Method of producing ketazine compound

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a ketazine compound of formula (1) from a ketone compound of formula (2), ammonia and an oxidising agent, where a solution containing a ketone compound of formula (2) and ammonia is brought into contact with aqueous solution of sodium hypochlorite or hydrogen peroxide in a tubular reactor, having flow channel width between 2 and 10000 mcm where R1 and R2 are identical or different and each denotes a C1-6 alkyl group, or R1 and R2 are bonded to form a C2-7alkylene group with a straight chain where R1 and R2 are as described above and each of the liquids is in laminar flow state.

EFFECT: obtaining ketazine compounds with high output and with inhibition of by-products.

4 cl, 1 tbl, 2 ex, 2 dwg

 

The technical field to which the invention relates

The present invention relates to a method for Katasonov connections.

The level of technology

Ketzin is suitable for use as intermediate compounds obtained by the obtaining of hydrazine hydrate. It is known that cetain can be obtained from hydrogen peroxide, ammonia and a ketone (non-patent literature 1 and 2). Hydrazine obtained in the course involved in the way of reactions, interacts with the remaining oxidizing agent, and the hydrazine is decomposed with the occurrence probability of reducing output required kitashinagawa product. In addition, the ketone, amine and hydrazine lead to the emergence of complex side reactions, obtaining high-boiling organic by-products, which are represented, for example, by formula (A) or (B) and which are difficult to delete

(A)(C)

where R1and R2are the same or different and each represents methyl or ethyl.

Respectively used ketone and ammonia, which are taken in large excess to quickly spend the used oxidizing agent. However, the use of large amounts of ketone and ammonia greatly reduces the concentration Katsina in the reaction is MESI to the level which is usually reduced to 3%.

[Non-patent literature 1] Kirk-Othmer 3rd Ed., Vol. 12, pp. 734-755.

[Non-patent literature 2] Toshio Yokota "Hydrazine, Properties and Application thereof," Chijin Shokan, March 1968.

Hydrazine hydrate is obtained from Katsina obtained, usually by distillation under pressure of an aqueous solution obtained Katsina.

However, if the concentration Katsina in the reaction mixture is low, there is the problem that distillation under pressure for the implementation of the reaction to produce hydrazine hydrate requires large amounts of energy.

When the reaction is carried out at high concentrations Katsina to resolve this problem by-products are mixed as impurities with hydrazine hydrate, which must be received, in addition to the lowering of the output Katsina.

The aim of the present invention is to provide a method of producing Katasonov compounds, which ensures obtaining kitashinagawa connection with high yield, with inhibition of by-products and provides the reaction mixture with a high concentration kitashinagawa connection.

Description of the invention

The present invention provides the following.

1. The method of obtaining kitashinagawa the compounds of formula (1) of the ketone compounds of formula (2), ammonia and an oxidizing agent, where the solution with the holding ketone compound of the formula (2) and ammonia, is brought into contact with an aqueous solution of oxidizing agent in a tubular reactor, with the width of the channel to flow from 2 to 10000 microns

where R1and R2are the same or different and each represents a C1-6alkyl group, or R1and R2unite with each other in C2-7alkylenes group with a straight chain

where R1and R2are as described above.

2. The method, as defined above, where the oxidizing agent is a peroxide or sodium hypochlorite.

3. The method, as defined above, where the use 2-5 mol of ketone compounds of the formula (2) and 2-10 mol of ammonia per mole of hydrogen peroxide.

4. The method, as defined above, where the use 2-50 mol of ketone compounds of the formula (2) and 2-400 mol of ammonia per mole of effective chlorine bleach.

5. The method, as defined above, where the mixture, which must interact and containing a solution containing the ketone compound of the formula (2) and ammonia, and an aqueous solution of oxidizing agent contains an oxidizing agent in an amount from 1.6 to 20% wt.

The authors have carried out intensive studies to achieve the above objectives and found that when the reaction is carried out in a tubular reactor, having a very small sirinyali for a thread, to obtain Katsina of ketone, ammonia and an oxidizing agent, Kyazimovoy connection can be obtained with high yield while inhibiting the formation of by-products, even if the reaction mixture contains a high concentration kitashinagawa connection. This is the present invention.

Deputies discussed here indicate the following :

Examples of C1-6alkyl groups are alkyl group with straight chain or branched chain having 1-6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl and isohexyl.

Examples of C2-7alkilinity groups with direct chain are ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and heptamethine.

