Method for preparing fluorinated benzonitrile

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of tetrafluorobenzonitrile of the formula (2): Method involves hydrogenolysis of a single cyano-group of tetrafluorodicyanobenzene of the formula (I): by effect of hydrogen at temperature above 100°C in the presence of the hydrodecyanidation catalyst of platinum group and synthetic zeolite. Invention shows economy profit in the industrial aspect of method for synthesis of tetrafluorobenzonitrile that can be used as agrochemical and medicinal intermediate compound.

EFFECT: improved method of synthesis.

7 cl, 13 ex

 

The SCOPE of the INVENTION

The present invention relates to a method of producing tetrafluorobenzoate used as intermediate compounds for agrochemicals, pharmaceuticals, electrochemical means, photochemical substances, certain chemicals, some polymers, etc. Tetrafluorobenzoate is appropriate intermediate compound to obtain esters cyclopropanecarbonyl acids, have good insecticidal activity.

The LEVEL of TECHNOLOGY

It is known that ether of 2,2-dimethyl-3-halogenated vinyl cyclopropanecarbonyl acid benzyl alcohol, substituted from 1 to 4 fluorine atoms and from 0 to 2 chlorine atoms, has excellent insecticidal activity. In particular, DE-A-3705224 indicates that the ether cyclopropanecarbonyl acid 2,3,5,6-tetrafluorobenzyl alcohol has a high insecticidal activity and that it is less toxic to mammals than ether cyclopropanecarbonyl acid pentafluorobenzyl alcohol, and therefore is the best insecticide.

WO 9808795 discloses a method of obtaining a fluorinated benzyl alcohol, in which the method of fluorination of dicyanobenzene includes hydrogenolysis in the presence of a catalyst to gidrogenizirovanii only one ceanography to obtain fluorinated Bentonit the sludge and conversion ceanography fluorinated benzonitrile in hydroxymethylene group. This method is suitable for the production of 2,3,5,6-tetrafluorobenzyl alcohol of high purity and in high yields.

However, the above-mentioned receiving fluorinated benzonitrile by hydrogenolysis fluorinated dicyanobenzene includes large amounts of catalyst, which greatly affects the cost of production.

The PURPOSE of the INVENTION

The aim of the invention is to provide an industrial method of producing tetrafluorobenzoate, a useful intermediate for agrochemicals, pharmaceuticals, electrochemical means, photochemical substances, certain chemicals, some polymers, etc., hydrogenolysis of tetraphenylborate with the use of the catalyst in small quantities, the INVENTION

It was found that when carrying out the hydrogenolysis of tetraphenylborate formula (I):

in the presence of a catalyst of gidrogenizirovanii only one ceanography with getting tetrafluorobenzoate formula (2):

the amount of catalyst can be reduced by using in the reaction of synthetic zeolite.

The present invention is entirely based on this discovery.

The present invention relates to:

The method of producing tetrafluorobenzoate formula (2)

including hydrogenolysis only one ceanography tetrafluorobenzene formula (I):

under the influence of hydrogen at a temperature above 100°in the presence of a catalyst of gidrogenizirovanii platinum group and synthetic zeolite.

The way in which synthetic zeolite represents at least one zeolite selected from zeolites 3A, 4A and 5A.

The way in which the synthetic zeolite is a zeolite 4A and/or 5A.

The way in which the synthetic zeolite is a zeolite 5A.

The manner in which the catalyst is a palladium on charcoal.

The way in which the water content of the substances in the reaction system, in addition to zeolite, is not more than 3000 ppm of the total number of substances in the reaction system, excluding the zeolite.

The way in which tetraphenylborate is tetraferriphlogopite and tetrafluorobenzoate is a 2,3,5,6-tetrafluorobenzoate.

The BEST WAY of carrying out the INVENTION

The present invention is described next.

Source tetraphenylborate formula (1) can be obtained by known methods and are commercially available. Examples include tetraterpenoids, tetrameristaceae and thecraft terephthalonitrile.

