, M., 1984, p. 233-537;

KliegelW., Vogue in Biologic, Medizin und Pharmazic, B.-, 1980. Yu. N. Bubnov.

Synthesis of organosilicon monomers, M., 1961;

Andrianov K. A., Methods of organoelement chemistry. Kremniy, M., 1968;

Sobolevsky M.V., Muzovskaya O.A., Popeleva G.S., Properties and areas of application of organosilicon products, M., 1975;

Voronkov M. G., Zelchan G. I., Lukevits E. Ya., Silicon and Life, 2nd ed., Riga, 1978; Khananashvili L. M., Andrianov K. A., Technology of organoelement monomers and polymers, 2nd ed., M., 1983, p. 11-139, 376-400;

Voorhoeve R. J. H., Organohalosilanes. Precursors to silicones, Amst. - N. Y. - L, 1967;

Bazant V., Chvalovsky V., Rathousky J., Organosilicon compounds, v. 1-10, Prague, 1965-1983;

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course work, added 06/03/2012


Definition of complex compounds and their general characteristics. The nature of the chemical bond in a complex ion. Spatial structure and isomerism, classification of compounds. Nomenclature of complex molecules, dissociation in solutions, compound reactions.

abstract, added 03/12/2013


Use of organomagnesium compounds and chemistry of organoelement compounds. Preparation of compounds of various classes: alcohols, aldehydes, ketones, ethers. History of discovery, structure, preparation, reactions and applications of organomagnesium compounds.

course work, added 12/12/2009


Life as a continuous physical and chemical process. General characteristics of natural compounds. Classification of low molecular weight natural compounds. Basic criteria for the classification of organic compounds. Types and properties of bonds, mutual influence of atoms.

presentation, added 02/03/2014


abstract, added 02/21/2009


The concept of heterocyclic compounds, their essence and characteristics, basic chemical properties and general formula. Classification of heterocyclic compounds, varieties, distinctive features and methods of preparation. Electrophilic substitution reactions.

abstract, added 02/21/2009


General characteristics of complex metal compounds. Some types of complex compounds. Complex compounds in solutions. Characteristics of their reactivity. Special systems for compiling chemical names of complex compounds.

test, added 11/11/2009


The concept and essence of connections. Description and characteristics of aromatic heterocyclic compounds. Preparation and formation of compounds. Reactions on atomic nitrogen, electrophilic observation and nucleic substitution. Oxidation and reduction. Quinoline.

lecture, added 02/03/2009


Carbon: position in the periodic table, occurrence in nature, free carbon. Carbon atoms in graphite. Fullerenes are a class of chemical compounds whose molecules consist of carbon. The first method for producing solid crystalline fullerene.

Organoelement compounds are organic substances whose molecules contain an element-carbon chemical bond. This group, as a rule, does not include substances containing carbon bonds with nitrogen, oxygen, sulfur and halogen atoms. According to this classification, one of the organoelement compounds is considered, for example, methyl sodium CH 3 Na, but sodium methoxide CH 3 ONa does not belong to them, since it does not have an element-carbon bond.

Organoelement compounds differ both in chemical and physical properties, and in the methods of their preparation. A large group is represented by organometallic compounds. The first of them - diethylzinc (C 2 H 5) 2 Zn - was obtained in 1849 by E. Frankland. Zinc compounds were widely used in syntheses by A. M. Butlerov and other chemists of the late 19th century. The discovery of organomagnesium and organomercury substances played a decisive role in the development of the chemistry of organoelement compounds. They are used in the synthesis of many organoelement and organic compounds.

Organomagnesium compounds were discovered in 1900 by the French chemist F. Barbier and deeply studied by his colleague V. Grignard. The latter developed a method for their synthesis from halogen-containing hydrocarbons: RX + Mg → RMgX (R-hydrocarbon radical, for example CH 3, C 2 H 5, C 6 H 5, etc., and X is a halogen atom). In modern times, reactions similar to the Grignard reaction have become a common method for the preparation of organometallic compounds (Li, Be, Mg, Ca, Sr, Ba, Al and Zn). Moreover, if the metal atom is not monovalent, then it forms organometallic compounds containing both organic radicals and halogen atoms: CH 3 MgCl, C 6 H 5 ZnBr, (C 2 H 5) 2 AlCl.

Research in the field of organomercury compounds, as well as compounds of lead, tin and other metals, was started by A. N. Nesmeyanov in 1922. Organomercury compounds are used for the synthesis of substances containing less electronegative elements in the voltage series up to Hg (see Voltage series) . This is how very active compounds of alkali metals and aluminum are obtained:

(C 2 H 5) 2 Hg + 2Na → 2C 2 H 5 Na + Hg

Various hydrocarbon derivatives have been obtained using organometallic compounds.

Many organometallic compounds react extremely easily with various substances. Thus, methyl sodium and ethyl sodium explode on contact with air; Organic compounds Be, Ca, Ba, B, Al, Ga, etc. spontaneously ignite in air. Li, Mg and Be compounds ignite even in a CO 2 atmosphere.

