Physico chemical properties of elementogenic compounds. What is chemistry of elementogenic connections? Tasks for self solutions
Elementorganic connections - organic substanceswhose molecules contain chemical communications "Element - carbon." This group, as a rule, do not include substances containing carbon bonds with nitrogen, oxygen, sulfur and halogen atoms. According to such a classification, one of the element organic compounds For example, methyl sodium CH 3 Na is considered, but it does not apply to the sodium methylate CH 3 ONA, since it does not have the connection "element - carbon".
Elementorganic compounds differ as chemical and physical propertiesand according to the methods of their receipt. Metal organogenic connections are a large group. The first of them is dimethyl cycink (CH 3) 2 Zn, diethyl cyca (C 2 H 3) 2 Zn - were obtained in 1849 by the English chemist E. Frankland. Zinc compounds were widely used in synthesis A.M. Butlerov and other chemist scientists end XIX. in. A decisive role in the development of chemistry of elementogenic compounds was played by the opening of magnesium and mercury and mercury. They are used in the synthesis of many elementogenic and organic compounds.
Magniorganic compounds were opened in 1899 by the French chemist F. Barbie and deeply studied by his colleague V. Grignar. The latter developed the method of their synthesis of halogen-containing hydrocarbons: Rx + Mg → RMGX (R is a hydrocarbon radical, for example CH 3, C 2 H 5, C 6 H 5, et al., And X is a halogen atom). Nowadays, the reaction time, similar reactions of Grignar, became a common method of producing metal organic compounds (Li, BE, MG, CA, SR, BA, AL and Zn). Moreover, if the metal atom is not monovalent, it forms metal organic compounds containing both organic radicals and halogen atoms: CH 3 MgCl, C 6 H 5 ZnBr, (C 2 H 5) 2 ALCL.
Studies in the field of mercury compounds, as well as lead compounds, tin and other metals were launched by A. N. Nesmeyanov in the 1920s. Mercury compounds are used for the synthesis of substances containing less electronegative elements in a row of voltages to Hg (see a series of stresses). So the very active compounds of alkali metals and aluminum are obtained.
(C 2 H 5) 2 HG + 2 Na → 2c 2 H 5 Na + HG
With the help of metal organic compounds, various hydrocarbon derivatives were obtained.
Many organometallic compounds are extremely easily reacting with different substances. So, methyl natriotic and ethyl natriot explodes when contacting air; Spontaneously flammable in air organic compounds BE, CA, BA, B, B, AL, GA, etc.
The Li, Mg and BE compounds are flammored even in the CO 2 atmosphere.
Since metal organic compounds are very easily oxidized, work with them requires special equipment. Significantly resistant essential solutions of magnesium organic substances. They are usually used in laboratory practice.
The chemical bond "element - carbon" in elementogenic compounds can be as polar (ion) and non-polar. Metals whose cations have a small volume and a large charge form covalent bonds; Thus there are mercury compounds and compounds of elements IV and V groups. Metals, easily sending electrons, i.e. having a large volume and small charge of the nucleus, for example, alkali metals form ionic bonds in which the carbon atom C is negative -\u003e C - M + (M is a metal atom). The presence of a negative charge on the carbon atom of such compounds allows them to be used as polymerization reaction catalysts when producing synthetic rubbers. With the help of aluminum and titanium metal compounds, polyethylene, polypropylene and other polymers are obtained.
In the elementogenic compounds of phosphorus and arsenic communication element - carbon is polarized in the opposite, compared to other organometallic compounds, direction. Therefore, they chemical properties They differ very different from the properties of other substances of similar composition. Related carbon Element of silicon forms strongly low-polar connections with it. At the same time, it is possible to use silicon ability to replace through chemical reactions Unstable (unstable) communication -\u003e Si-Cl, -\u003e Si-H and -\u003e Si-Oh in touch -\u003e Si-O-Si<− с образованием полимерных цепей. Кремнийорганические полимеры ценны тем, что сохраняют свои свойства как при высоких, так и при низких температурах, устойчивы к действию кислот и щелочей. Покрытия из таких полимеров надежно защищают материалы от разрушающего действия влаги. Эти соединения являются отличными электроизоляторами. Из линейных кремнийорганических полимеров изготовляют смазки, гидравлические жидкости, выдерживающие и высокие, и низкие температуры, а также каучуки.
Elementorganic compounds are increasingly used in various fields of human activity. Thus, mercury and arsenaganic substances are used in medicine and in agriculture as bactericidal, drugs and antiseptic drugs; Tinzganic compounds - as insecticides and herbicides, etc.
Ministry of Education Survey
Ural State University. A. M. Gorky
Methodical instructions on a special rate
Chemistry of elementogenic compounds
for independent work of undergraduates 1 and 2 years of study
chemical faculty
Yekaterinburg
Methodical instructions are prepared by the Department
organic chemistry
Compiler: Yu. G. Yatluk
Ural State University
Chemistry of elementogenic compounds is a fundamental scientific discipline that studies the compound of carbon containing the bonding element-carbon. In a broader sense, the words in the elementogenic compounds also include compounds in which there is a connection of metal-monetall carbon, where nonmetall, as a rule, oxygen, nitrogen, sulfur. Such compounds are customary to be called organic compounds of elements. On the other hand, compounds containing carbon bonds with nitrogen, oxygen, gray and halogens are usually not related to elementogenic compounds. In the present course, both elementorganic and organic compounds of elements are considered. Certain attention is paid to the compounds of sulfur and halogen in unusual valences. When studying the course, students get acquainted with the most important laws that bind the structure and properties of elementogenic compounds, as well as with their use in industry, agriculture and other areas of human activity.
When mastering the course of chemistry of elementganic compounds, students must learn:
- It is true to call the connections used in accurately compliance with the rules of the rational nomenclature, the nomenclature of the Jew, to know their trivial names;
- distinguish between the basic classes of elementogenic compounds, understand the features of their structure, methods for obtaining, understanding the relationship of chemical and physical properties, to know the applications;
- to make reasonable assumptions about chemical reaction mechanisms with the participation of elementogenic compounds and use these knowledge to predict the possible conditions for the flow of chemical reactions;
The basis for the successful solution of these tasks is a conscientious attitude to audit classes (lectures, seminars, colloquums). Independent homework is also needed (preparation for seminars, colloquiums, testing work). The independent study of the material that is not read on lectures is obligatory.
Brief program program
Classification of elementogenic compounds (organometallic compounds: compounds with tie metal-carbon, salts, compounds with anion radicals; organic compounds of alkali metals: alkoxides, chelates b.-Dicarbonyl compounds). Structure. Nomenclature. Physical properties. Methods of receipt.
Lithiumorganic compounds in organic synthesis. Connection to multiple links. Reaction reaction. Rearrange. The reactions of lithium (sodium, potassium) organic compounds with anion radicals. Reactions of amides and lithium, sodium and potassium alkoxides. The dependence of the reactivity of the chelates from the alkali metal of it forming.
Metallometallic compounds of alkaline earth metals (dialkyl (aryl) derivatives, alkyl (aryl) of metalhelery). Structure. Nomenclature. Physical properties. Methods of receipt.
Magniorganic compounds in organic synthesis. Connection to multiple links. Reaction reaction. Rearrange. Synthesis of other organometallic connections. Calcium and Baroorganic compounds. Magnesium alkoxides. Magnafthalin. MetoximagniumMetalkarbonate.