Hydrogenolysis of tetraphenylborate carried out in the presence of a catalyst and zeolite. Examples of catalysts are the catalysts of the platinum group metals, such metals include palladium, platinum, Nickel, ruthenium and rhodium. Especially preferred is palladium. These metals can catalyze themselves or in the form of a catalyst on the carrier. Examples of carriers for catalysts include activated carbon, silicon dioxide and aluminum oxide. As a preferred catalyst is palladium on charcoal.

As a result of adding zeolite reaction according to the invention may be almost finished (conversion of 95% or above) with catalyst used in amounts of 5% or less by weight, especially 2% or less by weight. This amount of catalyst is the mass percent (mass%) of the metal acting as the catalyst, the amount of the original tetraphenylborate.

Without the use of a zeolite gidrogenizirovanii of tetraphenylborate ends during the reaction with such small quantities of catalyst, 5% or less by mass, so that the conversion can be increased. To increase conversion rates and achieve output of at least 70%must be used catalyst in the amount of 10% or more by weight, or even 20% or more by weight of the of traffordcentre.

The zeolite preferably is a synthetic zeolite. Examples of synthetic zeolite for use in the above reaction include zeolites 3A, 4A, 5A, 10X and H. Of them, preferred are zeolites 3A, 4A and 5A, and more preferred are zeolites 4A and/or 5A, and particularly preferred is zeolite 5A. Synthetic zeolite is preferably used in amounts of 10% or more by weight of the original tetraphenylborate. No particular limitation on the upper limit of the amount of zeolite does not exist due to end action, but adding excessive amounts leads to difficulty mixing or to such problems impeding the reaction. In fact, the zeolite is used in quantities not exceeding the amount of the solvent, preferably no more than half the amount of the solvent. Zeolite can be used separately or in combination.

The solvent for use in the above reaction is not particularly limited since it does not affect the reaction. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and mesitylene; aliphatic hydrocarbons such as hexane and cyclohexane; alcohols such as methanol, ethanol, 1-propanol, 2-propanol and n-butanol; ethers, such as tetrahydrofuran, 1,4-dioxane and dieting collimation ether. Aromatic hydrocarbons are particularly preferred. The amount of solvent is not particularly limited within the normal range, but is preferably equivalent to or more than 50 times, more preferably from two to twenty times greater than the number of source tetraphenylborate.

Since the introduction of synthetic zeolite does not provide a sufficient effect when the water content in the reaction system is high, the water content is preferably reduced to such an introduction. If the zeolite is added last, the water content prior to the introduction ideally, is not more than 3000 ppm. In this case, the water content in the reaction system can be reduced by azeotropic distillation, etc. Because the sequence of the introduction of synthetic zeolite, the source of raw materials, etc. can be arbitrary, the total water content in the solvent, raw materials, etc. ideally reduce not more than 3000 ppm of the total amount of these substances, excluding synthetic zeolite, when synthetic zeolite added to the reaction system in the earlier stages.

The reaction temperature is preferably 100°s or higher, more preferably 150°C or higher. The reaction temperature is preferably as high as possible, if this temperature is PE is not boiling solvent, disconnection, etc. is Practically difficult to increase the temperature to 350°s or greater.

The reaction may be carried out under atmospheric pressure. When using a solvent with a low boiling point, the reaction temperature should increase with increasing pressure.

Carrying out the reaction are not particularly limited, and the reaction can be carried out by conventional methods.

After the catalyst and the zeolite is separated from the reaction product by filtration, centrifugation, sedimentation, etc. received tetrafluorobenzoate can be isolated/purified by distillation, etc.

EXAMPLE

The present invention is described in the following Examples.

Conditions of analysis gas chromatography in the following Examples.