Since organometallic compounds oxidize very easily, working with them requires special equipment. Ether solutions of organomagnesium substances are much more stable. They are usually used in laboratory practice.

The chemical bond element - carbon in organoelement compounds can be both polar (ionic) and non-polar. Metals whose cations have a small volume and a large charge form covalent bonds; This is how organomercury compounds and compounds of elements of groups IV and V arise. Metals that easily donate electrons, i.e., having a large volume and a small nuclear charge, for example alkali metals, form ionic bonds in which the carbon atom C carries a negative charge (M metal atom). The presence of a negative charge on the carbon atom of such compounds allows them to be used as catalysts for polymerization reactions in the production of synthetic rubbers. Using organometallic compounds of aluminum and titanium, polyethylene, polypropylene and other polymers are produced.

In the organometallic compounds of phosphorus and arsenic, the element-carbon bonds are polarized in the opposite direction compared to other organometallic compounds. Therefore, their chemical properties are very different from the properties of other substances of similar composition. The element silicon, which is related to carbon, forms strong low-polar bonds with it. In this case, it becomes possible to use the ability of silicon to replace unstable (unstable) bonds with bonds through chemical reactions with the formation of polymer chains. Organosilicon polymers are valuable because they retain their properties at both high and low temperatures and are resistant to acids and alkalis. Coatings made from such polymers reliably protect materials from the destructive effects of moisture. These connections are excellent electrical insulators. Linear silicon-organic polymers are used to make lubricants, hydraulic fluids that can withstand both high and low temperatures, as well as rubbers.

Organoelement compounds are increasingly used in various fields of human activity. Thus, mercury and organoarsenic substances are used in medicine and agriculture as bactericidal, medicinal and antiseptic preparations; organotin compounds - as insecticides and herbicides, etc.

MINISTRY OF EDUCATION OF THE RUSSIAN FEDERATION

URAL STATE UNIVERSITY named after. A. M. GORKY

METHODOLOGICAL INSTRUCTIONS FOR A SPECIAL COURSE

CHEMISTRY OF ORGAN ELEMENT COMPOUNDS

for independent work of master's students of 1 and 2 years of study

Faculty of Chemistry

Ekaterinburg

Guidelines prepared by the department

organic chemistry

Compiled by: Yu. G. Yatluk

Ural State University

Organoelement chemistry is a fundamental scientific discipline that studies carbon compounds containing an element-carbon bond. In a broader sense, organoelement compounds also include compounds in which there is a metal-nonmetal-carbon bond, where the nonmetal is usually oxygen, nitrogen, or sulfur. Such compounds are usually called organic compounds of elements. On the other hand, compounds containing carbon bonds with nitrogen, oxygen, sulfur and halogens are usually not classified as organoelement compounds. This course examines both organoelement and organic compounds of elements. Some attention is paid to compounds of sulfur and halogens in unusual valences. When studying the course, students become familiar with the most important laws relating the structure and properties of organoelement compounds, as well as their application in industry, agriculture and other areas of human activity.

When mastering the chemistry course of organoelement compounds, students must learn:

– correctly name the compounds used in strict accordance with the rules of rational nomenclature, IUPAC nomenclature, know their trivial names;

– distinguish the main classes of organoelement compounds, understand the features of their structure, methods of preparation, understand the relationship of chemical and physical properties, know the areas of application;

– make reasonable assumptions regarding the mechanisms of chemical reactions involving organoelement compounds and use this knowledge to predict possible conditions for the occurrence of chemical reactions;

The basis for successfully solving these problems is a conscientious attitude to classroom activities (lectures, seminars, colloquia). Independent homework is also required (preparing for seminars, colloquiums, completing tests). Independent study of material not covered in lectures is required.

Brief course program

Classification of organoelement compounds (organometallic compounds: compounds with a metal-carbon bond, salts, compounds with radical anions; organic compounds of alkali metals: alkoxides, chelates b-dicarbonyl compounds). Structure. Nomenclature. Physical properties. Receipt methods.

Organolithium compounds in organic synthesis. Joining multiple bonds. Substitution reactions. Regroupings. Reactions of lithium (sodium, potassium) organic compounds with radical anions. Reactions of amides and alkoxides of lithium, sodium and potassium. Dependence of the reactivity of chelates on the alkali metal that forms it.

Organometallic compounds of alkaline earth metals (dialkyl(aryl) derivatives, alkyl(aryl)metal halides). Structure. Nomenclature. Physical properties. Receipt methods.

Organomagnesium compounds in organic synthesis. Joining multiple bonds. Substitution reaction. Regroupings. Synthesis of other organometallic compounds. Calcium and organobarium compounds. Magnesium alkoxides. Magnesium naphthalene. Methoxymagnesium methyl carbonate.

