Method for reduction of unsaturated ketones to saturated ketones

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of saturated ketones from corresponding unsaturated compounds (enones) using sodium dithionite as a reducing agent in an aqueous-organic medium based on surface-active substances. Method is carried out by reduction of unsaturated ketones of the general formula (I): to saturated ketones of the general formula (II): wherein R means lower alkyl or phenyl; R1 means hydrogen atom, (C3-C6)-alkyl or phenyl; R2 means alkyl or (C3-C6)-cycloalkyl, or alkyl substitutes R1 and R2 can form in common 5-6-membered carbocycle; R3 means hydrogen atom. The reduction reaction is carried out with sodium dithionite in an aqueous-organic microemulsion medium containing a surface-active substance as a solubilizing agent, aliphatic alcohols of normal or branched structure with number of carbon atoms from 3 to 5 as a co-solubilizing agent, and water in the mole ratio = 1:(4-6):(200-400), respectively, in the presence of electrolyte. The end substance is isolated by extraction. Method involves using anionic or cationic surface-active substances of the general formula: CnH2n+1X wherein X means -OSO3M, -SO3M, -COOM, -NMe3Hlg (wherein M means alkaline metal or ammonium; Hlg means halide); n = 11-16. Alkaline metal carbonates or hydrocarbonates are used as an electrolyte. Invention provides using inexpensive available reducing agent, simplifying process, enhancing purity and yield of the end substance.

EFFECT: improved method of synthesis.

3 cl, 9 ex

 

The invention relates to the synthesis of organic compounds, specifically to obtain saturated ketones by the reaction of recovery unsaturated ketones, and may find wide application in the chemical industry, in particular in the production of odoriferous substances, as well as in the agricultural and pharmaceutical industries.

Known methods of recovery of various organic compounds including unsaturated ketones using dithionite sodium. So, from EN 2167661, 27.05.2001 known to produce 7-deoxy-13-dihydro-14(N-morpholino)daunomycin recovery 13-dihydro-14(N-morpholino)daunomycin.

To a solution of 13-dihydro-14(N-morpholino)daunomycin (0,240 g, 0,494 mmol) in dimethylformamide (16 ml) was added with stirring at room temperature in an argon atmosphere is added dropwise a solution of dithionite sodium (2.15 g, of 1.23 mmol) in water (8 ml). After stirring for 1 hour at room temperature, the reaction mixture was poured into water (250 ml) and extracted with ethyl acetate (6×25 ml).

The layers separated, the organic layer washed with water, dried over sodium sulfate and evaporated to obtain 300 mg of the crude product, which is then cleaned using column chromatography on silica gel (eluent: chloroform/methanol 96:4 by volume). Specified in the title compound (116 mg, 50%) was isolated as a red powder and then translate it to the corresponding hydrochloride by adding a stoichiometric amount of hydrogen chloride in methanol, followed by planting diethyl ether.

From RU 2104281, 10.02.1998 known method of obtaining a mixture of sennosides a, b and A1formula

containing less than 100 million-1sennosides C, D, and D1and components of aloe-emodina, in which a mixture of sennosides, highlighted by the extraction of medicinal plants, subjected to restore dithionite alkali metal with product recovery, containing failure to comply-9 Andron-8-glucoside. Product recovery is extracted using a two-phase solvent-containing aqueous phase and phase 2-butanol in a volume ratio of phases 1:5:40, respectively, transferred to the aqueous phase in the extraction failure to comply-9 Andron-8-glucoside oxidized by oxygen at pH 6-7 or salt of iron(III) at pH 8.0-8.5 to relevant sennosides with their subsequent selection. Dithionite Na2S2O4(the technical name of hydrosulfite sodium) is readily available cheap the reducing agent. It has long been known the use of this reagent for the recovery of carbonyl compounds to alcohols1, 2, in benzyl benzoin in aqueous-alcoholic medium3, halogen in heme-dibromopropane4, azobenzenes to hydrazobenzene5, nitro compounds to anilines and hydroxylamino6, 7including immobilized on polymeric substrates8. The wide use of this is a powerful reducing agent is constrained by its complete insolubility in organic solvents, , both polar and non-polar (see, for example,8). Reactions with organic compounds having at least partial solubility in water, is carried out in aqueous-organic media. For the vast majority of organic compounds, is completely insoluble in water and aqueous media, the use of this reducing agent was previously almost impossible, although there are several techniques that can be used to partially solve the problem. In some cases, it is shown that it is possible to use additional vectors of the electron type viologen5, 7, 9, 10or similar polymeric catalysts11without vectors reaction is practically not occur. Also used interphase catalysts of the type trialkylaluminium (commercial name Aliquat 336 and Adogen 464)12-16and for the efficient recovery of water-insoluble compounds requires the use of 20 to 30-fold excess carrier, which is not always gives a positive result due to incomplete recovery17the low speed of the reaction18that required the use of large excess of reducing agent19. Another technique is the use of cyclodextrins as phase transfer catalysts20-24cannot be used for preparative purposes because of the low transfer efficiency and high is stoimosti cyclodextrins.