[Conditions of analysis gas chromatography]

Apparatus: NR (manufactured by Hewlett-Packard Company)

Column: DB-1 (manufactured by J&W)

0.32 mm * 30 m, 1.0 μm thick

Gas carrier: No

Flow rate: 1.2 ml/min (constant flow)

The dividing ratio of flux: 50

Detector: FID

Temperature during injection: 300°

Outlet temperature: 300°

Temperature analysis: 80° (10 minutes) - 10°C/min

→200° - 15°C/min

→300°C (5 min)

Internal standard: o-dichlorobenzene

Example 1

51.02 g of dry tetrafluorethylene (purity 98%, 50.0 g of pure tetrafluorethylene the La), 1.0 g of dry 5% Pd/C, 37.5 g of a powder of zeolite 4A molecular size 4A, manufactured by Union Showa K.K.) and 200.0 g of toluene were placed in a steel autoclave of 500 ml (model NU-4, manufactured by Nitto Koatu Co., Ltd.) and the autoclave was filled with nitrogen. After that, the contents were heated to 160°under stirring and introducing hydrogen under a pressure above the pressure in the autoclave at 0.1 MPa at the above temperature for initiation hydrogenolysis. The rate of hydrogen absorption is reduced 2 hours after injection of hydrogen so that the pressure in the autoclave was raised by hydrogen to 0.05 MPa. The introduction of hydrogen was completed, when the absorption of hydrogen has reached 125 mole percent (mol tetrafluorethylene under standard conditions). The above reaction was completed after 8 hours. Cooled to room temperature, the liquid reaction solution was filtered and the filtrate was analyzed on a gas chromatograph.

The analysis showed a conversion of 98.0% and the yield of the reaction 78.0% (product: 2,3,5,6-tetrafluorobenzoate).

The solvent of the above-mentioned reaction solution was removed using an evaporator, and the residue was distilled under reduced pressure, getting 2,3,5,6-tetrafluorobenzoate in one of the factions, under the pressure of 50 mm Hg at 88°C.

Example 2

56.69 grams of water tetrafluorethylene (water content 10%, purity 98%, 50.0 g of pure tetrafluorethylene),2.38 g of aqueous 5% Pd/C (water content of 58%, 1.0 g of pure Pd) and 200.0 g of toluene were placed in a three-neck glass flask of 500 ml equipped with a stirrer, thermometer, tube Clausen and water fridge. The contents were heated to evaporate the toluene and water only in the number 150.2, After cooling, was added 143.0 g of toluene and the measured water content was 150 ppm. The resulting reaction solution was placed in a steel autoclave of 500 ml (NU-4 model, manufactured by Nitto Koatu Co., Ltd.) and then added 37.5 g of powder of zeolite 4A molecular sieve 4A, manufactured by Union Showa K.K.). Then, the autoclave was filled with nitrogen. After that, the contents were heated to 160°under stirring and introducing hydrogen under a pressure above the pressure in the autoclave at 0.1 MPa at the above temperature for initiation hydrogenolysis. The rate of hydrogen absorption is reduced 2 hours after injection of hydrogen so that the pressure in the autoclave was raised by hydrogen to 0.05 MPa. The introduction of hydrogen was completed, when the absorption of hydrogen has reached 125 mole percent (mol tetrafluorethylene under standard conditions). The above reaction was completed after 8 hours. Cooled to room temperature, the liquid reaction solution was filtered and the filtrate was analyzed on a gas chromatograph. The analysis showed the conversion of 96.8% and the yield of the reaction 76.9% (product: 2,3,5,6-tetrafluorobenzoate).

Example 3

The reaction was carried out as in Example 2, except that the amount of 5% Pd/C was reduced by half to 1.18 g (water content of 58%, 0.5 g of pure Pd). The reaction was completed after 10 hours. The analysis showed the conversion of 96.5% and the yield of the reaction 76.0% (product: 2,3,5,6-tetrafluorobenzoate).