In accordance with the present invention, the solution containing the ketone compound of the formula (2) and ammonia is brought into contact with an aqueous solution containing an oxidizing agent, in a tubular reactor, obtaining kitashinagawa the compounds of formula (1).

Examples of the ketone compounds of the formula (2) for use in the method of obtaining kitashinagawa compounds of the present invention are acetone, 2-pentanone, 3-pentanone, methyl ethyl ketone, methylisobutylketone, methyl isobutyl ketone, cyclo is alanon, Cyclopentanone and cyclohexanone. Especially preferred are acetone, methyl ethyl ketone and methyl isobutyl ketone.

Ammonia, which must be used in the method according to the present invention may be a commercially available ammonia water, but is preferred obtaining ammonia water at any desired high concentration by introducing gaseous ammonia into the water. The solution containing the ketone compound of the formula (2) and ammonia is an aqueous solution obtained by dissolving ketone compound of the formula (2) and ammonia in water. The solution can be obtained, for example, by mixing the ketone compounds of formula (2) with ammonia water and diluting the resulting solution to the desired concentration if necessary. Alternatively, the solution can be obtained by mixing an aqueous solution of compounds of formula (2) with ammonia water.

An aqueous solution containing the ketone compound of the formula (2) and ammonia and prepared in advance, may be injected into the tubular reactor for interaction, or an aqueous solution of the ketone compounds of formula (2) and ammonia water may enter the tubular reactor via the corresponding inputs and brought into contact with each other in the channel for the stream.

It is believed that in the solution containing the ketone compound of the formula (2) is ammonia, these compounds interact partially or completely with the formation of Klimentovo the compounds of formula (3)below

where R1and R2are the same as above.

One mol Klimentovo connection corresponds to 1 mol of the ketone compounds of formula (2) and 1 mol of ammonia.

Examples of oxidizing agents for use in the method according to the present invention are sodium hypochlorite and hydrogen peroxide.

The hydrogen peroxide can be an industrial product. Usually used 30-90 wt.%. an aqueous solution of hydrogen peroxide. This peroxide may contain phosphoric acid or similar stabilizer, which is usually used for hydrogen peroxide.

Sodium hypochlorite, which should be used is an aqueous solution of commercially available sodium hypochlorite and has a concentration of effective chlorine 10-20 wt.%, or wialenove sodium hypochlorite, in which the content of sodium chloride is lowered, which is produced as a by-product, depending on the devices or arrangements.

In the case when the oxidizing agent used hydrogen peroxide, a ketone compound of the formula (2), ammonia and an oxidizing agent is used, for example, in such quantities that use 2-5 mol, prefer the Ino from about 3 to about 4 mol, the ketone compounds of formula (2) and 2 to 10 mol, preferably from about 3 to about 4 mol, of ammonia per mole of hydrogen peroxide.

In the case when the oxidizing agent used sodium hypochlorite, use 2-50 mol, preferably from about 4 to about 40 mol, ketone compounds of formula (2) and 2-400 mol, preferably from about 3 to about 300 mol, of ammonia per mole of effective chlorine bleach.

In the production method of the present invention the oxidizing agent is used at a concentration that can be determined in a wide range. In the mixture, which must interact and containing a solution containing the ketone compound of the formula (2) and ammonia, and an aqueous solution containing an oxidizing agent, the oxidizing agent is used at a concentration of from 0.1 to 30 wt.%, preferably 1.6 to 20 wt.%, more preferably from 2 to 15% wt.

Upon receipt Katsina, generally considered to be the preferred implementation of the method in such a way that the mixture, which must interact, will be the concentration of hydrazine or Katsina to 3% wt. in order to control the reaction with hydrazine in the reaction. From this it follows that when using hydrogen peroxide, the concentration of the oxidizing agent should be limited to about 1% wt.

The method according to Nast is Adamu invention provides Kyazimovoy compound of formula (1), not allowing the concentration of oxidizing agent in the mixture, which must interact to affect the output, regardless of whether the concentration is low or high. For example, when using 2% wt. oxidizing agent, the reaction mixture gives theoretically about 6.6 wt.%. kitashinagawa connection.

When hydrogen peroxide is used as oxidizing agent, it is desirable to use a catalytically active compounds.

Preferred for use are, for example, amide compound, ammonium salt or nitrile compound described in Japan patent JP2004-67633A, and the working fluid, which is prepared by dissolving the organic arsenic compounds and carboxylic acid in a solvent mixture of water and alcohol.