All these techniques are impractical for use in technology of fine organic synthesis, used as supplements are extremely expensive, which completely destroys the economic effect from the use of cheap reductant.

Known, in particular, the method of recovering unsaturated ketones (enones) dithionite sodium in aqueous-organic medium in the presence of interfacial vectors12-14, 25. This known method has all the disadvantages listed above. The technical task is claimed as the invention of the method is a simplification of it (except expensive interfacial vectors, ease of selection of the reaction product), improving environmental safety while achieving a high yield of the target product.

The goal of the project is achieved in that in the method of recovering unsaturated ketones of General formula

in saturated ketones of General formula

where R is lower alkyl or phenyl

R1is hydrogen, alkyl With3-C6or phenyl,

R2is alkyl or cycloalkyl3-C6or alkyl substituents R1and R2together may form a 5 - or 6-membered carbocycle;

R3is hydrogen;

dithionite sodium in aqueous-organic medium with the respective allocation of the target product extraction, recovery dithionite sodium is carried out in aqueous-organic microemulsions, consisting of a solubilizer (detergent) - surfactants, coolability - aliphatic alcohols of normal and branched structure with the number of carbon atoms from 3 to 5, and water at a molar ratio of 1:4-6:200-400 and in the presence of an electrolyte - carbonate or bicarbonate of alkali metals or ammonium.

So, according to the invention the reaction of the recovery of unsaturated ketones by dithionite sodium is conducted in aqueous-organic micro-emulsions - a special environment with high solubility ability to hydrophobic water-insoluble organic substances. For such environments, a mixture of surface-active solubilizer, coolability, water and electrolyte in a ratio to achieve the optimal hydrophilic-lipophilic balance system. The resulting environment is thermodynamically stable, have visual homogeneity (transparent and not stratified by arbitrarily long ageing in the temperature range from room temperature up to 100° (C)capable of solubilizing without external signs of the formation of a new phase of a significant number of hydrophobic water-insoluble organic compounds (e.g., hydrocarbons, steroids) on the molar concentrations. As detergent used single-chain cationic or anionic detergent from a number CnH2n+1X, where X=OSO3M, SO3M, SOOMA, NMe3Hlg (M is alkali metal or ammonium, Hlg - halide), n=11-16.

As coolability used aliphatic alcohols normal or branched chain structure with a number of carbon atoms from 3 to 5.

The composition solubilizes environment - solubilizer-coolability-water in a molar ratio of 1:4-6:200-400. The components are mixed until a homogeneous solution, to be used further as a reaction medium. The amount of electrolyte may be in the range of 2-15 times by moles relative to the content of the detergent-solubilizer.

The following examples illustrate the invention but do not restrict it.