Meditanic connections. Dialkopratty. Copper acetylenes. Structure. Nomenclature. Methods of obtaining, reaction. Alkoxides of copper. Copper chelates based on b.-Dicarbonyl compounds. Silver acakes.
Zinc-, cadmium and mercury compounds. Structure. Methods of obtaining and reaction. Reaction S.N.reformatsky. Catalysis mercury compounds. Dual reactivity a.
Aluminumorganic connections. Properties, methods of obtaining, reaction. Aluminum hydrides in organic synthesis. Industrial value of aluminumorganic compounds. Tal liganic connections. Mono-, di-, trialkyl (aryl) Tal liganic compounds. Alkoxides, chelates, acyculations of monovalent thallium in organic synthesis.
Germany-, tin- and high-profile compounds. Properties, methods of obtaining and reaction. Industrial application of organic lead compounds. Hydride tin joints. Compounds of bivalent lead, diploma-lead connections.
Borochigans and their derivatives in organic synthesis. Organists. Salts of organoborates, their use in organic synthesis. Hallery boron and their reaction. Alkoxy and acyloxyborns, their receipt and properties.
Siliconic compounds (compounds with silicon-halogen connections, silicon-hydrogen, silicon-oxygen, silicon-nitrogen, silicon-carbon, silicon-silicon and silicon metal). Methods of obtaining, reactions, properties. Polymers based on silicone compounds.
Phosporganic compounds of different valence, oxidation degree and coordination number. Comparison of reactivity with arsenic compounds, antimony and bismuths. The use of organic phosphorus compounds in industry, inorganic - in organic synthesis.
Organic compounds of sulfur: thiol, sulphides, polysulfides, sulfonium salts, sulfoxides, sulfones, sulfue, sulfoxyl, sulfin, sulfonic acids. Organic sulfites and sulfates. Tyokarbonyl compounds. Selena and televorganic connections. Properties, methods of obtaining, reaction. Analogy with sulfur organic compounds, differences. Mixed sulfur and selenium compounds.
Compounds containing halogens in the form of positively charged atoms. Salts of iodonia, iodose and iodochable products. Similar connections of bromine and chlorine. Chlorine acid and its derivatives in organic chemistry.
Organic compounds of transition metals, s.- I. p.- complexes. Implementation reactions, rearrangement. Alkoxides of transition metals. Steric control. Polymerization reactions. Biological systems involving transition metals.
Common problems of chemistry of elementogenic compounds. Specificity of synthesis and use. The relationship of the reactivity with the position of the element in the periodic system. The possibility of regulating the reactivity by changing the valence and degree of substitution of metals and non-metals. Progress of methods of chemistry of elementogenic compounds.
Seminar Plans
Seminar 1.
Classification of organic compounds of alkali metal. Metal organic compounds (compounds with bonding me-c), alkali metal salts with anion radicals; Organic compounds of alkali metals (alkoxides, chelates b.-Dicarbonyl compounds. Building, nomenclature, physical properties. Methods of receipt.
Lithiumorganic compounds in organic synthesis. Connection to multiple bonds (C \u003d C, C \u003d O, C \u003d N). Reaction reaction. Rearrange. Reactions of lithium- (sodium, potassium) organic compounds. Anion-radical compounds of transition metals and their reaction. Reactions of amides and alkoxides of lithium, sodium, potassium. Dependence of the reactivity of chelates from the nature of the alkali metal of it forming.
Seminar 2.
Classification of organometallic compounds of alkaline earth metals dialkyl- (aryl) derivatives , Alkyl (aryl) of metalhelery). Structure. Nomenclature. Physical properties. Methods of receipt.
Magnesium organic compounds in organic synthesis. Connection to multiple bonds (C \u003d C, C \u003d O, C \u003d N). Reactions of substitution (halogens, alkoxy groups). Rearrange. Synthesis of other organometallic connections. Calcium- and Baroorganic compounds.
Magnesium alkoxides. Magnesium-naphthalene. MetoximagniumMetalkarbonate.
Seminar 3.
Meditanic connections. Dialkopratty. Copper acetylenes. Building, nomenclature. Methods of obtaining, reaction. Alkoxides of single and bivalent copper. Copper chelates based on b.-Dicarbonyl compounds. Silver acakes. Copper complexes in organic synthesis.
Seminar 4.
Zinc-, cadmium and mercury compounds. Building, methods of obtaining, properties. Reformat reaction. Catalysis mercury compounds. Dual reactivity a.-Mercured carbonyl compounds.
Seminar 5.
Aluminumorganic connections. Properties, method of obtaining, reaction. Aluminum hydrides as reducing agents. Alumina alkoxides in organic synthesis. Industrial value of aluminumorganic compounds.
Tal liganic connections. Mono-, di-, trialkyl (aryl) Tal liganic compounds. Alkoxides, chelates, acyculations of monovalent thallium in organic synthesis.
Seminar 6.
Tin- and high-profile compounds. Properties, methods of obtaining and reaction. Industrial application of organic lead compounds. Hydride tin joints. Compounds of two-, trivalent lead, connections with the connection of the PB -RB.
Seminar 7.
Borochigans and their derivatives in organic synthesis. Organists. Salts OP GA HO BO RATES, their use in organic synthesis. Hallery boron and their reaction. Alkoxy and acyloxyborne - receipt and reaction.
Siliconic compounds (compounds with silicon-halogen connections, silicon-hydrogen, silicon-oxygen, silicon-nitrogen, silicon-carbon, silicon-silicon and silicon metal). Methods for obtaining a reaction, properties. Polymers based on silicone compounds.
Seminar 8.
Phosporganic compounds: Pentacoordinated phosphorus derivatives, phosphoric acid derivatives (ethers, amides), polyphosphoric acid derivatives, phosphonic acid derivatives, phosphine derivatives, tertiary phosphine oxides, compounds of trivalent phosphorus. Phosphorus halides. Arsenic, antimony, bismuth and their elementorganic connections.
Seminar 9.
Organic compounds of sulfur: thiol, sulphides, polysulfides, Sulfony salts, susanifoxides, sulfones, sulfonic acids, sulfoxyluminous acids, sulfinic acids, sulfonic acids. Organic sulfites and sulfates. Tyokarbonyl compounds. The reactions of elemental sulfur, thionyl chloride and sulfuril chloride.
Selena and televoganic connections. Properties, methods of obtaining, reaction. Analogies with organic compounds of sulfur, differences. Mixed compounds containing sulfur and selenium.
Seminar 10.
Compounds containing halogens in the vice of positively charged atoms. Salts of iodonia, iodose and iodochable products. Similar connections of bromine and chlorine. Chlorine acid and its derivatives in organic synthesis.
Specificity of synthesis of fluororganic compounds. Special fluorinating agents. Fluorinated hydrocarbons in industry, fluorine-containing polymers. Biologically active fluororganic compounds.
Tasks for self-decide
Tasks for the seminar 1
1. Implement the transformation of RC but ® Rcor 'through dioxolanes, 1,3-dithianes and imidazolidines.
2. Consider the paths of the synthesis of ketones directly from carboxylic acids.
3. Get dibenzil from dimethylbenzilamin.
4. When processing lithium suspension in cetane chloride tert-but, followed by passing carbon dioxide and the destruction of the resulting mixture with water, in NMR 1 H spectrum of the reaction mixture there are two signals with a chemical shift 1.07 and 0.85 pp. Accordingly, the integral ratio of 4.67: 1. How was the reaction?