Preferably the working fluid is brought into contact or mixed with a solution containing the ketone compound of the formula (2) and ammonia, before bringing into contact or mixing with the aqueous solution containing the oxidizing agent.

Alternatively, the working fluid may be additive in the form of a portion of the ketone compounds of formula (2) or ammonia that should be used.

When using the working fluid, the concentration of the oxidizing agent for use in the mixture, which must interact, presented yet a concentration in the working fluid in the mixture, which contains the solution containing the ketone compound of the formula (2) and ammonia, and an aqueous solution containing an oxidizing agent.

The reaction can usually be carried out at 30-110°C, preferably at 30 to 70°C. If the reaction temperature is lower than 30°C, the yield of the reaction will be lower if the temperature is higher than 110°C, hydrogen peroxide or sodium hypochlorite will decompose, leading to a reduction in yield of the reaction. Although the reaction pressure is optimal, it is easy to carry out at atmospheric pressure.

Kyazimovoy compound of the formula (1)obtained by this reaction may be emitted from the reaction mixture with a known method, such as the separation of liquid-liquid using a mixer/settler or centrifuge extraction liquid-liquid or distillation, or a combination of such methods.

Tubular reactor for use in the present invention has an inlet for fluid, an outlet for fluid and a channel for the stream to force the liquid to flow from input to output. Preferably, the reactor has two or three inputs for receipt of various fluids through the respective inputs. After coming in contact with each other or with other liquid fluid out through the exit. The channel flow can be branched in a T-shape or Y-shape. Frequent the channel for the stream, designed to bring liquids into contact with each other, may be referred to hereinafter as "the reaction channel.

Such a tubular reactor can be manufactured by forming a channel for the flow in the surface of the substrate using various methods, including laminating, printing, etching, fashion LIGA (Lithographie, Galvanoformung, Abformung (lithography, electroplating, stamping)), cutting and molding. You can also use industrial reactors, such as Microfluidics chips produced Arbiotec, Ltd., the microreactors produced by the Institute fuer Mikrotechnik, Mainz GmbH, Selecto or Cytos produced Cellular Process Chemistry GmbH, and the like.

Channel flow is not in any way limited by the cross-sectional shape. For example, a channel may be triangular, square, rectangular, pentagonal, hexagonal, octagonal or other polygonal, circular or elliptical in cross section.

The channel for the stream may have a smooth surface or may have small protrusions or grooves or the spiral formed by these projections or recesses, when this is desirable.

The channel for the stream is wide 2-10000 μm, preferably 5-5000 μm. If the width of the channel for flow of less than 2 μm, the channel becomes more prone to clogging detachable solid products, at the same time, if the width is greater than 10000 μm, R is camping hard getting exposure, intended by the present invention. In this case, the term "channel width flow" refers to the greatest width of the portion of the channel for the stream, where at least two liquids may be brought in contact with each other. When the channel flow is round in cross section, this width corresponds to the diameter.

The channel, i.e. the reaction channel is in length from about 0.01 to about 100 m, preferably about 0.05 to about 10 m Channel can be in the form of straight or curved pipe or a circular, elliptical, spiral, or helix, from square to rectangular, or may have a helical shape.

The method according to the present invention will be described briefly with reference to the tubular reactor shown in figure 1. An aqueous solution containing the ketone compound of the formula (2), enters through the inlet (a) 2, and an aqueous solution containing ammonia, is injected through the input (b) 3, and the solutions are mixed together in the channel to flow 5a to generate a solution containing the ketone compound of the formula (2) and ammonia. An aqueous solution containing an oxidizing agent is introduced through the inlet (c) 4. The solution containing the ketone compound of the formula (2) and ammonia, may be carried into contact and mixed with an aqueous solution containing an oxidizing agent, in the part of the channel for the stream, which houses Lorena further, along the flow from the inlet 4. The resulting received Kyazimovoy compound of formula (1) may be delivered from the output 6 together with the reaction mixture.

When using hydrogen peroxide, Kyazimovoy compound of formula (1) can be obtained by entering through the inlet (a) 2 aqueous solution obtained by mixing in advance of an aqueous solution containing the ketone compound of the formula (2)with an aqueous solution of ammonia, the introduction of the working fluid through the inlet (b) 3 to coming into contact or mixing in the channel (5a) with the formation of a solution containing the ketone compound of the formula (2) and ammonia, and receipt of an aqueous solution (aqueous hydrogen peroxide solution containing an oxidizing agent, through the entrance (c)4.