Organocopper compounds. Lithium dialkyl cuprate. Copper acetylenides. Structure. Nomenclature. Preparation methods, reactions. Copper alkoxides. Copper based chelates b-dicarbonyl compounds. Silver acylates.

Zinc, cadmium and organomercury compounds. Structure. Methods of preparation and reaction. Reaction of S.N. Reformatsky. Catalysis by mercury compounds. Dual reactivity a

Organoaluminum compounds. Properties, methods of preparation, reactions. Aluminum hydrides in organic synthesis. Industrial significance of organoaluminum compounds. Organothallium compounds. Mono-, di-, trialkyl(aryl)organothallium compounds. Alkoxides, chelates, acylates of monovalent thallium in organic synthesis.

Germanium, organotin and lead compounds. Properties, methods of preparation and reactions. Industrial use of organic lead compounds. Tin hydride compounds. Compounds of divalent lead, compounds with a lead-lead bond.

Borohydrides and their derivatives in organic synthesis. Organylboranes. Salts of organoborates, their use in organic synthesis. Boron halides and their reactions. Alkoxy and acyloxyboranes, their preparation and properties.

Organosilicon compounds (compounds with silicon-halogen, silicon-hydrogen, silicon-oxygen, silicon-nitrogen, silicon-carbon, silicon-silicon and silicon-metal bonds). Preparation methods, reactions, properties. Polymers based on organosilicon compounds.

Organophosphorus compounds of different valence, oxidation state and coordination number. Comparison of reactivity with compounds of arsenic, antimony and bismuth. The use of organic phosphorus compounds in industry, inorganic ones in organic synthesis.

Organic sulfur compounds: thiols, sulfides, polysulfides, sulfonium salts, sulfoxides, sulfones, sulfenic, sulfoxylic, sulfinic, sulfonic acids. Organic sulfites and sulfates. Thiocarbonyl compounds. Selenium and organotellurium compounds. Properties, methods of preparation, reactions. Analogy with organic sulfur compounds, differences. Mixed compounds of sulfur and selenium.

Compounds containing halogens in the form of positively charged atoms. Iodonium salts, iodine and iodine derivatives. Similar compounds of bromine and chlorine. Perchloric acid and its derivatives in organic chemistry.

Organic transition metal compounds, s- And p- complexes. Reactions of implementation, regrouping. Transition metal alkoxides. Steric control. Polymerization reactions. Biological systems involving transition metals.

General problems of the chemistry of organoelement compounds. Specifics of syntheses and uses. The relationship between reactivity and the position of an element in the periodic table. Possibility of regulating reactivity by changing the valence and degree of substitution of metals and non-metals. Progress of methods of chemistry of organoelement compounds.

Seminar lesson plans

Seminar 1

Classification of organic compounds of alkali metals. Organometallic compounds (compounds with an Me-C bond), alkali metal salts with radical anions; organic compounds of alkali metals (alkoxides, chelates b-dicarbonyl compounds. Structure, nomenclature, physical properties. Receipt methods.

Organolithium compounds in organic synthesis. Addition to multiple bonds (C=C, C=O, C=N). Substitution reactions. Regroupings. Reactions of lithium (sodium, potassium) organic compounds. Anion-radical compounds of transition metals and their reactions. Reactions of amides and alkoxides of lithium, sodium, potassium. Dependence of the reactivity of chelates on the nature of the alkali metal that forms it.

Workshop 2

Classification of organometallic compounds of alkaline earth metals dialkyl-(aryl) derivatives , alkyl(aryl)metal halides). Structure. Nomenclature. Physical properties. Receipt methods.

Magnesium organic compounds in organic synthesis. Addition to multiple bonds (C=C, C=O, C=N). Substitution reactions (halogens, alkoxy groups). Regroupings. Synthesis of other organometallic compounds. Organic calcium and barium compounds.

Magnesium alkoxides. Magnesium naphthalene. Methoxymagnesium methyl carbonate.

Workshop 3

Organocopper compounds. Lithium dialkyl cuprate. Copper acetylenides. Structure, nomenclature. Preparation methods, reactions. Mono- and divalent copper alkoxides. Copper based chelates b-dicarbonyl compounds. Silver acylates. Copper complexes in organic synthesis.

Seminar 4

Zinc, cadmium and organomercury compounds. Structure, methods of production, properties. Reformatsky's reaction. Catalysis by mercury compounds. Dual reactivity a-mercurated carbonyl compounds.

Seminar 5

Organoaluminum compounds. Properties, production method, reactions. Aluminum hydrides as reducing agents. Aluminum alkoxides in organic synthesis. Industrial significance of organoaluminum compounds.

Organothallium compounds. Mono-, di-, trialkyl(aryl)organothallium compounds. Alkoxides, chelates, acylates of monovalent thallium in organic synthesis.

Workshop 6

Organotin and lead compounds. Properties, methods of preparation and reactions. Industrial use of organic lead compounds. Tin hydride compounds. Compounds of di- and trivalent lead, compounds with a Pb-Pb bond.