Example 4

56.69 grams of water tetrafluorethylene (water content 10%, purity 98%, 50.0 g of pure tetrafluorethylene), 1.18 g of aqueous 5% Pd/C (water content of 58%, 0.5 g of pure Pd) and 200.0 g of toluene were placed in a three-neck glass flask of 500 ml equipped with a stirrer, thermometer, tube Clausen and water fridge. The contents were heated to evaporate the toluene and water only in the number of 187.5, After cooling, was added 187.5 g of toluene and the measured water content was 150 ppm. The resulting reaction solution was placed in a steel autoclave of 500 ml (NU-4 model, manufactured by Nitto Koatu Co., Ltd.) and then added 45 g of powder of zeolite 5A molecular sieve 5A, manufactured by Union Showa K.K.). Then, the autoclave was filled with nitrogen. After that, the contents were heated to 160°under stirring and introducing hydrogen under a pressure above the pressure in the autoclave at 0.1 MPa at the above temperature for initiation hydrogenolysis. The rate of hydrogen absorption is reduced approximately 5 hours and 30 minutes after start of the reaction, and entered the e hydrogen ceased at the end of the reaction. Absorption of hydrogen was 116 mole percent (mol tetrafluorethylene under standard conditions). The above reaction was completed after 8 hours. Cooled to room temperature, the liquid reaction solution was filtered and the filtrate was analyzed on a gas chromatograph. The analysis showed the conversion of 97.8% and the yield of the reaction 84.4% (product: 2,3,5,6-tetrafluorobenzoate).

Example 5

The reaction was carried out as in Example 4, except that the amount of 5% Pd/C was changed to 2.38 g (water content of 58%, 1.0 g of pure Pd) and that the amount of powder of zeolite 5A was changed to 37.5 g (molecular size 5A, manufactured by Union Showa K.K.). In the hydrogenolysis reaction has ended after 5 hours and 30 minutes, and the absorption of hydrogen was 114%. The analysis showed the conversion of 98.2% and the yield of the reaction 87.5% (product: 2,3,5,6-tetrafluorobenzoate).

Example 6

The reaction was carried out as in Example 4, except that the amount of 5% Pd/C was changed to 1.43 g (water content of 58%, 0.6 g of pure Pd). In the hydrogenolysis reaction has ended after 5 hours and 20 minutes, and the absorption of hydrogen was 121%. The analysis showed a conversion of 99.4% and the yield of the reaction 86.2% (product: 2,3,5,6-tetrafluorobenzoate).

Example 7

The reaction was carried out as in Example 4, except that the temperature hydrogenolysis was 170°C. In react what I hydrogenolysis over 5 hours and 30 minutes and the absorption of hydrogen was 111%. The analysis showed the conversion of 99.3% and the yield of the reaction 87.5% (product: 2,3,5,6-tetrafluorobenzoate).

Example 8

The reaction was carried out as in Example 4, except that the temperature hydrogenolysis was 180°C. the resulting reaction hydrogenolysis over 5 hours and 10 minutes, and the absorption of hydrogen was 114%. The analysis showed the conversion of 99.3% and the yield of the reaction 89.1% (product: 2,3,5,6-tetrafluorobenzoate).

Example 9

The reaction was carried out as in Example 4, except that used additional toluene in the amount of 147,5, the hydrogenolysis reaction is ended after 5 hours and 30 minutes, and the absorption of hydrogen was 112%. The analysis showed the conversion of 98.9% and the yield of the reaction 87.0% (product: 2,3,5,6-tetrafluorobenzoate).

Example 10

The reaction was carried out as in Example 4, except that used additional toluene in the amount 107.5, In the hydrogenolysis reaction has ended after 5 hours and 30 minutes, and the absorption of hydrogen was 108%. The analysis showed the conversion of 98.7% and the yield of the reaction 86.5% (product: 2,3,5,6-tetrafluorobenzoate).

Example 11

The reaction was carried out as in Example 4, except that the zeolite was replaced by zeolite MS-13X. In the hydrogenolysis reaction has ended after 5 hours and 30 minutes, and the absorption in the of aroda was 52%. The analysis showed the conversion of 69.7% and the yield of the reaction 34.7% (product: 2,3,5,6-tetrafluorobenzoate).