Example 1. Restore chalcone 1.3-diphenylpropane-1

In a three-neck flask of 1 l equipped with a stirrer, reflux condenser and addition funnel, was placed a microemulsion prepared from 20 ml of ISO-butanol, 20 g of hexadecyltrimethylammonium and 30 ml of water (molar ratio of 4:1:300). The mixture was stirred at room temperature until, until it formed a clear homogeneous solution (about 5 min). To the obtained solution under stirring was added 20.8 g (0.1 mol) of chalcone and added 45 g Carbo is ATA sodium. The mixture was heated in a stream of nitrogen to a boil and added 34.8 g (0.2 mol) of dithionite sodium. The resulting solution was heated at boiling, adding chunks 34.8 g (0.1 mol) of dithionite sodium. The reaction mixture was cooled to room temperature, was added 200 ml of methylene chloride and 300 ml saturated NaCl solution. After 10 min stirring and separation of the phases have separated the organic layer, washed with water (2×200 ml), saturated NaCl (1×200 ml) and dried over Na2SO4. The solution was evaporated on a rotary evaporator under vacuum, the solid residue was dissolved in 100 ml diethyl ether and filtered through a layer of silica gel, the solution was evaporated in vacuo and recrystallize from ethanol. Received 19 g (90% of theory.) yellowish crystals with TPL 71-73°C.

PMR (ppm, CDCl3, 500 MHz): 3.02 (2H, m), 3.27 (2H, m), 7.1-7.5 (10H, m)

Example 2. As example 1, but the microemulsion comprised of 19 ml of ISO-amyl alcohol, 13 g of potassium palmitate (C15H31COOK) and 200 ml of water (molar ratio of 4:1:250). Got 18.5 g (88% of theory.) white crystals with TPL 72-73°C.

Example 3. Recovery of beta ionone at dihydro-beta-ionon (fragrant substance, an intermediate in organic synthesis).

In a three-neck flask of 100 ml equipped with a stirrer, reflux condenser and addition funnel, was placed a microemulsion prepared with the th of 2 ml of ISO-butanol, 2 g of hexadecyltrimethylammonium and 30 ml of water (molar ratio of 4:1:300). The mixture was stirred at room temperature until, until it formed a clear homogeneous solution (about 5 min). To the obtained solution under stirring was added 1.92 g (0.01 mol) of beta ionone and 4.5 g of potassium bicarbonate. The mixture was heated in a stream of nitrogen to a boil and added 3.48 g (0.02 mol) of dithionite sodium. The resulting solution was heated at boiling, adding chunks 3.48 g (0.02 mol) of dithionite sodium. The reaction mixture was cooled to room temperature, was added 25 ml of methylene chloride and 20 ml of a saturated solution of NaCl. After 10 min stirring and separation of the phases have separated the organic layer, washed with water (3×50 ml), saturated NaCl (1×50 ml) and dried over Na2SO4. The solution was evaporated on a rotary evaporator under vacuum, the solid residue was dissolved in 100 ml diethyl ether and filtered through a layer of silica gel, the solution was evaporated in vacuo, and purified flash chromatography. Yield 1.76 g (91% of theory) of a yellowish oil. PMR (CDCl3, 500 MHz): 2.45 (2H, m), 2.20 (2H, m), 2.07 (3H, s), 1.87 (2H, m), 1.30-1.55 (7H, m), 0.93 (6N, C).

Example 4. As in example 3, but the microemulsion comprised of 3 ml of isoamyl alcohol, 1.3 g of potassium salt of lauric acid (C11H23The Cooke) and 30 ml of water (molar ratio 5:1:300). Yield 1.6 g (82% of theory) b-black. oil. The PMR SPECTRUM, as the example 5.