Seminar 7

Borohydrides and their derivatives in organic synthesis. Organylboranes. Salts of op ga but borates, their use in organic synthesis. Boron halides and their reactions. Alkoxy and acyloxyboranes – preparation and reactions.

Organosilicon compounds (compounds with silicon-halogen, silicon-hydrogen, silicon-oxygen, silicon-nitrogen, silicon-carbon, silicon-silicon and silicon-metal bonds). Methods for obtaining reactions, properties. Polymers based on organosilicon compounds.

Seminar 8

Organophosphorus compounds: pentacoordinate phosphorus derivatives, phosphoric acid derivatives (esters, amides), polyphosphoric acid derivatives, phosphonic acid derivatives, phosphinic acid derivatives, tertiary phosphine oxides, trivalent phosphorus compounds. Phosphorus halides. Arsenic, antimony, bismuth and their organoelement compounds.

Seminar 9

Organic sulfur compounds: thiols, sulfides, polysulfides, sulfonium salts, sulfoxides, sulfones, sulfenic acids, sulfoxylic acids, sulfinic acids, sulfonic acids. Organic sulfites and sulfates. Thiocarbonyl compounds. Reactions of elemental sulfur, thionyl chloride and sulfuryl chloride.

Selenium and tellurium compounds. Properties, methods of preparation, reactions. Analogies with organic sulfur compounds, differences. Mixed compounds containing sulfur and selenium.

Seminar 10

Compounds containing halogens as vice positively charged atoms. Iodonium salts, iodine and iodine derivatives. Similar compounds of bromine and chlorine. Perchloric acid and its derivatives in organic synthesis.

Specifics of the synthesis of organofluorine compounds. Special fluoridating agents. Fluorinated hydrocarbons in industry, fluorinated polymers. Biologically active organofluorine compounds.

Problems to solve independently

Problems for seminar 1

1. Carry out the transformation of RC BUT ® RCOR' via dioxolane, 1,3-dithiane and imidazolidine.

2. Consider the ways of synthesizing ketones directly from carboxylic acids.

3. Obtain dibenzyl from dimethylbenzylamine.

4. When treating a suspension of lithium in cetane with chloride rubs-butyl followed by passing carbon dioxide and destroying the resulting mixture with water, two signals with a chemical shift of 1.07 and 0.85 ppm are observed in the 1H NMR spectrum of the reaction mixture. respectively, and the integral ratio is 4.67:1. How did the reaction go?

5. Carry out the transformation:

RCH2COOH ® RC(CH3)2COOH

Compare with the industrial method of obtaining higher isoacids.

6. Obtain dibenzoylmethane from styrene (consider options).

7. Synthesize acrolein diethyl acetal from allyl ethyl ether.

8. Compare the possibilities of direct metalation of benzene and toluene in the subgroup of alkali metals.

Problems for seminar 2

1. Consider the possibilities of interaction of trifluoroacetaldehyde with organomagnesium compounds.

2. Compare methods for the synthesis of propionic aldehyde from various derivatives of formic acid.

3. Write diagrams of the processes of methyl ketones with organomagnesium compounds, magnesium alkylamides and alkoxides, as well as magnesium naphthalene.

4. Characterize the possibilities of interaction of hexahalobenzenes with methylmagnesium iodide depending on the halogen used.

5. Synthesize vinyl malonic ester from butyrolactone.

6. Consider the reactions of organoberyllium compounds depending on the structure of the organic radical.

7. Compare the reactivity of phenylacetylenides of alkaline earth metals depending on the position of the metal in the periodic table.

Problems for seminar 3

1. Obtain 6-oxoheptanoic acid from adipic acid.

2. Obtain butanol-2 from propanol-2.

3. From propargyl alcohol, obtain ethyl ester of 3,4-pentadienoic acid.

4. Obtain 2,6-diphenic acid from benzonitrile.

5. From hexafluoropropylene, obtain 2-bromofluoropropane.

6. Consider the possibilities of reactions of interaction of silver carboxylates with halogens.

7. Obtain chlorobenzene from aniline without diazotization.

Problems for seminar 4

1. Obtain methyl acetoacetic ester and methyl acetylacetone using the same raw materials.

2. Obtain methyl methacrylate from dimethyl oxalate.

3. Obtain methylallyl ketone from acetonitrile.

4. Obtain cinnamic acid without using the Perkin reaction.

5. Present the nature of oxidation of cyclic ketones catalyzed by mercury salts.

6. Obtain styrene from phenylacetic aldehyde.

7. Obtain isopropylacetamide from propylene.

Objectives for the seminar 5.

1. Using organoaluminum compounds, obtain butyraldehyde, butylamine and butyl vinyl ether.

2. Synthesize triacetylmethane using all possible methods.

3. Obtain phenylmaldehyde from cinnamaldehyde.

4. Synthesize 1,1-diethoxyethylene from methyl chloroform.

5. Synthesize cyclopentanecarboxylic acid and its aldehyde from cyclohesanol.

6. Synthesize 1,4-diphenylbutadiene from styrene.

7. Consider the possibilities of synthesizing glycidol esters using thallium compounds, compare the synthesis method with methods used in industry.