It is desirable that the tubular reactor for use in the method according to the present invention was designed so that when at least two of the fluid flowing through the inputs brought into contact or mixed with each other and flow through the reaction channel, each of the liquids will be in the form of a laminar flow.

This state of laminar flow harakterizuetsya the Reynolds number from the following equation (1). This number is preferably less than 2300, more preferably less than 100

Re = LUρ/η (1)

where Re represents : the Reynolds, L represents the channel length for flow, U is the flow velocity of the fluid, ρ is the density of the fluid and η represents the viscosity of the liquid.

For a reactor having a detailed structure for use in the present invention, the smaller the change in pressure of the liquid flowing through the reactor, the higher the efficiency of the contact or mixing. This suppresses the increase of the local temperature, inhibits side reactions and leads to higher efficiency of the reaction.

Variations of pressure should be up to 5%, preferably up to 2%, more preferably up to 1%.

If variations of pressure not less than 5%, the flow velocity and the flow rate is changed in such variations, with the result that the reactor cannot maintain uniform contact or mixing ratio, which leads to a decrease in the reaction efficiency.

The method of fluids is not in any way limited, insofar as the method can enter the liquid at a stable flow rate (flow velocity) and with a steady pressure and can form a stable laminar flow. Preferred for use are the pumps, such as syringe pump, reciprocating piston pump, diaphragm pump, plunger pump, gear pump, peristalic the economic pump, spiral pump and diffuser pump. These pumps can be used singly or at least two species of them may be used in combination.

Tubular reactor for use in the present invention may be used with appropriately selected, attached devices, in accordance with the reaction conditions. These devices include, for example, the cooling unit, heater, electric controller and the analyzer.

When multiple tubular reactors of the type described is used as a system of parallel or superimposed on other layers, it becomes possible to obtain quantities of the product on an industrial scale.

Brief description of drawings

Figure 1 is a diagram showing an example of a tubular reactor for use in the method according to the present invention; and

Figure 2 is a diagram showing an example of the tubular reactor used in the Examples of the present invention.

1: substrate, 2: input (a)3: input (b)4: input (c), 5: channel flow, 5a: part of the channel for the stream. 6: exit.

The best way of carrying out the invention

The present invention will be described below in detail with reference to Reference examples, Examples and Experimental examples that the present invention is in no with what you learn is not limited.

Reference example 1(Manufacture of tubular reactor)

The tubular reactor is made under the following conditions using a cutting machine (with small machining EGX-300, made by Roland) for sheet silicate glass having a size of 30 mm×70 mm×2 mm

Drill-milling:bars with elecrodeposition diamonds (A2505 and A2502. products MINIMO Co., Ltd.) having dimensions of 0.5 mm in length and 0.2 mm in diameter.

Cutting conditions:speed in the directions of the axes of the XY-0.5 mm/sec, the velocity in the Z axis direction is 0.5 mm/sec, a step of cutting 0.01 mm, the number of revolutions of the drive shaft - 15000 rpm

Input and output:milled through the use of cutters of solid carbide (A2501), 1.00 mm in diameter.

The raw glass sheet put on the obtained milled sheet silicate glass and meld with him at 660°C for at least 5 hours for the manufacture of the reactor (figure 2)having a channel for flow of 100-500 μm in width, 100-200 μm in depth and 150 mm [(a)-(b): 50 mm, (b)output: 100 mm] in length.

The reactor is equipped with a thermostat, and each of the inputs (inputs A-C) is supplied syringe pump (KD, is Scientific Inc.)

Example 1

The working fluid (100 g) prepared by mixing 33% wt. cacodylate acid, 7% wt. methylarsonic acid, 20% wt. acetic acid, 7% wt. water, 6% wt. ammonia and 27% wt. of ethylene glycol.

When thermostat established at 50°C, for a tubular reactor made in Reference example 1, syringe pumps are used for feeding the working fluid into the reactor through the inlet A, an aqueous solution of 24 g 23% ammonia water and 46 g of methyl ethyl ketone through the inlet B and 17 g of 60% aqueous hydrogen peroxide solution through the entrance C. These solutions are injected in such a way that they can be mixed together at the ratio 10:7:2. The flow velocity of the reaction mixture (as (b) output figure 2) is equal to 4.5 ml/min, the Reynolds Number is equal to about 2.

The excess of methyl ethyl ketone added to the reaction mixture coming out of the exit, and subjecting the mixture to high-performance liquid chromatography (HPLC) under the following conditions. The number of received methylethylketone measured by comparing with the authentic product.