5. Make transformation:
RCH 2 COOH ® RC (CH 3) 2 COOH
Compare with the industrial method of obtaining higher isocoslot.
6. Get dibenzoylmethane from styrene (consider options).
7. Synthesize acrolein diethyl acetal from allyletyl ether.
8. Compare the possibilities of direct metallization of benzene and toluene in a subgroup of alkali metal.
Tasks for the seminar 2
1. Consider the possibilities of interaction of trifluoroacetaldehyde with magniaorganic compounds.
2. Compare methods for the synthesis of propionone aldehyde from various derivatives of formic acid.
3. Write the schemes of methylketones processes with magnesium organic compounds, alkylamide and magnesium alkoxides, as well as magnesium-naphtalin.
4. Describe the possibilities of interaction of hexagohenobenzols with methylmagneideidide, depending on the halogen used.
5. Synthesize vinylmalon ester from butyrolactone.
6. Consider the reactions of birilorganic compounds, depending on the structure of an organic radical.
7. Compare the reaction capacity of phenylacetylene alkaline earth metals depending on the position of the metal in the periodic system.
Tasks to the seminar 3
1. Get 6-oxogenic acid from adipine.
2. Get butanol-2 from propanol-2.
3. From propargyl alcohol to obtain ethyl ester of 3,4-pentadiene acid.
4. From benzonitrile to obtain 2,6-diphenic acid.
5. From hexafluoropropylene to get 2-bromplefluoropropane.
6. Consider the possibilities of reactions of the interaction of silver carboxylates with halogens.
7. Get chlorobenzene from aniline without diazotizing.
Tasks for the seminar 4
1. Get the methyl auxous ether and methyl acetylacetone using the same raw material.
2. Get methyl methacrylate from dimethyloxalat.
3. Get a methylallilketon from acetonitrile.
4. Get a cortic acid without the use of perkin reaction.
5. Represent the nature of the oxidation of cyclic ketones during catalysis salts of mercury.
6. Get styrene from Phenyluxus aldehyde.
7. Get isopropylacetamide from propylene.
Tasks for the seminar 5.
1. Using aluminumorganic compounds, to obtain oil aldehyde, butylamine and butylvinyl ether.
2. Synthesize triacetylmethane by all possible ways.
3. Get phenylmalon aldehyde from cinnamon aldehyde.
4. From methyl chloroform to synthesize 1.1-diethoxyethylene.
5. From cyclogesanol, synthesize cyclopentaxarboxylic acid and its aldehyde.
6. Synthesize 1,4-diphenylbutadiene styrene.
7. Consider the capabilities of the synthesis of glycidol esters using thallium compounds, compare the synthesis method with methods used in industry.
Tasks for the seminar 6
1 Compare the reduction of valerian and ally lugenic acid chloridrides using tin hydrides.
2. From malonic acid to get acetone, lactic acid, acetic aldehyde.
3. From propionic acid to obtain ethanol, ethylene and chloride and iodide ethyls.
4. From ethylamine to get methyl acetamide.
5. From heptaol to get 4-oxogenic acid
6. Compare industrial methods for obtaining tetraethylswin. Consider possible replacement of this compound in the production of high-octane gasoline.
Tasks for the seminar 7
1. From methyl ethyl ketone to get boutinol and diethyl ketone.
2. Get tripropalkarbinol from acetone.
3. from trimethylbore and naphthalene get b.-tftol.
4. From the phenyltrimethylsilane to synthesize the benzophenone.
5. Is trimethylallilsilana Get 1,1-dimethylbutene-4-ol-1.
6. Get phenylpropionic acid from Malon Ether.
7. From acetone to synthesize isopropylamine.
8. Compare Envol's Silyl ethers methods
Tasks for the seminar 8
1. Get vinyltrifhenylphosphonium bromide. Describe its interaction with salicyl aldehyde.
2. Suggest the synthesis of diphenylphosphinylitium, use it to deny the anisole and phenetol, explain the differences.
3. Describe the interaction of methyl ether of peyrogradic acid with trimethylphosphite.
4. Consider the interaction of triethylphosphite with orthosatic nitrobenzenes.
5. Consider changing the nature of the interaction of hexametapol with cyclohexanone at different interaction time
6. Compare methods for producing mono-, di- and trieters phosphoric and phosphorous acids.
Tasks for the seminar 9
1. Suggest a method for producing dibutyl sulfate from affordable reagents.
2. From benzillsulfochloride get methylphenylsulfon.
3. 2,4-dinitrophenylsulfenyl chlorides are used to identify organic compounds, describe how.
4. Describe the reactions of the interaction of alkylbenzenes with thionyl chloride in the presence of pyridine.
5. Get 4-dimethylaminopyridine from pyridine.
6. Write a sulfur interaction scheme with cumol in the presence of a strong base.
Tasks for the seminar 10
1. Suggest a method for the synthesis of arylfluorides without the use of tetraftorborators of diazonia.
2. Using diethylamine and trifluorchlorethylene, get methyl fluoride.
3. Describe the interaction of trifluoromethylphenylketon with triphenylphosphine and sodium chlordifluoroacetate.
4. Using enantum and perfluoronantic acid, get a semi-powered dodecan.
5. Compare the reagents of direct hydrocarbon fluorination, select the most affordable laboratory reagent.
6. Use of chlorine acid instead of Lewis acids. To compare the reaction capacity of the substrates.
Colloquium plans
Colloquium 1. Metallometallic connections
The formation of carbon-carbon bonds in the reactions of mattalorganic connections. Grignar reagents like electric flaws. Alkylation (reaction with carbonyl compounds, nitriles, azomethanes, a.,b.-Natched compounds, etc.). Other organometallic compounds and electricifications (lithium, zinc-, cadmium and honeyzorganic compounds).
Nucleophilov reactions (lithium, sodium, magnesium derivatives). Alkynyl copper compounds.
Metal alkoxide reactions ( tert-butula potassium, branched sodium alkoxides, thallium alkoxides). Catalysis of alkoxide reactions, metals with high coordination numbers (aluminum, titanium, vanadium, chromium). Amida alkaline and alkaline earth metals as bases, their reactions (lithium and magnesium amides). Amidia of titanium amides or systems of Titanium Titanium (Silicon, Tin) - amine.
Metal carboxylates. Silver carboxylates, lead, thallium and bismuth - specific organic synthesis reagents
Colloquium 2. Organic compounds Nemmetalov
Hinoborization with complex borants and alkylbores. Reactions of bororganic compounds (transformation into alcohols, amines, halogen derivatives). Thermal transformations, reactions with acids and carbon oxide. Hydrocking of unsaturated compounds.
Phosporganic reagents. The formation of double carbon-carbon ties (Vittig reaction). Transforming functional groups (replacement of hydroxyl per halogen, formation of amides, esters, etc.) Comparison of the reactivity of Vittig reagents in V subgroup of the periodic system.
Restoration of nitrogen-containing functions using trivalent phosphorus compounds.