Example 5: Receiving 7,8-dehydroisoandrosterone recovery isoelectron

In a three-neck flask of 1 l equipped with a stirrer, reflux condenser and addition funnel, was placed a microemulsion prepared from 16 ml of n-butanol, 16 g of hexadecyltrimethylammonium and 260 ml of water (molar ratio of 4:1:330). The mixture was stirred at room temperature until, until it formed a clear homogeneous solution (about 5 min). To the obtained solution under stirring was added a solution of 19.7 g (0.05 mol) of 7,8-dehydroisoandrosterone in 70 ml of toluene and was added 40 g of sodium bicarbonate. The mixture was heated in a stream of nitrogen to a boil and added 17.4 g (0.1 mol) of dithionite sodium. The resulting solution was heated at boiling, adding chunks 17.4 g (0.1 mol) of dithionite sodium. The reaction mixture was cooled to room temperature, was added 200 ml of methylene chloride and 300 ml saturated NaCl solution. After 10 min stirring and separation of the phases have separated the organic layer, washed with water (2×200 ml), saturated NaCl (1×200 ml) and dried over Na2SO4. The solution was evaporated on a rotary evaporator under vacuum, the solid residue was dissolved in 100 ml diethyl ether and filtered through a layer of silica gel, the solution was evaporated in vacuo and recrystallize from methanol. Received 18.2 g (92% of those who RV) of white crystals with TPL 110-111°C. PMR SPECTRUM (CDCl3, 500 MHz): 0,70 (3H), 0,81 (6N), TO 0.92 (3H), 1,02 (6N), 1,1-2,1 (complex multiplet), and 5.2 (2H).

Example 6. As in example 5, but the microemulsion was from 1.5 g of tetradecyltrimethylammonium, 1.6 ml of n-butanol and 30 ml of water (molar ratio of 4:1:380). Received 1.8 g (90% of theory.) white crystals with TPL 109-111°C. PMR SPECTRUM, as in example 5.

Example 7. As in example 5, but the microemulsion was from 1.5 g of tetradecyltrimethylammonium, 2 ml n-propanol and 25 ml of water (molar ratio 6:1:380). Received 1.6 g (82% of theory.) white crystals with TPL 107-108°C. PMR SPECTRUM, as in example 5.

Example 8. As in example 5, but the microemulsion was from 1.35 g of dodecyltrimethylammonium, 2 ml of n-butanol and 20 ml of water (molar ratio 5:1:250). Received 1.5 g (76% of theory.) white crystals with TPL 107-109°C. PMR SPECTRUM, as in example 5.

Example 9. As in example 5, but the microemulsion was from 1.26 g of sodium dodecyl sulfate, 2 ml of ISO-butanol and 24 ml of water (molar ratio 5:1:300). Received 1.5 g (76% of theory) of white crystals with TPL 106-109°C. PMR SPECTRUM, as in example 5.

Thus, the claimed method relates to the recovery of unsaturated ketones using technical dithionite sodium for recovery of water-insoluble organic compounds without the use of expensive additives and catalysts. Proposed meditive opens the possibility of using this readily available cheap reductant in fine organic synthesis production of aromatic substances, pharmaceutical and agrochemical drugs such as steroids, stimulants and other advantages of the method -

a) the use of environmentally and technologically secure environment reaction - microemulsion, the main component of which is water rather than an organic solvent;

b) the exclusion of expensive imported interface Perevozchikova used in the method prototype in large quantities (up to 20-30-fold relative to the substrate reaction), which further creates formidable problems in the allocation of the reaction products (the formation of stable nerasseivayushchee emulsions during extraction of the product);

C) the achievement of high yields of the target products and the absence of side products of the comprehensive recovery of alcohols;

d) ease of selection of the reaction product from the reaction mixture.

Sources of information

[1] Giordano, S.; Perdoncin, G.; Castaldi, G. Angewandte Chemie-International Edition In English 1985, 24, 499-500.

[2] Castaldi, G.; Perdoncin, G.; Giordano, C.; Minisci, F. Tetrahedron Letters 1983, 24, 2487-2490.

[3] Heilmann, S.M.; Rasmussen, J..; Smith, H.K. Journal Of Organic Chemistry 1983, 48, 987-992.

[4] Khurana, J.M.; Sehgal, A. Synthetic Communications, 1996, 26, 3791-3798.

[5] Park, K.; Han, S.Y. Tetrahedron Letters 1996, 37, 6721-6724.

[6] Khurana, J.M.; Singh, S. Journal of the Indian Chemical Society 1996, 73, 487-488.

[7] Park, K.; Oh, S.; Sim, W.J. Journal of ORGANIC Chemistry 1995, 60, 6202-6204.

[8] Scheuerman, R. A.; Tumelty, D. Tetrahedron Letters 2000, 41, 6531-6535.