[Conditions HPLC]

Column: Inertsil ODS-3, (dia. a 4.6×250 mm, is made by GL Science) temp. column: 40°C

Mobile phase: acetonitrile/20 mmol of phosphate acid buffer (pH 7)=2/8

Flow rate: 1.0 ml/min

Detector: UV (λ = 235 nm)

The injected quantity: 3 ál

As a result, the yield of the desired product, methylethylketone, as found, is 95%, relative to that used hydrogen peroxide.

Example 2

Syringe pumps are used to introduce 813 g of a 23% aqueous ammonia solution in a tubular reactor made in Siloc the om example 1 through the entrance A, 174 g of acetone through the inlet B and 253 g of an aqueous solution of sodium hypochlorite, which is the effective content of chlorine is 17%, through input C. These solutions come to be mixed together at the ratio 81:17:25. The flow velocity of the reaction mixture (as (b) output figure 2) 1.5 ml/min, the Reynolds Number is approximately 1.5.

The reaction mixture resulting output, analyzed by chromatography, and the number dimethylketene determined by a calibration curve using authentic product.

[Conditions for chromatographic analysis]

Column: PEG 20M+KOH (10+10%) on Chromosorb W N AW 80/100 mesh, 2.1 m

The column temperature: 170°C

The pace. injection: 230°C

Carrier gas: N240 ml/min

Detector: FID

The injected quantity: 0,5 ál

As a result, the yield of the desired product dimethylketene is 96% compared to the effective content of chlorine in the sodium hypochlorite.

Reference example 2

The reaction mixture containing methylethylketone and obtained in Example 1, distil at high pressure (internal temperature: up to 150°C, 2229 hPa), and the time when the content of methyl ethyl ketone in the fractions obtained reaches a level that is no longer detected, or below, take as the end (gazokhromatograficheskie).

The obtained residue optionally distil under reduced pressure to 160 GPa and bring it to a place that he was to be an 80% aqueous solution of hydrazine hydrate. This 80% aqueous solution of hydrazine hydrate is cooled to room temperature, and then filtered to separate the insoluble products and precipitate to give the desired 80% aqueous solution of hydrazine hydrate (yield: 96% of Katsina).

The content of hydrazine hydrate is calculated using the following titration method.

[Content of hydrazine hydrate]

10-ml volume of sample accurately measure using a whole pipette and placed into a volumetric flask (100 ml) and additionally put deionized water to obtain a given quantity. A 10 ml quantity of the resulting mixture is then transferred to the Erlenmeyer flask using a whole pipette. Subsequently, about 90 ml of deionized water and placed in it about 5 ml of sulfuric acid (1+1) [which is a concentrated sulfuric acid, diluted with the same volume of water] in addition, and the resulting mixture is evaporated until the mixture is reduced by half. A slight excess of sodium bicarbonate is added to the mixture under cooling (to such an extent that there remains a certain amount of crystals) and the mixture is titrated with a 0.1-n is Smolnogo iodine. Starch is used as indicator. The content of hydrazine hydrate (wt./volume %) is calculated from the following equation. The content of hydrazine hydrate (wt./volume %)=

100×(0,00125×100×F×A/10×10)=0,125×F×A,

where a: number 1/10N iodine used for titration (ml);

F: titr/10N iodine = measured value for iodine/25,3809 (g) dissolved in 1000 ml deionized water.

Reference example 3

Using the same method as in Comparative example 2, 80% aqueous solution of hydrazine hydrate prepared from the reaction mixture obtained in Example 2 and containing dimethyltin (yield: 95% of Katsina).

Comparative example 1

200-CC reactor (chetyrehosnuju flask)equipped with a stirrer, was placed 100 g of the working fluid containing 33 wt.%. cacodylate acid, 7% wt. methylarsonic acid, 20% wt. acetic acid, 7% wt. water, 6% wt. ammonia and 27% wt. of ethylene glycol. The working fluid support at 60°C and add 24 g of a 23% aqueous solution of ammonia, 46 g of methyl ethyl ketone and 8.5 g of 60% aqueous hydrogen peroxide to the liquid at the same time, for a period of 30 minutes, with subsequent interaction within 80 minutes. The reaction mixture is analyzed under the HPLC conditions described in Example 1 to find that methylethylketone get with exit 67% relative to that used hydrogen peroxide.

80% aqueous solution of hydrazine hydrate additionally receive the same manner as in Reference example 2 (yield: 89% of Katsina). By-products A and B are detected as being present in quantities 205 ppm 101 ppm, respectively.

