The method of obtaining ferrocene

 

(57) Abstract:

Describes an improved method of producing ferrocene. The method consists in the interaction of potassium hydroxide (sodium) with cyclopentadiene in the form of 15-30% solution (wt.) in n-pentane at a molar ratio of his and potassium hydroxide (sodium) of 1.2 to 1.4:1.0 in the environment of dimethyl sulfoxide, which impose additional 5-10 wt.% water, and then adding to the resulting cyclopentadienide potassium (sodium) of ferric chloride in dimethyl sulfoxide at a ratio cyclopentadienide potassium (sodium) and ferric chloride 2,0: 1,0 (mol.). This method prevents the formation cyclopentadiene resins in the reaction mixture and improves the quality of the target product. 1 C.p. f-crystals, 1 Il.

The invention relates to the field of ORGANOMETALLIC compounds, namely bis-cyclopentadienyl (ferrocene).

Ferrocene and its derivatives are widely used as anti-knock additives fuels, increase their octane number, and additives for engine oils, which improves their performance properties.

Polymers based on derivatives of ferrocene-resistant. possess good electrical and magnetic properties. Feroza used as drugs (Ferriere) for the treatment zhelezodificitnaya anemia and malignant tumors. Based on ferrocene is made of photosensitive materials, inhibitors of photodecomposition and oxidation of polymeric materials. Ferrocene and its derivatives are used as catalysts for the hydrogenation and isomerization of olefins.

For the first time ferrocene was synthesized in 1951 by Poonam and Seville. Ferrocene is obtained by processing svejeprigotovlennogo bromide cyclopentadienylmanganese (Grignard reagent) chloride iron in the environment ether of ethylene glycol:

2C5H5MgBr+FeCl2-->C5H5FeC5H5+MgBr2+MgCl2< / BR>
[A. N. Nesmeyanov, N. A. PL. Beginning organic chemistry, ch. II. - M.: Chemistry, S. 450].

Bromide cyclopentadienylmagnesium gogova of bromide of ateline and cyclopentadiene (CPD).

Ferrocene can be obtained by the interaction cyclopentadienylmanganese with iron acetylacetonate [P. Carrer. The course of organic chemistry.- M: Goskomizdat, 1960, S. 788]. However, the method refers to a preparative process for the production of ferrocene as getting it by thermolysis at 300oWith carbonyl derivatives cyclopentadienyls - dimers and tetramers formula

[(C5H5)Fe(CO)5]5and [(C5H5)Fe(CO)2)4< / BR>
Huelte Brian Appl. Organometall. Chem., 1989, 3, 2, S. 157-164].

A method of obtaining of ferrocene carbonyl iron and cyclopentadiene [M green. ORGANOMETALLIC compounds of transition metals. - M.: Mir, 1972, S. 129] . The process proceeds through the stage of obtaining PENTACARBONYL iron, boiling with JRC get dual core complex [(C5H5)Fe(CO)2]2which when reacted with the JRC, as with thermolysis, turns into a ferrocene. The multistage method, energy-intensive, along with ferrocene produces by-products.

A method of obtaining ferrocene by the interaction of the chloride of iron with cyclopentadienylsodium:

< / BR>
in turn, cyclopentadecanolide produced by interaction of the aqueous solution of titanium hydroxide Ti(OH)2with JRS [N. A. Kostromina, C. N. Kumok, N. A. Skorik. Chemistry of coordination compounds. - M.: Higher school, 1990, S. 114].

Way connected with the use of salts of titanium, which is uneconomical and environmentally unfriendly.

A method of obtaining ferrocene vapor transmission JRS over the iron powder at 300oWITH:

< / BR>
[Z. HAMPTON, Y. Graefe, H. The Reman. Organic chemistry. - M.: Chemistry, 1979, S. 245].

The method is quite complex for industrial implementation, e is

A method of obtaining ferrocene interaction JRS and metallic sodium in ethanol or tetrahydrofuran followed by the addition of iron salts:

C5H6+Na-->[C5H5]-Na++1/2H2;

2(C5H5)Na+FeCl2-->(C5H5)2Fe+2NaCl

[A. N. Nesmeyanov, N. A. PL. Beginning organic chemistry, T. II. - M. : Chemistry, 1974, S. 449].

The use of the method in industrial production of ferrocene is also problematic in view of its fire, explosion hazard.

Known electrochemical method of obtaining ferrocene or its derivatives from JRC, its halogen - or alkyl substituted and iron, which is the anode, using the electrolyte solution of the halides of Quaternary ammonium bases or alkali metal (Na or Li) NITRILES (MeCN) or N, N-dialkylamino (DMF). The cathode used any inert metal, such as Ni.