Problems for seminar 6

1 Compare the reduction of acid chlorides of valeric and allylacetic acids using tin hydrides.

2. From malonic acid, obtain acetone, lactic acid, and acetaldehyde.

3. From propionic acid, obtain ethanol, ethylene and ethyl chloride and iodide.

4. Obtain methyl acetamide from ethylamine.

5. Obtain 4-oxoheptanoic acid from heptanol

6. Compare industrial methods for producing tetraethyl lead. Consider possible replacements for this compound in the production of high-octane gasoline.

Problems for seminar 7

1. From methyl ethyl ketone, obtain butynol and diethyl ketone.

2. Obtain tripropylcarbinol from acetone.

3. Obtain from trimethyl borate and naphthalene b-naphthol.

4. Synthesize benzophenone from phenyltrimethylsilane.

5. From trimethylallylsilane obtain 1,1-dimethylbuten-4-ol-1.

6. Obtain phenylpropionic acid from malonic ester.

7. Synthesize isopropylamine from acetone.

8. Compare methods for obtaining silyl ethers of enols

Problems for seminar 8

1. Obtain vinyltriphenylphosphonium bromide. Describe its interaction with salicylic aldehyde.

2. Propose the synthesis of diphenylphosphine lithium, use it for dealkylation of anisole and phenetol, explain the differences.

3. Describe the interaction of pyruvic acid methyl ester with trimethylphosphite.

4. Consider the interaction of triethylphosphite with ortho-substituted nitrobenzenes.

5. Consider the change in the nature of the interaction of hexamethapol with cyclohexanone at different interaction times

6. Compare methods for producing mono-, di- and triesters of phosphoric and phosphorous acids.

Problems for seminar 9

1. Suggest a method for obtaining dibutyl sulfate from available reagents.

2. From benzene sulfonyl chloride, obtain methylphenyl sulfone.

3. 2,4-Dinitrophenylsulfenyl chlorides are used to identify organic compounds, describe how.

4. Describe the reactions of alkylbenzenes with thionyl chloride in the presence of pyridine.

5. Obtain 4-dimethylaminopyridine from pyridine.

6. Write a diagram of the interaction of sulfur with cumene in the presence of a strong base.

Problems for seminar 10

1. Propose a method for the synthesis of aryl fluorides without the use of diazonium tetrafluoroborates.

2. Using diethylamine and trifluorochloroethylene, obtain methyl fluoride.

3. Describe the interaction of trifluoromethylphenylketone with triphenylphosphine and sodium chlorodifluoroacetate.

4. Using enanthic and perfluoroenanthic acids, obtain semi-fluorinated dodecane.

5. Compare reagents for direct fluorination of hydrocarbons, select the most accessible laboratory reagent.

6. Using perchloric acid instead of Lewis acids. Compare the reactivity of the substrates.

Colloquium plans

Colloquium 1. Organometallic compounds

Formation of carbon–carbon bonds in reactions of organometallic compounds. Grignard reagents as electrophiles. Alkylation (reactions with carbonyl compounds, nitriles, azomethines, a,b-unsaturated compounds, etc.). Other organometallic compounds and electrophiles (lithium, zinc, cadmium and organocopper compounds).

Reactions of nucleophiles (lithium, sodium, magnesium derivatives). Alkynyl copper compounds.

Reactions of metal alkoxides ( rubs-potassium butoxide, branched sodium alkoxides, thallium alkoxides). Catalysis of reactions with alkoxides, metals with high coordination numbers (aluminum, titanium, vanadium, chromium). Amides of alkali and alkaline earth metals as bases, their reactions (amides of lithium and magnesium). Amidation with titanium amides or titanium tetrachloride (silicon, tin) – amine systems.

Metal carboxylates. Carboxylates of silver, lead, thallium and bismuth are specific reagents of organic synthesis

Colloquium 2. Organic compounds of non-metals

Hydroboration with complex boranes and alkylboranes. Reactions of organoboron compounds (conversion into alcohols, amines, halogen derivatives). Thermal transformations, reactions with acids and carbon monoxide. Hydroboration of unsaturated compounds.

Organophosphorus reagents. Formation of double carbon-carbon bonds (Wittig reaction). Transformations of functional groups (replacement of hydroxyl with halogen, formation of amides, esters, etc.) comparison of the reactivity of Wittig reagents in the V subgroup of the periodic table.

Restoration of nitrogen-containing functions using trivalent phosphorus compounds.