Comparative example 2

813-g quantity of 23% aqueous solution of ammonia and 174 g of acetone are placed in a reactor and optionally placed in him 1020 g of water, to bring the ammonia and acetone to a concentration of 18 wt.%. The mixture is then heated to a temperature of 60°C under stirring. Subsequently, 253 g of an aqueous solution of sodium hypochlorite at the effective content of chlorine 14% add to the mixture over a period of 80 minutes for interaction.

The reaction mixture is analyzed by the same method as in Example 1 to find that dimethylketene get with the release of 52% compared to the sodium hypochlorite. 80% Aqueous solution of hydrazine hydrate additionally receive the same manner as in Reference example 2 (yield: 90% of Katsina). By-products A and B are detected as being present in quantities 101 ppm 98 ppm, respectively.

Comparative example 3

81,3-g quantity of 23% aqueous solution of ammonia and 17.4 g of acetone are placed in a reactor and placed him in 1706 additional water to bring the interacting reagents to a concentration of 2%. The mixture is then heated to the temperature of 60°C under stirring. Subsequently to 25.3 g of an aqueous solution of sodium hypochlorite at the effective content of chlorine 14% add to the mixture over a period of 80 minutes for interaction.

The reaction mixture is analyzed by the same method as in Example 1 to find that dimethylketene get with the release of 86% compared to the sodium hypochlorite.

80% aqueous solution of hydrazine hydrate additionally receive using the same method as in Reference example 2 (yield: 92% of Katsina). By-products A and B are detected as being present in quantities of 41 ppm and 35 ppm, respectively.

Table 1 shows the results of Examples 1 and 2, Reference examples 2 and 3 and Comparative examples 1-3.

0,6
Table 1
Oxidizing agentKyazimovoy connectionHydrazine hydrate
AB
(% wt.)
Output (%)C
(%)
D
(ppm)
E
(ppm)
App.1 5.2420.394---
Ssylochku---96 (90,2)1621
PR7.55
(3.60)
10.996---
Ssylochku---95 (91.2)813
Cf. Ave 13,9911,06789 (59,6)205101
Cf. Ave 26,15
(2,93)
a 4.95390 (47,7)10198
Cf. Ave 30.46 (0,22)8692 (79,1)4135

A: Concentration in the mixture, which should interact a)

B: Concentration in the reaction mixture (b)

C: output c)

D: the Content of by-product in (d)

E: the Content of by-product in (e)

a) Concentration in the mixture, which must interact, oxidizing agent used for the reaction. The numerical values in brackets for Example 2 and Comparative examples 2 and 3 represent, each, the concentration of effective chlorine to sodium hypochlorite.

b) Concentration kitashinagawa compounds in the reaction mixture, as calculated with the output taken as 100%.

c) Release of hydrazine hydrate, obtained from kitashinagawa connection. The numerical values in parentheses represent the output from the oxidizing agent for the reaction of obtaining kitashinagawa connection.

d) the Content of by-product A, is present in the received hydrazine hydrate.

e) the Content of by-product B that is present in the received hydrazine hydrate.

Industrial applicability

The method of obtaining Katasonov compounds of the present invention provides a connection without lowering the concentration in the reaction mixture obtained from Katsina and suppresses the education side the products, at the same time, inhibiting the decomposition of hydrazine obtained in the course of the reaction, the oxidizing agent. Using the reaction mixture obtained by the method according to the present invention and containing Kyazimovoy connection, reduces the amount of energy required to obtain hydrazine hydrate, giving hydrazine hydrate with high yield and with fewer impurities.

1. The method of obtaining kitashinagawa the compounds of formula (1) of the ketone compounds of formula (2), ammonia and an oxidizing agent, where the solution containing the ketone compound of the formula (2) and ammonia is brought into contact with an aqueous solution of sodium hypochlorite or hydrogen peroxide in a tubular reactor, with the width of the channel to flow from 2 to 10000 μm,

where R1and R2are the same or different and each represents a C1-6alkyl group, or R1and R2unite with each other With2-7alkylenes group with a straight chain,

where R1and R2are the same as above, and each of the liquids is in the form of a laminar flow.

2. The method according to claim 1, in which use 2-5 mol of ketone compounds of the formula (2) and 2-10 mol of ammonia per mole of hydrogen peroxide.

3. The method according to claim 1, in which use 2-50 mol of ketone joint is of the formula (2) and 2-400 mol of ammonia per mole of effective chlorine bleach.