Chart of control events
№ |
Check occupation and its topic |
Literature |
1 |
Seminar 1. Alkali metal compounds. |
|
2 |
Seminar 2.Compounds of alkaline earth metals. |
|
3 |
Seminar 3.. Organic compounds of copper and silver. |
|
4 |
Seminar 4. Zinc-, cadmium and mercury compounds. |
|
5 |
Seminar 5. Aluminum and tallia organic connections. |
|
6 |
Seminar 6. Tin- and high-profile compounds. |
|
7 |
Colloquium 1. Metal organic connections. |
See above. |
8 |
Seminar 7. Boris and silicon compounds. |
|
9 |
Seminar 8. Phosporganic connections |
|
10 |
Seminar 9. Organic sulfur compounds. |
|
11 |
Seminar 10. Fluorogenic compounds, compounds of higher valence halogen. |
|
12 |
Colloquium 2. Organic compounds of non-metals. |
See above. |
Change and introduction of functions in chemistry of elementogenic compounds
1. Reactions without changing the degree of oxidation
|
IN ¯ Of ® |
-\u003e C -H |
\u003e C \u003d CR-H |
RC = Ch |
AR-H. |
|
|
-\u003e C-H |
|||||
|
\u003e C \u003d CR-M |
|||||
|
RC = C-M. |
|||||
|
AR-M. |
|||||
|
-\u003e C-B< |
|||||
|
-\u003e C-P< |
|||||
|
-\u003e C -Si<- |
Characteristic examples
MH 2 O.
1-1 R-X ¾ ® R-M. ¾ ® R-H.
C 2 H 5 COOH
(C 6 H 13) 3 B ¾ ¾ ¾ ¾ ® C 6 H 14
H 2 O.
Arso 3 H. ¾ ® ARH
1-3PHC. = Ch ¾ ® Phc. = CNA
Buli.
Alkc. = Ch ¾ ® Phc. = CLI
Cu (NH 3) 4 +
Phc. = Ch ¾ ¾ ¾ ¾ ® Phc. = Cu.
1-5c 6 H 5 Na
C 6 H 5 CH 3 ¾ ¾ ¾ ¾ ® C 6 H 5 CH 2 NA
t-Buok.
CH 3 SOCH 3 ¾ ¾ ¾ ® CH 3 SOCH 2 K
CH 3 ONA
CH 3 NO 2 ¾ ¾ ¾ ® Nach 2 No 2
t-Buok.
PhCH 2 COOT-BU ¾ ¾ ¾ ® Phchkcoot-Bu.
1-6BF 3. Oet 2.
Phli. ¾ ¾ ¾ ® PH 3 B.
1-7pCl 3.
i-PR MGCL¾ ¾ ® I-PR 2 PCL
2. Recovery reactions
|
IN ¯ Of ® |
-\u003e C-x |
\u003e C \u003d C< |
|
|
-\u003e C-Li |
|||
|
-\u003e C-MG- |
|||
|
-\u003e C-ZN- |
|||
|
-\u003e C-Al< |
|||
|
-\u003e C-B< |
|||
|
-\u003e C-P< |
|||
|
-\u003e C-SI<- |
Characteristic 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 \u003d CHCH 2 BR ¾ ® CH 3 CH \u003d CHCH 2 ZNBR
2-7Phph 2 + CH 2 \u003d CHCN ¾ ® PHP (CH 2 \u003d CHCN) 2
H 2 PTCL 6
2-8RCH \u003d CH 2 + HSIME 3 ¾ ¾ ¾ ® RCH 2 CH 2 SIME 3
3. Oxidation reactions
|
IN ¯ Of ® |
|||
|
ROH (R) |
|||
|
RNH 2. |
|||
|
RPX 2. |
|||
|
RS-, SO 2 -, SO 3 - |
3-10 |
Characteristic examples
SO 2.
C 12 H 25 MgBR ¾ ¾ ® C 12 H 25 SO 2 H
SO 2 Cl 2
Phmgcl ¾ ¾ ® Phso 2 Cl. ¾ ® Phso 3 H.
3-10
Literature
1. Talalaeva T.V., Kocheshkov K.A. Methods of elementogenic chemistry. Lithium, sodium, potassium, rubidium, cesium. KN.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 elementogenic chemistry (magnesium, beryllium, calcium, strontium, barium). M., from the USSR Academy of Sciences, 1963.
4. Keri F., Sancenderg R. In-depth Course of Organic Chemistry. M., Chemistry, 1981, vol. 2, p. 165-184.
5. Shevhendina N.I., Kocheshkov K.I. Methods of elementogenic chemistry. Zinc, cadmium. M., Science, 1964.
6. Makarova L.G. Nesmeyanov A.N. Methods of elementogenic chemistry. Mercury. M., Science, 1965.
7. Nesmeyanov A.N., Sokolik R.A. Methods of elementogenic chemistry. Bor, aluminum, gallium, indium, thallium. M., Science, 2 tons 1964.
8. Kocheshkov K.A., Earthsky N.I., Sheverdina N.I. et al. Methods of elementogenic chemistry. Germany, Tin, Lead. M., Science, 1968.
9. General organic chemistry. M., Chemistry, vol. 6, 1984.
10. Andriyanov K. A. Methods of elementodorganic chemistry. Silicon. M., Science, 1968.
11. Mikhailov B.M., Bubnov Yu.N. Boroorganic compounds in organic synthesis. M., Science, 1977.
12. General organic chemistry. M., Chemistry, vol. 4, 1983, p.595-719.
13. General organic chemistry. M., Chemistry, vol. 5, 1984.
14. Nifantiev E.E. Chemistry of phosphauses. M., Chemistry, 1971.
15. General organic chemistry. M., Chemistry, vol. 1, 1981, p. 622-719.
16. Gubitsky M. Chemistry of fluorine organic compounds. M. Goshimzdat, 1961.
17. Sheppard W., Charts K. Organic Chemistry Fluoride. M. published, 1972.
18. Dorofenko G.N., Zhdanov Yu.A., Dulelenko V.I. and other chlorine acid and its compounds in organic synthesis. Rostov, from in RHU, 1965.
additional literature
1. Rohov Yu., Herd D., Lewis R. Chemistry of metal organic compounds. M., published, 1963.
2. Fizer L., Fizer M. Reagents for organic synthesis. M., Mir, t. I -VII, 1970-1978.
Introduction3.
Brief course program4.
Seminar Plans6.
Tasks for self-decide9
Colloquium plans14
Schedule of control measures16.
In the history of the development of organic chemistry there are many examples when some sections of this science that have not previously attracted the great attention of researchers, began to grow violently due to the unexpected practical application of a class of compounds or identifying their new properties.
Some data from the history of elementogenic compounds
One such example is associated with sulfamis. The use of sulfamed preparations as valuable medical agents has served as the beginning of the intensive development of this area of \u200b\u200borganic chemistry - in a short time several thousand new sulfamed drugs were synthesized.
Chemistry of elementogenic compounds is now in a similar stage of rapid development. This can be seen from many examples. Chemistry of phosphorus compounds, for a long time representing only theoretical interest, in connection with the extensive use of organic phosphorus derivatives in various fields of national economy, is currently developing. The development of chemistry of organic compounds of titanium and aluminum was accelerated after the discovery of aluminumorganic compounds in 1954 in 1954 in a mixture with titanium tetrachloride to cause ethylene polymerization, as well as NATTA detection in 1955. The possibilities of stereospecific polymerization of unsaturated compounds in the presence of various complex catalysts.