Schedule of control activities

№	Test lesson and its topic	Literature
1	Seminar 1.Alkali metal compounds.
2	Seminar 2.Alkaline earth metal compounds.
3	Workshop 3. Organic compounds of copper and silver.
4	Seminar 4.Zinc, cadmium and organomercury compounds.
5	Seminar 5.Aluminum and organothallium compounds.
6	Seminar 6.Organotin and lead compounds.
7	Colloquium 1. Organometallic compounds.	See above.
8	Seminar 7. Boron and organosilicon compounds.
9	Seminar 8.Organophosphorus compounds
10	Seminar 9.Organic sulfur compounds.
11	Seminar 10.Organofluorine compounds, compounds of higher valence halogens.
12	Colloquium 2. Organic compounds of non-metals.	See above.

Changing and introducing functions in the chemistry of organoelement compounds

1. Reactions without changing the oxidation state

IN ¯ From ®	->C -H	>C=CR-H	R.C. = CH	Ar-H
->C-H
>C=CR-M
R.C. = C-M
Ar-M
->C-B<
->C-P<
->C -Si<-

Typical examples

MH2O

1-1 R-X ¾ ® R-M ¾ ® R-H

C2H5COOH

(C 6 H 13) 3 B ¾ ¾ ¾ ¾ ® C6H14

H2O

ArSO3H ¾ ® ArH

1-3PhC = CH ¾ ® Ph.C. = CNa

BuLi

AlkC = CH ¾ ® Ph.C. = CLi

Cu(NH 3) 4 +

Ph.C. = CH ¾ ¾ ¾ ¾ ® Ph.C. = Cu

1-5C 6 H 5 Na

C6H5CH3 ¾ ¾ ¾ ¾ ® C6H5CH2Na

t-BuOK

CH 3 SOCH 3 ¾ ¾ ¾ ® CH 3 SOCH 2 K

CH 3 ONa

CH3NO2 ¾ ¾ ¾ ® NaCH2NO2

t-BuOK

PhCH 2 COOt-Bu ¾ ¾ ¾ ® PhCHKCOOt-Bu

1-6BF 3 . OEt 2

PhLi ¾ ¾ ¾ ® Ph 3B

1-7PCl 3

i-Pr MgCl¾ ¾ ® i-Pr 2 PCl

2. Reduction reactions

IN ¯ From ®	->C-X		>C=C<
->C-Li
->C-Mg-
->C-Zn-
->C-Al<
->C-B<
->C-P<
->C-Si<-

Typical examples

2-1Li

RX ¾ ® RLi

2-2Mg

RX ¾ ® RMgX

2-3Mg

CH 3 OSO 2 OCH 3 ¾ ® CH 3 MgOSO 2 OCH 3

2-4Zn

CH 3 CH=CHCH 2 Br ¾ ® CH 3 CH=CHCH 2 ZnBr

2-7PhPH 2 + CH 2 =CHCN ¾ ® PhP(CH 2 =CHCN) 2

H2PtCl6

2-8RCH=CH 2 + HSiMe 3 ¾ ¾ ¾ ® RCH 2 CH 2 SiMe 3

3. Oxidation reactions

IN ¯ From ®
ROH(R)
RNH 2
RPX 2
RS-, SO 2 -, SO 3 -			3-10

Typical examples

SO 2

C12H25MgBr ¾ ¾ ® C 12 H 25 SO 2 H

SO2Cl2

PhMgCl ¾ ¾ ® PhSO2Cl ¾ ® PhSO3H

3-10

Literature

1. Talalaeva T.V., Kocheshkov K.A. Methods of organoelement chemistry. Lithium, sodium, potassium, rubidium, cesium. Book 1-2, M., from the USSR Academy of Sciences, 1963.

2. General organic chemistry. T.7, M., Chemistry, 1984.

3. Ioffe S.T.. Nesmeyanov A.N. Methods of organoelement chemistry (magnesium, beryllium, calcium, strontium, barium). M., from the USSR Academy of Sciences, 1963.

4. Carey F., Sandeberg R. Advanced course in organic chemistry. M., Chemistry, 1981, vol. 2, pp. 165-184.

5. Sheverdina N.I., Kocheshkov K.I. Methods of organoelement chemistry. Zinc, cadmium. M., Nauka, 1964.

6. Makarova L.G. Nesmeyanov A.N. Methods of organoelement chemistry. Mercury. M., Nauka, 1965.

7. Nesmeyanov A.N., Sokolik R.A. Methods of organoelement chemistry. Boron, aluminum, gallium, indium, thallium. M., Nauka, 2 vol. 1964.

8. Kocheshkov K.A., Zemlyansky N.I., Sheverdina N.I. and others. Methods of organoelement chemistry. Germanium, tin, lead. M., Nauka, 1968.