4. The method according to claim 1, in which the mixture, which must interact containing solution containing the ketone compound of the formula (2) and ammonia, and an aqueous solution of sodium hypochlorite or hydrogen peroxide, which contains sodium hypochlorite or hydrogen peroxide in an amount from 1.6 to 20 wt.%.



 

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SUBSTANCE: invention relates to alkylcobalt(III) complexes with tridentate Schiff's bases wherein alkyl ligand contains functional group, notably hydroxyl, carboxyl, or amino group, in accordance with general formula:

(I),

in which W represents two-moiety unsaturated hydrocarbon bridge group expressed by formula =C(H)=C(CH3)- (propene-1,2-diyl) or o-C6H4 (o-phenylene); X is OH, NH2 or COONa; Y monovalent anion: Cl-, Br-, NO3- or ClO4-; and Z polymethylene bridge group (CH2)n, wherein n=3-11 when X = OH or NH2 and n=2-11 when X = COONa. The complex are used as initiators of emulsion polymerization and copolymerization of diene and vinyl monomers to produce reactive bifunctional oligomers and polymers with terminal functions, which oligomers and polymers are suitable for further conjugation with corresponding reagents.

EFFECT: extended choice of specific polymerization catalysts.

3 tbl, 30 ex

FIELD: chemistry.

SUBSTANCE: catalyst is a product of reacting compounds (a) and (b). Compound (a) is a mixture of (i) a compound which contains at least one opxy group with (ii) a compound which contains an alcohol, amino-, thio- or carboxyl group and an aldehyde or ketone group. Compound (b) contains at least one primary amino group and at least one tertiary amino group.

EFFECT: use of the proposed non-volatile catalyst to produce polyurethane foam reduces the need for traditional volatile amine catalysts, speeds up bonding of organic polyisocyanates to polyhydroxyl or polyamino compounds and the reaction between isocyanate and foaming substance, and reduces the time for holding polyurethane foam material in the die mould and improves characteristics of the foam.

14 cl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a ketazine compound of formula (1) from a ketone compound of formula (2), ammonia and an oxidising agent, where a solution containing a ketone compound of formula (2) and ammonia is brought into contact with aqueous solution of sodium hypochlorite or hydrogen peroxide in a tubular reactor, having flow channel width between 2 and 10000 mcm where R1 and R2 are identical or different and each denotes a C1-6 alkyl group, or R1 and R2 are bonded to form a C2-7alkylene group with a straight chain where R1 and R2 are as described above and each of the liquids is in laminar flow state.

EFFECT: obtaining ketazine compounds with high output and with inhibition of by-products.

4 cl, 1 tbl, 2 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to aldimines of formula (I)

where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.

EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.

22 cl, 18 ex, 6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to production of dinitrophenol fragment-containing 2-hydroxy-3,5-dinitro-N-(salicylidene)-aniline or 2-hydroxy-3,5-dinitro-N-(4-dimethylaminobenzylidene)-aniline which scatter a proton gradient created by respiration and influence oxidative phosphorylation in mitochondria, by reacting 2-amino-4,6-dinitrophenol and salicylic aldehyde or p-dimethylamino benzaldehyde.

EFFECT: improved method.

1 cl, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a dialdimine of formula , where R is a radical of formula , where R1 and R2 are either independently univalent hydrocarbon radicals with 1-6 C atoms; R3 is a hydrogen atom; R4 is a radical of formula , where R5 is a linear or branched alkyl radical with 1-12 C atoms, A is a C4-C10 diamine group DA with two primary aliphatic amino groups after removal of both primary aliphatic amino groups and containing two ether groups, Q is a diisocyanate group DI after removal of both isocyanate groups; n equals 0 or an integer from 1 to 15; and where A and R do not contain groups which, in the absence of water, are capable of reacting with isocyanate groups. The invention also relates to a method of producing said dialdimine and use of dialdimine in emulsions for use as a curing or accelerating component for polymers with isocyanate groups.

EFFECT: invention provides two-component compositions which are fast-hardening and have exclusively high strength in the early period and do not have undesirable weak points.

22 cl, 2 tbl, 4 ex, 11 dwg

FIELD: chemistry.