Chemistry of silicone compounds also develops jumps like. The first compound containing silicon and carbon is the ethyl ether of orthocremary acid - was obtained by the French scientist Elemen in 1844. Later, in 1963, Freshel and Krafts synthesized the first silicone connection with the Si-C - Tetraeethylsilane. At the beginning of the development of chemistry of silicon-organic compounds, silicon, as the nearest carbon analogue, attracted great attention of researchers. It seemed that on the basis of silicon, it is possible to create only a wide area of \u200b\u200bchemical science as organic chemistry. But it turned out that silicon does not form a carbon of stable chains of molecules from sequentially connected SI atoms, and therefore interest in organic derivative of silicon immediately fell. However, the development of chemistry of high molecular compounds could not be limited to the use of carbon and organogenic elements (oxygen, halogen, nitrogen, sulfur) to construct polymer molecules; It, naturally, was directed towards the involvement of other elements of the periodic system. It was dictated by a number of considerations on which it was assumed that carbon replacement in the main chain of the molecule to other elements will 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) to construct the inorganic main chains of large molecules consisting of alternating silicon and oxygen atoms and framed by organic radicals. So a new class of silicone polymers appeared, known now called polyorganosiloxanes, siloxanes or silicones. Thus, the Soviet researchers first showed the possibility of using silicon compounds (cylinders) for the synthesis of polymers with inorganic chains of molecules and lateral organic groups. This stage has become a swivel in the chemistry of silicone polymers and served as the beginning of intensive studies of not only silicon polymers, but also other elementogenic high molecular weight compounds,
In the US, the first posts for polyorganosiloxanes appeared in 1941 (Y. Rohov). In the preface to the Russian publication of Mii Yu. Rokhov, D. Herda and R. Lewis "Chemistry of metalological compounds" (1963) Y. Rohov wrote: "As one of the followers of fundamental works K. A. Andrianova and L. M. Coton In the field of silicon chemistry organic compounds, I fully recognize the successes of Russian scientists in the field of synthesis and the study of metallo-organic compounds. "
Recently, elemental organic polymers show great interest on the part of various branches of farms, especially machinery and apparatus, aviation and rocket technology; At the same time, the highest requirements are presented to the thermal stability of polymers. We give an example energy. The expansion of the applications of energy units requires an increase in the scale of electrical equipment and in connection with this extremely large consumption of copper, magnetic materials, etc. In addition, due to the development of aviation, fleet and rocket technology, and the electrification of underground work becomes necessary to reduce the mass and reduce electrical equipment dimensions. All this causes designers to create electrical devices having a greater power at small mass and dimensions. When solving these issues, it is natural to increase the current density, and this leads to a sharp increase in the operating temperature of the machine or the machine. Since polymers are essential materials for the manufacture of any energy units, it is necessary to take into account that it is how the dielectrics are the first to perceive the heat allocated by conductive elements. And here it becomes especially important thermal stability of polymeric materials.
The introduction of atomic energy in the energy sector even more tightens the requirements for dielectrics. In particular, there are currently dielectrics that are capable of working for a long time at 180-200 ° C, and with short-term work to withstand the temperature of 250-350 ° C and higher. Another example can be brought from modern aviation. Now the speed of aircraft increases incredibly rapid pace; When landing such high-speed aircraft in aviation tires, the temperature is developing to 320 ° C and higher. Along with this, the protection of high-speed aircraft is extremely complicated by the heat of the heat released when moving in the atmosphere at high speed. Heat resistant polymers should also help the successful solution of the tasks of the development of outer space.
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 that new area that chemical science develops without copying natural substances or materials, since polymers of such a composition are unknown in nature and from beginning to end are developed in the laboratory. Studies of elementorganic high molecular compounds were particularly expanded in the post-war period, and now they are carried out in all industrial and developing countries. The number of publications and patents in this area is growing every year, and new works of a theoretical and applied appear continuously. In parallel with this, the industry of elementogenic polymers and monomers is rapidly developed; The global production of only silicon monomers and polymers have now reached 1 million tons per year.
In the field of view of researchers working on polymers synthesis, there are 45 elements of the periodic system. The most important elements attracted to the construction of 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
Features of chemistry in the technology of elementogenic compounds
Elementorganic compounds by properties and buildings are significantly different from organic, and from inorganic compounds - they occupy an intermediate position. Elementorganic compounds in nature are rare, they are obtained by synthetic.
In the chemistry of living organisms, the role of elementogenic compounds is not yet quite clear, nevertheless, it is safe to say that silicon, phosphorus and other elements play a significant role in the vital activity and metabolism of living organisms standing at a high level of evolutionary development, in particular humans. In human and animal organism, silicon-containing compounds are present in various forms, including in the form of silicon and complex compounds soluble in organic solvents. Nevertheless, for the silicone compounds, only one case of their detection in nature is known from the bird feathers, phosphorganic compounds play in the chemistry of living organisms, first and foremost, phosphoric and polyphosphoric acids are played out of the bird feathers. Thus, adenosine trifhosphate (ATP) is contained in lively fabric and plays a vital role as a source of energy.
In elementogenic compounds, several characteristic features that are fundamentally distinguish between carbon compounds can be distinguished.
1. The difference in the electoral affinity of the elements compared to carbon.
Electric positive 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 electrical elements (H, Si, B, Al, As, Sb, Bi, etc.), but stronger - with electronegative (o, n, CL, BR, F, etc.) than carbon.
When considering the electronegability of various elements, it can be seen that carbon (XC \u003d 2.5) occupies about the average position between the electronest element - fluorine (XF \u003d\u003d 4.0) and the electrical elements - cesium and francium (Xcs \u003d 0.7, HFR \u003d\u003d 0.7). The hemishemma of the electrical negativeness of these elements is CPS \u003d 2.35 and, therefore, an atom C has the smallest tendency to give or receive electrons, i.e. to form positive or negative ions. This means that carbon in the compounds is less ionized compared to electropositive or electronegative elements. For example, if the connection of Si-C1 is ionized by 30-50%, then the connection of C-C1 is about 6%. Therefore, carbon is least susceptible to an electrophyl or nucleophilic attack, which means that C-C-Communication is significantly more durable than e-e-bond (for example, B, Si-Si, A1-A1, Rr, AS-AS) , and on the contrary, for example, the C-O-communication, the hemishemma of the electronenence of which is equal to the CPS \u003d 3.0, less durable than the bonds of A1-O (CPS \u003d 2.5), Si-O (CPS \u003d 2.65), Si- N (HPS \u003d 2.4), etc. Comparing the energy of boron atoms of boron, silicon., Phosphorus, arsenic with a carbon atomic binding energy confirms these positions (Table 1).
Elementorganic compounds - organic substances whose molecules contain the chemical bond "element - carbon". This group, as a rule, do not include substances containing carbon bonds with nitrogen, oxygen, sulfur and halogen atoms. According to such a classification, one of the elementogenic compounds is considered, for example, methyl natrium CH 3 Na, but it does not apply to the sodium methylate CH 3 ONA, since it does not have the binding element - carbon.
Elementorganic compounds differ in both chemical and physical properties and according to methods of their preparation. Metal organogenic connections are a large group. The first of them is diethyl offshink (C 2 H 5) 2 Zn - was obtained in 1849 by E. Frankland. Zinc compounds were widely used in the synthesis of A.M. Butlerov and other scientists of the end of the XIX century. A decisive role in the development of chemistry of elementogenic compounds was played by the opening of magnesium and mercury and mercury. They are used in the synthesis of many elementogenic and organic compounds.