Comparative Example 1

The reaction was carried out as in Example 1, except that they had not used any of zeolite. In the hydrogenolysis reaction has ended after 4 hours and the absorption of hydrogen was 48%. The analysis showed the conversion of 55.2% and the yield of the reaction 24.1% (product: 2,3,5,6-tetrafluorobenzoate).

Comparative Example 2

The reaction was carried out as in Example 4, except that they had not used any of zeolite. In the hydrogenolysis reaction has ended after 3 hours and the absorption of hydrogen was 42%. The analysis showed the conversion of 50.4% and the yield of the reaction 20.7% (product: 2,3,5,6-tetrafluorobenzoate).

The EFFECT of the INVENTION

According to the present invention provides a method of producing tetrafluorobenzoate, which is advantageous industrially.

1. The method of producing tetrafluorobenzoate formula (2)

including hydrogenolysis only one ceanography of tetraphenylborate formula (I)

under the influence of hydrogen at a temperature above 100°in the presence of a catalyst of gidrogenizirovanii platinum group and synthetic zeolite.

2. The method according to claim 1, in which sinteticheski zeolite represents at least one zeolite, selected from zeolites 3A, 4A and 5A.

3. The method according to claim 1, wherein the synthetic zeolite is a zeolite 4A and/or 5A.

4. The method according to claim 1, wherein the synthetic zeolite is a zeolite 5A.

5. The method according to claim 1, wherein the catalyst is a palladium on charcoal.

6. The method according to any one of claims 1 to 5, in which the water content of the substances in the reaction system in addition to the zeolite is not more than 3000 ppm of the total number of substances in the reaction system, excluding the zeolite.

7. The method according to any one of claims 1 to 6, in which tetraphenylborate is tetraferriphlogopite and tetrafluorobenzoate is a 2,3,5,6-tetrafluorobenzoate.



 

Same patents:

The invention relates to the field of organic chemistry and relates to compounds of formula (I) and their pharmaceutically acceptable salts and difficult ether derivatives

< / BR>
where Ar represents a phenyl group which may be optionally substituted from 1 to 3 substituents selected from the group consisting of halogen atoms and triptorelin groups having antifungal activity

The invention relates to a new method of deriving biphenyl, namely 4-methyl-2'-cyanobiphenyl of formula (I)

< / BR>
4-Methyl-2'-cyanobiphenyl can find wide application as an intermediate product in the synthesis of derivatives of biphenylmethane described in applications EP-A-O 253310 and A

The invention relates to a method for producing substituted aromatic NITRILES by reacting an aromatic carboxylic acid with gaseous ammonia in the presence of a dehydration catalyst

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to a new method for synthesis of substituted aryl-condensed azapolycyclic compounds of formulas (II) and (VIII) , novel intermediates compounds and methods for their synthesis. Substituted aryl-condensed azapolycyclic compound of the formula (II) show the binding capacity with neurone nicotine/acetylcholine specific receptor sites and can be used for modulation of cholinergic function in treatment of different diseases. Method for synthesis of compound of the formula (II) wherein R represents hydrogen atom; R2 and R3 are chosen independently from hydrogen, halogen atom, (C1-C6)-alkyl optionally substituted with 1-3 fluorine atoms and (C1-C6)-alkoxy-group optionally substituted with 1-3 fluorine atom involves the hydrogenation reaction of compound of the formula: (1a'): synthesized from compound of the formula (III): to yield intermediate compounds of formulas (IX): and (VII): . Compound of the formula (VII) is cyclized in treatment with a base to yield compound of the formula (VIII) that is reduced. Compound of the formula (III) can be prepared by interaction of compound of the formula (IV): with compound of the formula (V): .

EFFECT: improved methods of synthesis.