SUBSTANCE: in formula :

A denotes either an amine residue after removing n primary n aliphatic amino groups and m HX- groups, or together with R7 denotes a (n+2)-valent hydrocarbon residue with 3-20 carbon atoms, which optionally contains at least one heteroatom, particularly in form of oxygen an ether or tertiary amine nitrogen; n equals 1-4, m equals 0-4; under the condition that (m+n) equals 2-5; R1 and R2 either, independently of each other, each denote a univalent hydrocarbon residue with 1-12 carbon atoms, or together denote a divalent hydrocarbon residue with 4-12 carbon atoms, which is part of an optionally substituted carbocycle with 5-8, preferably 6, carbon atoms; R3 denotes a hydrogen atom or an alkyl group or an arylalkyl group or an alkoxycarbonyl group, particularly with 1-12 carbon atoms; X denotes O or S, or N-R6, or N-R7, where values of radicals R4-R6 are given in the claim. The invention also relates to a curable or cured composition containing said compound, use of the compound in adhesives, sealants, filling compounds, coatings and an article containing the curable composition.

EFFECT: higher compound properties.

21 cl, 13 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel heterocyclic nitrogen- and oxygen-containing compounds having insecticidal activity. In formulae (A) (B) (C) (D) R1 is a 5- or 6-member heterocyclic ring containing a nitrogen, oxygen and/ or sulphur atom, a halogen-substituted 5- or 6-member heterocyclic ring containing a nitrogen, oxygen and/or sulphur atom, a substituted or unsubstituted phenyl, where the substitutes are one or more groups selected from a group consisting of halogen atoms, C1-4 halogen alkyl or C1-4 chloroalkoxyl; R5, R6, R7, R8 and R9 are H, saturated or unsaturated C1-4 alkyl, halogen atom, saturated or unsaturated C1-4 alkoxyl, saturated C1-4 halogenalkoxyl, C1-4 alkylcarbonyl, C1-8 alkyl ester, C1-4 alkylsulphonyl, phenyl, benzyl or trifluoromethane sulphonyl ether group; Y is nitro, cyano, trifluoromethyl, trifluoroacetyl or trifluoromethylsuphonyl. Values of radicals R, R2-R4 are given in the claim.

EFFECT: invention also relates to an agrochemical composition containing said compounds, use of the agrochemical composition in pest control and a method of producing said compounds.

12 cl, 7 tbl, 36 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of producing N-benzylidene benzylamine of formula . The method involves reacting benzylamine with CCl4 in the presence of a FeCl3·6H2O catalyst at 40-85°C in an open system for 0.5-8 hours, with molar ratio [catalyst]:[benzylamine]:[CCl4]=0.1-1:100:50-200.

EFFECT: method simplifies the technology, simplifies extraction and purification of the end product and enables to obtain the product with good output.

1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: claimed is a method of hydroamination of liquid acetylene hydrocarbons with an amine in the presence of a catalyst under conditions of UHF heating of a reaction mass with the power in the range of 1-10 W at a temperature of 110-150°C in the medium of a polar organic solvent. The catalyst contains nanosized particles of metallic gold on a carrier - titanium dioxide or mesoporous zeolite-like silicate MCM-41. The total content of gold is 1-5 wt %. As the polar organic solvent, for instance, dimethylformamide or a ionic liquid, preferably 1-n-butyl-3-methylimidazolium hexafluorophpsphate, or 1-n-butyl-3-methylimidazolium tetrafluoroborate is used. As the amine, for instance, aniline or pyperidine is used. As acetylene hydrocarbons linear hydrocarbons, for instance, hexyne, heptyne, octyne, and aromatic acetylene hydrocarbons, for instance, phenylacetylene, are used.

EFFECT: reduction of the time of the hydroamination reaction due to the application of polar solvents and UHF heating of the reaction mass and an increase of the process productivity with the preservation of a high degree of conversion of acetylene hydrocarbons.

7 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a ketazine compound of formula (1) from a ketone compound of formula (2), ammonia and an oxidising agent, where a solution containing a ketone compound of formula (2) and ammonia is brought into contact with aqueous solution of sodium hypochlorite or hydrogen peroxide in a tubular reactor, having flow channel width between 2 and 10000 mcm where R1 and R2 are identical or different and each denotes a C1-6 alkyl group, or R1 and R2 are bonded to form a C2-7alkylene group with a straight chain where R1 and R2 are as described above and each of the liquids is in laminar flow state.

EFFECT: obtaining ketazine compounds with high output and with inhibition of by-products.

4 cl, 1 tbl, 2 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: filler used is chromogenic ion-exchange dispersed silica with covalently grafted hydrazones or formazans.

EFFECT: high sensitivity and selectivity of detecting metals.

3 tbl, 4 dwg, 14 ex

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