Magniorganic compounds were opened in 1900 by the French chemist F. Barbie and deeply studied by his colleague by V. Grignar. The latter developed the method of their synthesis of halogen-containing hydrocarbons: RX + MG → RMGX (R-hydrocarbon radical, for example CH 3, C 2 H 5, C 6 H 5, etc., and a x-atom halogen). In our time, the reaction, similar reactions of Grignar, became a common method for producing metal organic compounds (Li, BE, MG, CA, SR, BA, A1 and Zn). Moreover, if the metal atom is not monovalent, it forms metal organic compounds containing both organic radicals and halogen atoms: CH 3 MgCl, C 6 H 5 ZnBr, (C 2 H 5) 2 ALSL.
Studies in the field of mercury compounds, as well as lead compounds, tin and other metals were launched by A. N. Nesmeyanov in 1922. Mercury compounds are used for the synthesis of substances containing less electronegative elements facing in a row of voltages to Hg (see a series of stresses) . This is so obtained by very active compounds of alkali metals and aluminum:
(C 2 H 5) 2 HG + 2NA → 2C 2 H 5 Na + HG
With the help of metal organic compounds, various hydrocarbon derivatives were obtained.
Many organometallic compounds are extremely easily reacting with different substances. So, methyl natriotic and ethyl natriot explodes when contacting air; Spontaneously flammable organic compounds BE, Ca, BA, B, Al, Ga, and others. Li, Mg and Be compounds are flammable even in the atmosphere of CO 2.
Since metal organic compounds are very easily oxidized, work with them requires special equipment. Significantly resistant essential solutions of magnesium-organic substances. They are usually used in laboratory practice.
Chemical bond element - carbon in elementogenic compounds can be as polar (ionic) and non-polar. Metals whose cations have a small volume and a large charge form for valence communications; Thus there are mercury compounds and compounds of elements IV and V groups. Metals, easily sending electrons, i.e. having a large volume and small charge of the nucleus, for example, alkali metals form ionic bonds in which carbon atom with carries a negative charge (M-atom of the metal). The presence of a negative charge on the carbon atom of such compounds allows them to be used as polymerization reaction catalysts when producing synthetic rubbers. With the help of aluminum and titanium metal compounds, polyethylene, polypropylene and other polymers are obtained.
In the elementogenic compounds of phosphorus and arsenic communication element - carbon is polarized in the opposite, compared to other organometallic compounds, direction. Therefore, their chemical properties are very different from the properties of other substances of similar composition. Related carbon Element of silicon forms strongly low-polar connections with it. In this case, it is possible to use the ability of silicon to replace with chemical reactions unstable (unstable) communication in touch 
with the formation of polymer chains. Silicon-organic polymers are valuable in that they retain their properties both at high and at low temperatures, resistant to the action of acids and alkalis. Coatings from such polymers reliably protect the materials from the destructive action of moisture. These compounds are excellent electrical insulators. From linear silicon-organic polymers produce lubricants, hydraulic fluids, withstanding and high, low temperatures, as well as rubber.
Elementorganic compounds are increasingly used in various fields of human activity. So, mercury - and the musicals are used in medicine and in agriculture as bactericidal, medicinal and antiseptic drugs; Tinzganic compounds - as insecticides and herbicides, etc.
Ministry of Education and Science of the Russian Federia
Federal State Budgetary Educational Institution
higher professional education
"Chuvash State Pedagogical University named after I.Ya. Yakovleva "
Faculty of natural science education
Department of Biology and Chemistry
COURSE WORK
by discipline
"Chemistry of elementogenic compounds"
Topic: Dimethylphosfite reaction.
Performed:
student Marsova Yu.V.
Profile BIX
Checked: Professor
departments of bioecologists
Doctor of Chemical Sciences
Mitrasov Yu.N.
Cheboksary, 2015.
Introduction
1. Preparation of ether from chloranhydrides. Phosphoric acid carbonates and esters
1.1 Synthesis of chloricarbonates and carbonates
1.2 Phosphoric acid esters
2. Application. Storage conditions and production.
3. The method of obtaining dimethylphospity
Conclusion.
Bibliography.
Introduction
The processes of hydrolysis, hydration, dehydration, esterification and amidations are very important in the industry of the main organic and petrochemical synthesis. Hydrolysis of fats, cellulose and carbohydrates have long received soap, glycerin, ethanol and other valuable products. In the field of organic synthesis, the processes under consideration are mainly used for the production of alcohols C 2 -C 5, phenols, ethers, aoxides, many unsaturated compounds, carboxylic acids and their derivatives (esters, anhydrides, nitriles, amides) and other compounds.
These substances have very important use as intermediate products of organic synthesis (alcohols, acids and their derivatives, aldehydes,-oxides), monomers and starting materials for the synthesis of polymer materials (phenol, acrylic and methacrylic acid esters, melamine, chloroolefins), plasticizers and Lubricants (esters), solvents (alcohols, simple and esters, chloroolefins), pesticides (ethers of carbamine and thiocarbamic acids). Very frequently considered reactions are an intermediate step in multistage synthesis of other target products.
The production of listed substances has a big scale. Thus, in the US, 500 thousand tons of ethanol and isopropanol are synthesized, 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 ether from chloranhydrides. Phosphoric acid carbonates and esters
Carboxylic acid esters are very rarely obtained from chloranhydrides, since the latter are expensive substances. In contrast to this carbonic acid ester (carbonates) and phosphorus acid esters are mainly synthesized from chlorohydrides, since the corresponding acids are not capable of esterification.
1.1 Synthesis of chloricarbonates and carbonates
These esters are obtained from phosgen COCI 2, which is a chlorine hydhydride of coalic acid (under normal conditions, it is a gas condensing into a liquid at +8 0 s). The reaction proceeds by substitution of chlorine atoms on an aloxy group in the absence of catalysts. At the same time, both chlorine atoms are able to replace, but the first of them quickly, and the second is much slower. This allows at a lower temperature and a molar ratio of 1: 1 reagents to obtain with high yield of chloroupole (chloricarbonates), which, on another classification, are also called chloroformists, i.e. ether of formic acid:
Coci 2 + RoH → Cicoor + HCI
In addition to the temperature and ratio of reagents, the order of loading of reagents is favored to high output: it is necessary to add alcohol to the excess of phosgene. Thus, in periodic conditions, the synthesis of chloricarbonates lead during cooling (up to 0 ° C) and stirring, gradually adding the required amount of alcohol to liquid phosgene. The product is fused from dissolved HCI and distilled, and the distinguished HCI is purified from phosgene and disposed of as of hydrochloric acid. Chloricarbonates are of great practical importance for the production of pesticide-esters of carbamic acid (carbamata) RNHcoor.
Coalic acid dieters (carbonates) are obtained from phosgene at 70 - 100 0 with and a small excess of alcohol:
COCI 2 + 2ROH → CO (OR) 2 + 2HCI
The adverse reaction consists in the formation of a chloroalkan of alcohol and HCI. If its role is essential, then the formed HCI can be born with dry soda, calcium carbonate or tertiary amine.
Upon receipt of the ethers of phenols, less reactive than alcohols, carry out a reaction with aqueous solutions of phenolates:
COCI 2 + 2ARONA → CO (OAR) 2 + 2NACI
In this case, in order to avoid side hydrolysis of phosgene, a process with a fairly concentrated solution of phenolate and in the presence of free phenol (to reduce the concentration of hydroxyl ions).