[9] Park, K.; Oh, C.H.; Joung, W.. Tetrahedro Letters 1993, 34, 7445-7446.

[10] Yang, D.L.; Fokas, D.; Li, J.Z.; Yu, L..; Baldino, C.M. Synthesis-Stuttgart 2005, 47-56.

[11] Noguchi, H.; Tsutsum, H.; Komiyama, M. Chemical Communications 2000, 2455-2456.

[12] Camps, F.; Coll, J.; Guitart, J. Tetrahedron 1986, 42, 4603-4609.

[13] Camps, F.; Coll, J.; Guitart, J. Tetrahedron 1987, 43, 2329-2334.

[14] Camps, F.; Coll, J.; Guitart, J. Journal of Chemical Research-S 1990, 38-38.

[15] Gabriels, S.; Van Haver, D.; Vandewalle, M.; De Clercq, P.; Verstuyf, A.; Bouillon, R. Chemistry-a European Journal 2001, 7, 520-532.

[16] Farrera, J.A.; Anglada, M. R.; Ribo, J.M. Monatshefte für Chemie 1995, 126, 355 to 360 above.

[17] Pommier, A.; Stepanenko, V.; Jarowicki, K.; Kocienski, P. J. Journal of Organic Chemistry 2003, 68, 4008-4013.

[18] Chakraborty, A.; Kar, G..; Ray, J.. Tetrahedron 1997, 53, 8513-8518.

[19] Toyota, M.; Nishikawa, Y.; Fukumoto, K. Tetrahedron 1996, 52, 10347-10362.

[20] Ravi, P.; Divakar, S. Journal of Inclusion Phenomena and Macrocyclic Chemistry 2003, 45, 191-194.

[21] Ravichandran, R.; Divakar, S. Journal of Inclusion Phenomena and Molecular Recognition in Chemistry 1994,18, 369-375.

[22] Ravichandran, R.; Divakar, S. Journal of Molecular Catalysis 1994, 93, L247-L251.

[23] Fornasier, R.; Marcuzzi, F.; Parmagnani, M.; Tonellato, U. Carbohydrate Research 1991, 217, 245-249.

[24] Fornasier, R.; Marcuzzi, F.; Tonellato, U. Journal of Inclusion Phenomena and Molecular Recognition in Chemistry 1994, 18, 81-92.

[25] Brosa, C.; Rodriguez-Santamarta, S. Tetrahedron 1999, 55, 1793-1798.

1. Method of recovering unsaturated ketones of General formula (1)

in saturated ketones of General formula (2)

where R is lower alkyl or phenyl;

R1is hydrogen, alkyl With3-C6or phenyl;

R2is alkyl or cycloalkyl3-C6or alkyl substituents R and R2together may form a 5 - or 6-membered carbocycle;

R3- hydrogen

dithionite sodium in aqueous-organic micro-emulsions containing the solubilizer - surfactant, coolability - aliphatic alcohols normal or branched chain structure with a number of carbon atoms from 3 to 5, and water at a molar ratio of 1:4-6:200-400 and in the presence of an electrolyte, followed by separation of the target product extraction.

2. The method according to claim 1, in which as a solubilizer detergent use anionic or cationic surfactants of General formula CnH2n+1X, where X=OSO3M, SO3M, SOOMA, NMe3Hlg (M is alkali metal or ammonium, Hlg - halide), n=11-16.

3. The method according to claim 1, in which as coolability use fatty alcohols normal or isotrate with the number of carbon atoms from 3 to 5 (n-propanol, isopropanol, n-butanol, Isobutanol, torbutrol, tertbutanol, isoamyl alcohol).

4. The method according to claim 1, in which the electrolyte used carbonates or bicarbonates of alkali metals.



 

Same patents:

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for oxidizing liquid hydrocarbons in barrier discharge carried out in the bubble reactor with mixtures of oxygen with helium, argon or nitrogen. Method involves using helium, argon and nitrogen taken in the amount 20-80%. The oxidation process is carried out in the presence of solid additives wherein aluminum, nickel, molybdenum, copper oxides or zeolite catalyst ZSM-5 comprising 1.2% of Fe is used. Method provides reducing energy consumptions for oxidation of the parent hydrocarbon in the barrier discharge.