9. General organic chemistry. M., Chemistry, vol. 6, 1984.

10. Andriyanov K. A. Methods of organoelement chemistry. Silicon. M., Nauka, 1968.

11. Mikhailov B.M., Bubnov Yu.N. Organoboron compounds in organic synthesis. M., Nauka, 1977.

12. General organic chemistry. M., Chemistry, vol. 4, 1983, pp. 595-719.

13. General organic chemistry. M., Chemistry, vol. 5, 1984.

14. Nifantiev E.E. Chemistry of organophosphorus compounds. M., Chemistry, 1971.

15. General organic chemistry. M., Chemistry, vol. 1, 1981, pp. 622-719.

16. Gublitsky M. Chemistry of organic fluorine compounds. M. Goskhimizdat, 1961.

17. Sheppard W., Sharts K. Organic chemistry of fluorine. M. Publishing House, 1972.

18. Dorofeenko G.N., Zhdanov Yu.A., Dulenko V.I. and others. Perchloric acid and its compounds in organic synthesis. Rostov, from the Russian State University, 1965.

Further reading

1. Rokhov Y., Hurd D., Lewis R. Chemistry of organometallic compounds. M., Publishing House, 1963.

2. Fizer L., Fizer M. Reagents for organic synthesis. M., Mir, vol. I -VII, 1970-1978.

Introduction3

Brief course program4

Seminar lesson plans6

Problems for independent solution9

Colloquium plans14

Schedule of control activities16

In the history of the development of organic chemistry there are many examples when some sections of this science, which had not previously attracted much attention from researchers, began to develop rapidly due to the unexpected practical application of one or another class of compounds or the identification of their new properties.

Some data from the history of organoelement compounds

One such example involves sulfonamides. The use of sulfa drugs as valuable therapeutic agents marked the beginning of the intensive development of this area of ​​organic chemistry - several thousand new sulfa drugs were synthesized in a short time.

The chemistry of organoelement compounds is now in a similar stage of rapid development. This can be seen from many examples. The chemistry of organophosphorus compounds, which for a long time were of only theoretical interest, is now rapidly developing due to the widespread use of organic phosphorus derivatives in various areas of the national economy. The development of the chemistry of organic compounds of titanium and aluminum was accelerated after the discovery by Ziegler in 1954 of the ability of organoaluminum compounds in a mixture with titanium tetrachloride to cause the polymerization of ethylene, as well as the discovery by Natta in 1955 of the possibility of stereospecific polymerization of unsaturated compounds in the presence of various complex catalysts.

The chemistry of organosilicon compounds is also developing in leaps and bounds. The first compound containing silicon and carbon, ethyl ester of orthosilicic acid, was obtained by the French scientist Ebelmain in 1844. Later, in 1963, Friedel and Crafts synthesized the first organosilicon compound with a Si-C bond - tetraethylsilane. At the beginning of the development of the chemistry of organosilicon compounds, silicon, as the closest analogue of carbon, attracted much attention from researchers. It seemed that on the basis of silicon it was possible to create the same broad field of chemical science as organic chemistry. But it turned out that silicon, like carbon, does not form stable chains of molecules from series-connected Si atoms, and therefore interest in organic derivatives of silicon immediately dropped. However, the development of the chemistry of high-molecular compounds could not be limited only to the use of carbon and organogenic elements (oxygen, halogens, nitrogen, sulfur) to build polymer molecules; it naturally aimed to involve other elements of the Periodic Table. This was dictated by a number of considerations, according to which it was assumed that replacing carbon in the main chain of the molecule with other elements would lead to a radical change in the properties of the polymer.

Silicon was the first element used by K. A. Andrianov (1937), and a little later by M. M. Coton (1939) for the construction of inorganic main chains of large molecules, consisting of alternating silicon and oxygen atoms and framed by organic radicals. Thus a new class of organosilicon polymers appeared, now known as polyorganosiloxanes, siloxanes or silicones. Thus, Soviet researchers for the first time demonstrated the possibility of using organosilicon compounds (silicones) for the synthesis of polymers with inorganic molecular chains and side organic groups. This stage became a turning point in the chemistry of organosilicon polymers and served as the beginning of intensive research not only on organosilicon polymers, but also on other organoelement high-molecular compounds,

In the USA, the first reports on polyorganosiloxanes appeared in 1941 (Yu. Rokhov). In the preface to the Russian edition of the book by Yu. Rokhov, D. Hurd and R. Lewis “Chemistry of organometallic compounds” (1963), Yu. Rokhov wrote: “As one of the followers of the fundamental works of K. A. Andrianov and L. M. Coton in the field of chemistry of silicon-organic compounds, I fully recognize the successes of Russian scientists in the field of synthesis and study of organometallic compounds."

Recently, great interest has been shown in organoelement polymers from various sectors of the economy, especially mechanical and apparatus engineering, aviation and rocketry; At the same time, the highest demands are placed on the thermal stability of polymers. Let's take energy as an example. Expansion of the areas of application of power units requires an increase in the scale of production of electrical equipment and, in connection with this, an exceptionally large consumption of copper, magnetic materials, etc. In addition, in connection with the development of aviation, navy and rocket technology, as well as the electrification of underground work, it becomes necessary to reduce weight and reduce the size of electrical equipment. All this forces designers to create electrical devices that have high power with low weight and dimensions. When solving these issues, it is naturally necessary to increase the current density, and this leads to a sharp increase in the operating temperature of the machine or apparatus. Since polymers are the most important materials for the manufacture of any energy units, it is necessary to take into account that they, as dielectrics, are the first to perceive the heat generated by conductive elements. And here the thermal stability of polymer materials becomes especially important.