Cyclic carbonates of glycols are of interest from the dieters of coalic acid
We are valuable solvents, and polycarbonates obtained from phosgene and alkaline solution of some bisphenols, especially diphenylolpropane:
Depend the attention of dithyoloic acid esters (Xatogenates). Alkylxanthenetic salts are obtained from alcohol alkali and surgel (dithioloic acid anhydride). Sodium isoprpilxanthane is used as effective herbicide; These are some xanthyenatdisulfides obtained by oxidation of alkylsanthenets:
1.2 Phosphoric acid esters
Phosphoric acid esters are obtained from PCI 3 phosphorus trichloride, Poci 3 phosphorus chloroxide and phosphoroid tiotrichloride PSCI 3. The reactivity of these chloranhydrides with respect to alcohols and phenols varies in a row: PCI 3\u003e Poci 3\u003e PSCI 3, and, as in the case of phosgene, the replacement of each subsequent chlorine atom is increasingly slowed down. This allows you to synthesize incomplete, full and mixed (with different alcohols) ethers.
The PCI 3 reactions with alcohols occur at low temperatures very vigorously with high heat release. The substitution is accompanied by waterbuzov embedded, and dialkylphosphite and alkyl chloride are formed:
PCI 3 + 3ROH → (RO) 2 HP \u003d O + RCI + 2HCI
Most often, Dimethylphosphite HPO (OCH 3) 2 is obtained by this path. 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 due to the evaporation of the solvent, the part of which is removed for cleaning and produce a commodity product. The resulting hydrogen chloride is caught as 20-30% hydrochloric acid. The purification of dimethylphosphite is carried out in the film evaporator with distillation in vacuo.
Dimethylphosphite is an intermediate product in the synthesis of other phosphorus-containing substances. Thus, the famous insecticide chlorofos is obtained from it, which is an alkyl phosphonic acid derivative. For this, dimethylphosphite is condensed with chloral when cooling:
There is also a one-step process in which the synthesis of dimethylphosphite is combined from CH 3 OH and PCI 3 and the synthesis of chlorofos from dimethylphosfite and chloral.
Poci 3 reactions with alcohols and phenols are mainly mainly for the synthesis of extractants (tributyl phosphate), plasticizers (tricrezyl phosphate, etc.) and flame retardants.
The interaction of phosphorus chloroxide with alcohols proceeds without catalysts and alkalis when cooling, and only for replacement of the last chlorine atom heating is required:
Poci 3 + 3 ROH → PO (OR) 3 + 3HCI
To avoid the side education of alkyl chloride
It is necessary to blow up HCI in the current gas current.
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
The hydrogen chloride is allowed to disappear from the reaction mixture and capture it in the form of concentrated hydrochloric acid. This way on a large scale (periodically or continuously) produce tricresilphosphate - plasticizer of polymeric materials.
PSCI 3 reactions with alcohols and phenols are used exclusively for pesticide synthesis. The first chlorine atom is replaced under the action of alcohols at 20-30 ° C, the alcoholic alkali alcohol solution is required for the third atom, for the third - interaction with alcoholate or phenolate. In the synthesis of most pesticides of this series, the first step is to obtain dialkyl chlorostophosphates with the same or different alkyl groups (usually with methyl and ethyl):
Metaphos and thiophos pesticides are then obtained from dimethyl and diethylchloroth phosphates and sodium n-n-nitrophenolate:
(RO) 2 PSCI + Naoc 6 H 4 NO 2 + NACI
The best results are obtained during the reaction in the acetone or methyl ethyl ketone environment, when both reagents are well homogenized. However, the process can be kept with aqueous solution Nitrophenolate, adding to it at 50 - 100 0 with dialkyl chlorordophosphate. In order to avoid a side reaction of hydrolysis, it is necessary to adjust the pH of the medium so that there is an excess of free phenol.
Similarly, of dimethylchlorostophosphate and-oxidethylsulfide, methylmercaptofors insecticide is obtained, which is partially isomerized in a thiol derivative and is a mixture of two substances:
There are many other pesticides of this class that are applications in national economy countries.
2. Application, storage conditions and production.
Dimethylphosphite is used to obtain flame retardants, chlorofos, dichlorofos, nitrophos, in the production of pesticides, in the pharmacological industry, in the production of phosphorodorganic drugs including pyrovotex and insecticides.
Chlorofos He is dilox, Tkouvon, Ricion - Coven to Insecticides. It is used in the damage to cattle skin heated, the same is widely used in the fight against clouds, ticks, trips, with pests in the planting industry, easily soluble in water and is virtually safe for warm-blooded creatures.
Storage conditions.
Dimethylphosphite is stored in the covered glassware made from staple steel stamps, aluminum alloys, or plastic capacities. The storage place should be protected from sunlight with a temperature not higher than 21 C using an inert gas reducing reactivity
The warranty storage period is at a temperature of 5 s - six months, and at a temperature of 20 s - three months.
Dimethylphosfit production.
Dimethylphosphite is synthesized during chlorine and dimethylphosphate condension.
Certification information.
Dimethylphosfit received a state registration certificate in the RPCHA.
Packaging.
Dimethylphosfite pumped in tanks (railway tanks, stainless steel containers, in two-toll stainless steel barrels, plastic containers, plastic cubes, plastic containers), or in container provided by the consumer.
Transportation.
Transportation is carried out by all types of transport besides water and air. When rail transport, stainless steel tanks are used. During road transport, the tanks of a smaller tonnage are used (cubes, containers, barrels).
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3. Proceeds of obtaining dimethylphosphite.
The invention relates to the field of organic compound technology, namely to an improved method for producing dimethylphosphite. The method of obtaining dimethylphosphite is described, comprising the interaction of the phosphorus three chloride with methanol in the medium of the evaporating chloride of methyl, under reduced pressure, the paypad of the volatile components and the subsequent purification of the product obtained by vacuum distillation, while the process is carried out with a molar methanol ratio to phosphorus three chloride 3.02-3.3 : 1, with their bulk ratio, respectively, 1,43-1.53: 1 and residual pressure 0.02-0.04 MPa. Technical result - Improving the technological and safety of the process. 1 Z.P. F-lies, 1 tab.
The invention relates to chemistry of phosphorodorganic compounds, namely to obtain dimethylphosphite used as an intermediate product in organic chemistry in the production of insecticides, herbicides, flames, etc.
A classic method for producing lower dialkylphosphites by the interaction of phosphorus three chloride and alcohol with a molly ratio of reagents 1: 3, the process leads to a gradual addition of phosphorus three chloride to alcohol, in the solvent medium and when cooled the reaction mixture. Cooling is carried out by using a solvent with a low boiling point, which, evaporating during the reaction, removes the heat released. Hydrogen chloride and halogen alkyl, remaining in the mixture, are removed by passing the dry gas current, the traces of hydrogen chloride are neutralized with ammonia, and the target product is purified by distillation under reduced pressure (D. Purdelia, R. Vyslchan. Chemistry of organic phosphorus compounds, M.: Chemistry, 1972 , p.183).
In the reaction of the interaction of the phosphorus three chloride with methanol, the rate of flow and heat of the reaction is relatively high, the second phase and the liquid system appears. Upon contact with hydrogen chloride under conditions of reduced temperature, dimethylphosphite decomposes with the formation of monomethyl phosphite and in the future - phosphorous acid (with an elevated content of hydrogen chloride in the reaction mass). With a lack of methanol, unstable, inclined to decomposition with highlighting large number Energy (explosive), chlorine-containing quasi-sofonium compounds. The presence of these impurities both during the synthesis and in the dedicated dimethylphosphite raw reduces the safety of the technological process and complicates further purification of the product by distillation. Many conditions are required for the safe and at the same time technological process.