14 cl, 12 sch, 64 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to method for production of 4-(ω-hydroxyalkyloxy)-4'-cyanobyphenyls by reaction of 4-hydroxy-4'-cyanobyphenyl with ω-chloro-1-alkanols under heating. Reaction is carried out in boiling dimethylformamide medium in presence of potash for 2-4 h in the next molar ratio: (4-hydroxy-4'-cyanobyphenyl):(ω-chloro-1-alkanol):(potash) = 1:(1-1.2):(1-1.2).

EFFECT: accelerated, simplified method of decreased cots; increased yield of target product.

1 tbl, 1 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to continuous process for hydrogenation of compounds containing nitrile and nitro groups to produce amino or aminonitrile compounds in presence of heterogeneous hydrogenation catalyst and a basic compound. Into reactor, at stirring, are fed: first stream of reactant to be hydrogenised, second stream of catalyst, third stream of alkali compound, fourth stream of hydrogen to maintain hydrogen pressure in reactor. From reactor is withdrawn at least fifth stream composed of reaction mixture and containing hydrogen bubbles dispersed therein. Fifth stream circulates in at least one circulation circuit coming out of lower section into top section of reactor. Fifth stream remove excess heat released in hydrogenation reaction and so temperature of reaction mixture is maintained below 150°C. Fifth stream circulating in one of circuits is passed through filter medium to produce sixth stream containing a part of hydrogenate separated from catalyst. From reactor and one of circulation circuit, seventh stream is picked and sent to liquid and solid phase separation stage to produce liquid phase comprised of hydrogenate without catalyst and catalyst-containing solid phase. The latter is subjected to reduction before being recycled into the second catalyst stream fed into reactor.

EFFECT: increased selectivity and productivity of hydrogenation process and enabled reduction and reuse of catalyst.

18 cl, 2 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitrile of the general formula: NC-R-CN wherein R means linear or branched alkylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitrile in the liquid medium. Method is carried out in the presence of a catalyst, such as nickel or Raney nickel comprising an activating element taken among rhodium or iridium wherein the weight ratio (Rh or Ir)/Ni is from 0.05% to 10%. Method provides enhancing yield of aminonitrile.

EFFECT: improved and enhanced method.

21 cl, 3 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitriles of the general formula: NC-R-CN (I) wherein R means linear or branched alkylene or alkenylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitriles. Method involves using hydrogen in the presence of catalyst based on nickel, cobalt, Raney nickel or Raney cobalt comprising, possibly, an activating element that is taken among the 6 group of the Periodic system of element by the IUPAC nomenclature in the presence of strong mineral base representing a derivative of alkaline or earth-alkaline metal or ammonium hydroxide. In carrying out the hydrogenation process the parent mixture comprises water in the weight concentration at least 0.5 weight% of the total content of liquid components of the above said mixture, diamine and/or aminonitrile that can be form from the hydrogenating dinitrile and non-converted dinitrile wherein the weight concentration of all three indicated components is from 80% to 99.5%. The semi-hydrogenation reaction is carried out in the presence of at least one the selectivity-enhancing agent that is taken among the group comprising the following components: - compound comprising at least one cyano-group not bound with carbon atom that is taken among the group comprising hydrogen cyanide, lithium, sodium, potassium, copper cyanide, chelate cyanides of K3[Fe(CN)6], K4[Fe(CN)4], K3[Co(CN)6], K2[Pt(CN)6], K4[Ru(CN)6], ammonium or alkaline metal cyanides, tetrabutyl ammonium cyanide, tetramethyl ammonium thiocyanide, tetrapropyl ammonium thiocyanide; - organic isonitrile that is taken among the group including tert.-octylisonitrile, tert.-butylisonitrile, n-butylisonitrile, isopropylisonitrile, benzylisonitrile, ethylisonitrile, methylisonitrile and amylisonitrile; - tetraalkyl ammonium or tetraalkylphosphonium hydroxide or fluoride is taken among the group comprising tetramethyl ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrabutylphosphonium; - the chelate coordination compound formed by at least one metal atom and at least carbonyl radicals that is taken among the group comprising organic compounds including carbonyl, phosphine, arsine or mercapto-groups bound with metal and taken among the group comprising iron, ruthenium, cobalt, osmium, rhenium, iridium and rhodium. Method provides enhancing the selectivity by the aminonitrile group.