The introduction of nuclear energy into the energy sector further tightens the requirements for dielectrics. In particular, at present we need dielectrics that can operate for a long time at 180-200°C, and during short-term operation withstand temperatures of 250-350°C and higher. Another example comes from modern aviation. Airplane speeds are now increasing at an incredibly fast pace; When landing such high-speed aircraft, temperatures in aircraft tires reach 320°C and higher. Along with this, it becomes extremely difficult to protect high-speed aircraft from the heat generated when moving through the atmosphere at high speed. Heat-resistant polymers should also help to successfully solve the problems of space exploration.

Polyorganosiloxanes, as already mentioned, were the first representatives of high-molecular compounds with inorganic main chains of molecules framed by organic groups. These polymers opened up a new area that chemical science is developing without copying natural substances or materials, since polymers of this composition are unknown in nature and were developed from beginning to end in the laboratory. Research on organoelement high-molecular compounds especially expanded in the post-war period, and is now being carried out in all industrialized and developing countries. The number of publications and patents in this area is growing every year, and new works of a theoretical and applied nature are constantly appearing. In parallel with this, the industry of organoelement polymers and monomers is rapidly developing; World production of organosilicon monomers and polymers alone has currently reached 1 million tons per year.

Researchers working on the synthesis of polymers focus on 45 elements of the Periodic Table. The most important elements involved in constructing polymer chains are listed below:

• II group Mg, Zn

• III group B, Al

• IV group C, Si, Ti, Ge, Zr, Sn, Pb

• V group N, P, V, As, Sb, Bi

• VI group O, S, Cr, Se, Mo

• VIII group Fe, Co, Ni

Indeed, it turned out that many of them (B, Al, Si, Ti, Sn, Pb, P, As, Sb, Fe) are capable, in combination with oxygen and nitrogen, of forming inorganic chains of polymer molecules with side organic and organosiloxane groups; Some of these polymers have already found industrial application. It should be expected that in the coming years the development of new synthesis methods will lead to the production and introduction into industry of new organoelement polymers with important properties.

Features of chemistry in the technology of organoelement compounds

Organoelement compounds differ significantly in properties and structure from both organic and inorganic compounds - they occupy an intermediate position. Organoelement compounds are rare in nature; they are obtained synthetically.

In the chemistry of living organisms, the role of organoelement compounds is not yet entirely clear, however, it can be said with confidence that compounds of silicon, phosphorus and other elements play a significant role in the life activity and metabolism of living organisms at a high level of evolutionary development, in particular humans. In the human and animal body, silicon-containing compounds are present in various forms, including in the form of organosilicon and complex compounds, soluble in organic solvents. Nevertheless, for organosilicon compounds, only one case of their discovery in nature is known - an individual ester of orthosilicic acid with the composition Si(OC34H69)4 was isolated from bird feathers. Organophosphorus compounds, primarily esters of phosphoric and polyphosphoric acids, play a major role in the chemistry of living organisms. Thus, adenosine triphosphate (ATP) is found in living tissue and plays a vital role as an energy source.

Organoelement compounds have several characteristic features that fundamentally distinguish them from carbon compounds.

1. Differences in the selective affinities of elements compared to carbon.

Electropositive elements (Si, B, Al, P) have a much greater affinity for electronegative elements than carbon. In other words, silicon, boron, aluminum, phosphorus and other elements form weaker bonds with electropositive elements (H, Si, B, Al, As, Sb, Bi, etc.), but stronger bonds with electronegative ones (O, N, Cl, Br, F, etc.) than carbon.

When considering the electronegativity of various elements, it is clear that carbon (xC = 2.5) occupies approximately a middle position between the most electronegative element - fluorine (xF == 4.0) and the most electropositive elements - cesium and francium (xCs = 0.7, xFr == 0.7). The half-sum of the electronegativities of these elements is xpc = 2.35 and, therefore, the C atom has the least tendency to give or receive electrons, that is, to form positive or negative ions. This means that the carbon in the compounds is less ionized compared to electropositive or electronegative elements. For example, if the Si-C1 bond is ionized by 30-50%, then the C-C1 bond is approximately 6% ionized. Therefore, carbon is least susceptible to electrophilic or nucleophilic attack, which means that the C-C bond is much stronger than the E-E bond (for example, BB, Si-Si, A1-A1, P-P, As-As) , and vice versa, for example, the C-O bond, the half-sum of electronegativity of which is equal to xpc = 3.0, is less strong than the A1-O (xpc = 2.5), Si-O (xpc = 2.65), Si- N (xps = 2.4), etc. Comparison of the bond energy of boron, silicon, phosphorus, arsenic atoms with the bond energy of carbon atoms confirms these provisions (Table 1).