EFFECT: improved oxidizing method.

3 cl, 2 tbl, 10 ex

The invention relates to a method for producing carbonyl compounds with the number of atoms2-C40

The invention relates to the field of synthesis of terpenoid ketones, and in particular to an improved method of obtaining Fiona, which can be used in the synthesis of vitamins E and K

The invention relates to the field of production of oxygen-containing organic compounds, ketones, unsaturated alcohols and possibly aldehydes by isomerization WITH5-epoxides in the presence of a homogeneous catalyst
The invention relates to a method for producing 1-phenyl-1-(alkyl)phenylacetone, which is an intermediate for obtaining rodenticide preparations of 2-(-phenyl--(alkyl)phenylacetyl)indandione-1,3, in particular ethylbenzene(alkyl R = C2H5and izinduna (alkyl R = ISO-C3H7) used for the control of rodents

The invention relates to the production of lower ketones liquid-phase dehydrogenation of secondary alcohols in the presence of a fixed catalyst - Nickel metal or activated hydrogen Nickel metal or Nickel on the carrier in the environment paraffins C12-C20that process is used as solvent, the drying means, the environment for the activation of the catalyst and carrier

The invention relates to a method for producing ketones, in particular to a method for producing ketones using reaction paired diolefines and water, and thus obtained ketones

The invention relates to a method for producing CIS-verbenol, used to control harmful insects, as well as being intermediate for the synthesis of valuable aromatic and medicinal substances, such as citral, menthol and other

The invention relates to methods for producing propanol-2, which is widely used as a solvent in the manufacture of surfactants, plasticizers, additives to oils, medicines
The invention relates to the production of isotope labeled products with high chemical and isotopic purity, namely to obtain isopropyl-D8alcohol

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of saturated ketones from corresponding unsaturated compounds (enones) using sodium dithionite as a reducing agent in an aqueous-organic medium based on surface-active substances. Method is carried out by reduction of unsaturated ketones of the general formula (I): to saturated ketones of the general formula (II): wherein R means lower alkyl or phenyl; R1 means hydrogen atom, (C3-C6)-alkyl or phenyl; R2 means alkyl or (C3-C6)-cycloalkyl, or alkyl substitutes R1 and R2 can form in common 5-6-membered carbocycle; R3 means hydrogen atom. The reduction reaction is carried out with sodium dithionite in an aqueous-organic microemulsion medium containing a surface-active substance as a solubilizing agent, aliphatic alcohols of normal or branched structure with number of carbon atoms from 3 to 5 as a co-solubilizing agent, and water in the mole ratio = 1:(4-6):(200-400), respectively, in the presence of electrolyte. The end substance is isolated by extraction. Method involves using anionic or cationic surface-active substances of the general formula: CnH2n+1X wherein X means -OSO3M, -SO3M, -COOM, -NMe3Hlg (wherein M means alkaline metal or ammonium; Hlg means halide); n = 11-16. Alkaline metal carbonates or hydrocarbonates are used as an electrolyte. Invention provides using inexpensive available reducing agent, simplifying process, enhancing purity and yield of the end substance.

EFFECT: improved method of synthesis.

3 cl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining hexafluorisopropanol applied as solvent for some polymer materials, as valuable emulsifier and as raw material for obtaining sevoflurane, a new generation anesthetic. Method involves recovery of hexafluoroacetone by reducer. Hexafluoroacetone trihydrate is recovered by using hydrazine-hydrate as reducer at mol ration of hexafluoroacetone trihydrate to hydrazine-hydrate of 1:(1.1-1.5), with further addition of hydrogen peroxide in the form of 36-50% solution.

EFFECT: obtaining pure target product at high output rate by cost-effective and simple method.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of fragrant compounds selected from a mixture of compounds (5a-d), (6a-d), (6a'-6d'), (7a-d) and (7a'-7d'), to a method of preparing said mixtures, to fragrant, perfumed and cosmetic compositions, as well as to household chemicals based on said compounds and to use of said mixtures or fragrant compositions based on said compounds as a fragrant agent, an agent which masks or neutralises smell. (5a-d), (6a-d) and (7a-d), where R denotes a methyl group, (6a'-6d') and (7a'-7d'), where R denotes an ethyl group.