EFFECT: improved preparing method.

13 cl, 2 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process comprises hydrogen reduction of halogenated aromatic nitrile represented by general formula 1:

in which X denotes chlorine or fluorine atom, m integer from 1 to 5, n integer from 1 to 5, and m+n ≤ 5, provided than when n≥ 2, all X can be the same or different, using hydrogenation catalyst selected from group consisting of optionally modified porous nickel and optionally modified porous cobalt and in presence of organic acid in solvent to form halogenated aromatic methylamine represented by general formula 2: , in which X, m, and n are as defined above and "a" is integer from 1 to m).

EFFECT: enabled efficient large-scale production of desired product with high output.

20 cl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing fluorinated dicyanobenzene represented by the formula (2): wherein m means a whole number from 1 to 4; n means 0 or a whole number from 1 to 3, and m + n = 4. This substance is useful as an intermediate and the parent compound for synthesis of medicinal and pharmaceutical products, agricultural reagents and polymers. Method involves interaction of tetrachlorodicyanobenzene represented by the formula (1): with a fluorinated agent at temperature from 80oC to 200oC in the presence of a non-protonic polar solvent taken in the amount from 0.1 to 3 parts by mass per 1 part by mass of indicated tetrachlorodicyanobenzene. Method involves carrying out the reaction with destruction of volume solid materials containing in the reaction mixture and/or by removing volume solid materials adhered inside of reaction vessel. Method provides preparing fluorinated dicyanobenzene with high yield at low temperature for short time.

EFFECT: improved preparing method.

13 cl, 7 ex

The invention relates to a method for producing 2,2'-azobisisobutyronitrile used as a blowing agent and polymer initiator of radical polymerization of unsaturated hydrocarbons

The invention relates to the chemistry of adamantane derivatives, and in particular to a new method of obtaining adamantylidene NITRILES of General formula

where R1=H: R2=H, CH3WITH2H5, (CH3)2CH2WITH6H5WITH10H5C5H10N, C5H10NCH2, (CH2)3JV; R1=CH3: R2=CH3,

which are important intermediates in the synthesis of some biologically active substances

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing fluorinated dicyanobenzene represented by the formula (2): wherein m means a whole number from 1 to 4; n means 0 or a whole number from 1 to 3, and m + n = 4. This substance is useful as an intermediate and the parent compound for synthesis of medicinal and pharmaceutical products, agricultural reagents and polymers. Method involves interaction of tetrachlorodicyanobenzene represented by the formula (1): with a fluorinated agent at temperature from 80oC to 200oC in the presence of a non-protonic polar solvent taken in the amount from 0.1 to 3 parts by mass per 1 part by mass of indicated tetrachlorodicyanobenzene. Method involves carrying out the reaction with destruction of volume solid materials containing in the reaction mixture and/or by removing volume solid materials adhered inside of reaction vessel. Method provides preparing fluorinated dicyanobenzene with high yield at low temperature for short time.

EFFECT: improved preparing method.

13 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process comprises hydrogen reduction of halogenated aromatic nitrile represented by general formula 1:

in which X denotes chlorine or fluorine atom, m integer from 1 to 5, n integer from 1 to 5, and m+n ≤ 5, provided than when n≥ 2, all X can be the same or different, using hydrogenation catalyst selected from group consisting of optionally modified porous nickel and optionally modified porous cobalt and in presence of organic acid in solvent to form halogenated aromatic methylamine represented by general formula 2: , in which X, m, and n are as defined above and "a" is integer from 1 to m).

EFFECT: enabled efficient large-scale production of desired product with high output.