The method of obtaining dialkylphosphites is known by the interaction of phosphorus three-chloride with lower aliphatic alcohol in an organic solvent medium and removing the formed hydrogen chloride, in which, in order to simplify technology, the process of obtaining dimethylphosphite is carried out in a preheated column at a temperature in the reaction zone of 45-110 ° C (SU patent №910123, cl. C 07 F 9/142, publ. 28.02.82). In the method, the emerging boiling temperature gradient in a row of reagents is used: alcohol, three-chicken phosphorus, solvent, resulting products and by-products of reaction (alkyl chlorides and hydrogen chloride). This method is obtained by a product containing 96 wt.% Dimethylphosphite and up to 0.6 wt.% Monomethyl phosphite.
The closest in technical essence and the result achieved is the method of obtaining lower dialkylphosphites, which consists in the fact that a mixture of phosphorus three chloride and methanol and a low-boiling solvent, for example, methyl chloride, at a temperature of minus 30 ° C to plus 10 ° C under pressure, the jet is supplied to the reactionary The column where the evaporation of the solvent occurs, which makes the formed hydrogen chloride. Dimethylphosphite, assembled at the bottom of the column, is sent to the second column with reduced pressure to remove dissolved residues of hydrogen chloride and solvent (parting) dissolved in it, and then clean the dimethylphosphite distillation under vacuum (US No. 2631161, CL. 260-461, 1953) .
The invention solves the problem of increasing the processability and safety of the process by optimizing the composition of the reaction mass and the resulting dimethylphosphite raw for further purification by vacuum distillation, in particular decrease in the reaction mass and dimethylphosphite-raw amount of impurities: monomethyl phosphite, phosphorous acid, and non-identifiable impurities.
This problem is solved in the fact that in the known method of obtaining dimethylphosphite by the interaction of the phosphorus three chloride with methanol in the medium of the evaporating chloride of methyl under reduced pressure, the paypad of volatile components and the subsequent purification of the product obtained by vacuum distillation, according to the invention, the interaction is carried out with a molly ratio of methanol to the phosphorus three chloride 3.02 -3.3: 1, with their bulk ratio, respectively, 1.43-1.53: 1 and residual pressure 0.02-0.04 MPa. In addition, the interaction is mainly at a temperature of 0-30 ° C.
The synthesis of dimethylphosfite according to the proposed method is carried out in the reactor, which is a vertical cylindrical hollow apparatus with a conical bottom, made from a corrosion-resistant steel, equipped with a distributor for feeding a methyl chloride, built into the bottom of the reactor, and two siphons for supplying phosphorus three chloride and methanol, mounted diametrically in conical part of the reactor. The content of methyl chloride in the reaction mass is constantly and maintained at 4.8-5.2 wt.%.
The temperature of the synthesis of 0-30 ° C in the reactor is maintained automatically by evaporation of the methyl liquid chloride supplied to the reaction zone, and the required vacuum in the reactor is supported by a vacuum pump to remove from the zone of the volatile-chloride hydrogen chloride, methyl chloride and excess methanol. Not fully freed from the volatile products of dimethylphosphite raw from the reactor through the hydraulicum enters the stripping column for full release From the residues of volatile products, and then purification of dimethylphosphite with distillation under vacuum.
The use of the proposed method allows to obtain dimethylphosphite-raw consistently constant composition with a reduced content of unwanted impurities, which, in turn, makes it possible to highlight the target product of higher quality and improve the safety of the process.
Reducing the molar ratio of methanol to phosphorum three chloride, the volumetric ratio of methanol to the phosphorum three chloride is below 1.43 and the residual pressure below 0.02 MPa, in addition to increasing the content of the reaction mass and dimethylphosphite-raw monomethyl phosphite and phosphorous acid, leads to the development of intermediate products Methydichlorphosfite and dimethyl chlorphosphite, which are very reactive compounds that can cause an explosion, and an increase in the molar ratio of methanol to the phosphorus three chloride above 3.3: 1, the volumetric ratio of methanol to the phosphorum three chloride above 1.53 and residual pressure above 0.04 MPa leads to an increase Contents in the target product of unidentifiable impurities and reducing the exit.
The process leads with a molar ratio of methanol components to phosphorus three chloride 3.24: 1 and with their volume ratio of components 1.50: 1.
The continuous volume flow rate of reagents and methyl chloride (refrigerant) is:
Phosphorus three chloride - 0.3-0.8 m 3 / h;
Methanol - 0.4-1.2 m 3 / h;
Methyl chloride - 0.5-2.5 m 3 / h.
Dimethylphosfit - raw from the synthesis reactor through the hydraulic system continuously enters the stripping column for the full separation of the remnants of volatile products. The stripping column consists of a cylindrical, nozzle, filled with rolling rings and a hollow cubic part, made in the form of a cone and equipped with a ferry heating shirt. The paypark of light pall tile products is carried out in a continuous film mode at a cube of a column of 70-90 ° C and a residual pressure of 0.093 MPa.
The abnormal components (methyl chloride, hydrogen chloride, methanol) are condensed in the heat exchanger and return to the reactor, and dimethylphosphite raw, freed from the volatile components, continuously enters the distillation into two sequentially arranged rotary-film evaporators (RPI).
The process was carried out in mode:
Volumetric flow rate of dimethylphosphite-raw nutrition of the RPI not more than 0.6 m 3;
Temperature in the vapor phase is not more than 90 ° C;
Residual pressure of at least 0.093 MPa.
The target product thus obtained contains 99.35% dimethylphosphite.
Examples 2-10. The process led analogously to example 1, changing the molar and volumetric ratio of reagents, temperature regime and pressure.
The results are presented in the table.
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MOLID SOTH WORK M: TF |
Volumetric I Wear M: TF |
Temperature in the reaction. Most |
Residual pressure, MPa |
Exit in synthesis in terms of TF |
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Notes: M - methanol; |
Conclusion:
Widespread use in production and in the life of phosphorodorganic
compounds (chlorophos, thiophos, carbofos, etc.) led to the increased
the frequency of poisoning them.
Modern views on the principles of treatment of poisoning phos
based on the provisions of evidence-based medicine (EBM). Choice of funds
the relief of the main syndromes from EBM standpoints should be based on
ideas about the mechanism and pathogenesis of intoxication (principle
validity) and modern information of the pharmacopoeia (principle of efficiency). Fundamental importance should be given antidote
therapy. Since the leading pathological processes occur in
synapses, then antidote therapy is aimed at normalizing
nerve impulses in them.
An important role belongs to measures for the prevention of poisoning
phosporganic connections.
Bibliography:
1. Gabrielyan O. S., Ostrumov I. G. Chemistry. M., Drop, 2008;
2. Chichibabin A. E. The main principles of organic chemistry. M., Goshimzdat, 1963. - 922 p.;
3. Lebedev N. N. Chemistry and technology of the main organic and petrochemical synthesis. M., Chemistry. 1988. - 592 p.;
4. Paushkin J. M., Adelson S. V., Vishnyakova T. P. Technology of petrochemical synthesis. M., 1973. - 448 p.;
5. Yukelson I. I. Technology of the main organic synthesis. M., "Chemistry", 1968.
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