EFFECT: preparing the mixtures of fragrant compounds.

16 cl, 1 dwg, 8 ex

FIELD: chemistry.

SUBSTANCE: method involves reducing hexafluoroacetone (HFA) in an aqueous medium, wherein the hexafluoroacetone is used in trihydrate form or 50% aqueous solution, and the reducing agent used is phosphorous acid in the presence of aqueous ammonia solution in molar ratio HFA:H3PO3NH3 (1:1.2-1.3:3), with catalysis by transition metal salts.

EFFECT: invention enables to obtain the end product in a single step using cheap and nontoxic reactants.

2 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: as a reducer applied is diisobutylaluminiumhydride (DIBAH), taken in a molar ratio of verbenone: DIBAH, equal to 1:1.8-2.2, and as organic solvent - dichloromethane, the process is carried out at temperatures of minus 78C - minus 65C for 90-120 min, and separation of the target product is carried out by processing a reaction mixture with water, taken in a quantity of 300-400% of a stoichiometrically necessary one for decomposition of DIBAG excess, separation of sediment and its washing with dichloromethane, removal of water remains from the filtrate above sodium sulphate and evaporation of an organic solvent under reduced pressure.

EFFECT: method makes it possible to increase stereo-selectivity of the reaction and increase the output of the target product.

1 tbl

FIELD: chemistry.

SUBSTANCE: method consists in the reduction of hexafluoroacetone with formic acid derivatives. Hexafluoroacetone is applied in the form of its sesquihydrate and reduction is realised by the interaction of the claimed sesquihydrate with salts of formic acid at boiling and the following ratio of reagents (CF3COCF31.6H2O):M(HCOO) 1:1.5-4, where M=NH4, Na, K.

EFFECT: method makes it possible to obtain hexafluoroisopropanol with high output.

1 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for oxidizing liquid hydrocarbons in barrier discharge carried out in the bubble reactor with mixtures of oxygen with helium, argon or nitrogen. Method involves using helium, argon and nitrogen taken in the amount 20-80%. The oxidation process is carried out in the presence of solid additives wherein aluminum, nickel, molybdenum, copper oxides or zeolite catalyst ZSM-5 comprising 1.2% of Fe is used. Method provides reducing energy consumptions for oxidation of the parent hydrocarbon in the barrier discharge.

EFFECT: improved oxidizing method.

3 cl, 2 tbl, 10 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of saturated ketones from corresponding unsaturated compounds (enones) using sodium dithionite as a reducing agent in an aqueous-organic medium based on surface-active substances. Method is carried out by reduction of unsaturated ketones of the general formula (I): to saturated ketones of the general formula (II): wherein R means lower alkyl or phenyl; R1 means hydrogen atom, (C3-C6)-alkyl or phenyl; R2 means alkyl or (C3-C6)-cycloalkyl, or alkyl substitutes R1 and R2 can form in common 5-6-membered carbocycle; R3 means hydrogen atom. The reduction reaction is carried out with sodium dithionite in an aqueous-organic microemulsion medium containing a surface-active substance as a solubilizing agent, aliphatic alcohols of normal or branched structure with number of carbon atoms from 3 to 5 as a co-solubilizing agent, and water in the mole ratio = 1:(4-6):(200-400), respectively, in the presence of electrolyte. The end substance is isolated by extraction. Method involves using anionic or cationic surface-active substances of the general formula: CnH2n+1X wherein X means -OSO3M, -SO3M, -COOM, -NMe3Hlg (wherein M means alkaline metal or ammonium; Hlg means halide); n = 11-16. Alkaline metal carbonates or hydrocarbonates are used as an electrolyte. Invention provides using inexpensive available reducing agent, simplifying process, enhancing purity and yield of the end substance.

EFFECT: improved method of synthesis.

3 cl, 9 ex

Up!