20 cl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitriles of the general formula: NC-R-CN (I) wherein R means linear or branched alkylene or alkenylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitriles. Method involves using hydrogen in the presence of catalyst based on nickel, cobalt, Raney nickel or Raney cobalt comprising, possibly, an activating element that is taken among the 6 group of the Periodic system of element by the IUPAC nomenclature in the presence of strong mineral base representing a derivative of alkaline or earth-alkaline metal or ammonium hydroxide. In carrying out the hydrogenation process the parent mixture comprises water in the weight concentration at least 0.5 weight% of the total content of liquid components of the above said mixture, diamine and/or aminonitrile that can be form from the hydrogenating dinitrile and non-converted dinitrile wherein the weight concentration of all three indicated components is from 80% to 99.5%. The semi-hydrogenation reaction is carried out in the presence of at least one the selectivity-enhancing agent that is taken among the group comprising the following components: - compound comprising at least one cyano-group not bound with carbon atom that is taken among the group comprising hydrogen cyanide, lithium, sodium, potassium, copper cyanide, chelate cyanides of K3[Fe(CN)6], K4[Fe(CN)4], K3[Co(CN)6], K2[Pt(CN)6], K4[Ru(CN)6], ammonium or alkaline metal cyanides, tetrabutyl ammonium cyanide, tetramethyl ammonium thiocyanide, tetrapropyl ammonium thiocyanide; - organic isonitrile that is taken among the group including tert.-octylisonitrile, tert.-butylisonitrile, n-butylisonitrile, isopropylisonitrile, benzylisonitrile, ethylisonitrile, methylisonitrile and amylisonitrile; - tetraalkyl ammonium or tetraalkylphosphonium hydroxide or fluoride is taken among the group comprising tetramethyl ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrabutylphosphonium; - the chelate coordination compound formed by at least one metal atom and at least carbonyl radicals that is taken among the group comprising organic compounds including carbonyl, phosphine, arsine or mercapto-groups bound with metal and taken among the group comprising iron, ruthenium, cobalt, osmium, rhenium, iridium and rhodium. Method provides enhancing the selectivity by the aminonitrile group.

EFFECT: improved preparing method.

13 cl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for semi-hydrogenation of dinitrile of the general formula: NC-R-CN wherein R means linear or branched alkylene group comprising from 1 to 12 carbon atoms to the corresponding aminonitrile in the liquid medium. Method is carried out in the presence of a catalyst, such as nickel or Raney nickel comprising an activating element taken among rhodium or iridium wherein the weight ratio (Rh or Ir)/Ni is from 0.05% to 10%. Method provides enhancing yield of aminonitrile.

EFFECT: improved and enhanced method.

21 cl, 3 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to continuous process for hydrogenation of compounds containing nitrile and nitro groups to produce amino or aminonitrile compounds in presence of heterogeneous hydrogenation catalyst and a basic compound. Into reactor, at stirring, are fed: first stream of reactant to be hydrogenised, second stream of catalyst, third stream of alkali compound, fourth stream of hydrogen to maintain hydrogen pressure in reactor. From reactor is withdrawn at least fifth stream composed of reaction mixture and containing hydrogen bubbles dispersed therein. Fifth stream circulates in at least one circulation circuit coming out of lower section into top section of reactor. Fifth stream remove excess heat released in hydrogenation reaction and so temperature of reaction mixture is maintained below 150°C. Fifth stream circulating in one of circuits is passed through filter medium to produce sixth stream containing a part of hydrogenate separated from catalyst. From reactor and one of circulation circuit, seventh stream is picked and sent to liquid and solid phase separation stage to produce liquid phase comprised of hydrogenate without catalyst and catalyst-containing solid phase. The latter is subjected to reduction before being recycled into the second catalyst stream fed into reactor.

EFFECT: increased selectivity and productivity of hydrogenation process and enabled reduction and reuse of catalyst.

18 cl, 2 dwg

Up!