The extract is evaporated, the crystals cyclopentadienyls (ferrocene) is separated. Yield 88% [U.S. Pat. Germany 2720165, CL 25 l 33/12, Appl. 05.05.77, publ. 18.01.79].

The method is complex in terms of technology, energy-intensive, insufficient yield of the target product.

A known way to the floor):

< / BR>
[M. Green. ORGANOMETALLIC compounds of transition elements.- M.: Mir, 1972, S. 128].

This method, using as a strong base diethylamine, and as a halide of iron chloride tetrahydrate iron implemented in domestic production of ferrocene (g Redkino, Moscow region):

2C5H6+FeCl24H2O+2(C2H5)2NH-->(C5H5)2Fe+2(C2H5)2NHCl+4H2O

The disadvantage of this method is the formation of resins due partly dimenisonal JRC (up to 5 wt.%), present in the JRS, irreversible loss of expensive diethylamine, low output (up to 88 wt.%) ferrocene.

These disadvantages and the method of obtaining ferrocene when used as a strong base hydroxide sodium (NaOH) [Chemical encyclopedia, so 5. - M.: Scientific publishing house "Great Russian encyclopedia", 1998, S. 165].

A common method of obtaining ferrocene is a process involving the interaction of freshly prepared cyclopentadiene K or Na in tetrahydrofuran (THF) or 1,2-dimethoxyethane anhydrous halides of iron or other salts:

< / BR>
[M. Green. M is s prior cyclopentadienide Na (K).

Along with ferrocene produces by-products, for example products of partial recovery of ferrocene, due to high activity cyclopentadienide alkali metal (in particular, its great resilience) at elevated temperatures.

The closest to the technical nature of the claimed is a method for ferrocene by the interaction of alkali metal hydroxide (e.g., KOH) with cyclopentadiene in the environment of DMSO followed by the addition of a solution of ferric chloride in dimethyl sulfoxide [Japan's Bid 1-213289, MKI407 F 17/02, Appl. 22.02.88, publ. 28.08.89, publ. in RICH 1990, 22 H 204 P].

The alkali metal hydroxide is dissolved in dimethyl sulfoxide (DMSO), in the mixture at ordinary temperature and under stirring in nitrogen atmosphere serves cyclopentadiene, then slowly but drops, add a solution of ferric chloride (for example, iron chloride tetrahydrate) in dimethyl sulfoxide. The molar ratio of the JRC: ferric chloride is 2.0:1.0 in.

After the addition of ferric chloride the mixture is intensively stirred for one hour, then it azeotropic distillation under reduced pressure, distilled off the mixture of Fe is Oh. Get ferrocene with access to 97.5 wt.%, with a melting point 173.5 metricoC.

The method recommended for industrial use. The disadvantage of this method is the formation of cyclopentadiene resins in the reaction mixture at the stage of selection of ferrocene and, as a consequence, lowering the quality of the target product. It is known that part of the cyclopentadiene is in a state of reversible equilibrium with Dicyclopentadiene:

ZPDCPG.

The number DCPD can reach 5 wt.% and more towards a mixture of JRS+DCPD.

In conditions of azeotropic distillation of ferrocene and DMSO at temperatures up to 150oWith free molecules JRS, including those resulting from thermal decomposition DCPD come with DCPD in the oligomerization reaction heat with the formation of tri-, Tetra -, and other higher oligomers JRS [C. W. feldblum, S. Y. Rozov and other Thermal oligomerization of cyclopentadiene in the liquid phase. Industry SC, 1980, 3, S. 4. C. N. Vostrikova, E. C., Ambrozaitis. The change in the quality of petrochemical Dicyclopentadiene high purity when gerpicheskoy processing. Industry SC, 1982, 3, S. 2].

The state of aggregation of oligomers with increasing chain length of the molecule passes from viscous to paraplane different masses and deposited partially on the walls of the equipment, which leads as their accumulation to his driving.

Since the boiling temperature of ferrocene is within the boiling temperature of the lower oligomers JRC (180-260oC) part of their distillation remains as impurities in the target product, reducing its quality.

The aim of the invention is the prevention of cyclopentadiene resins in the preparation of ferrocene, improve the quality of the product.

This goal is achieved by the fact that ferrocene is obtained by interaction of a hydroxide of an alkali metal (K, Na) dissolved in dimethyl sulfoxide containing 5-10 wt.% water, with cyclopentadiene dissolved in n-pentane, followed by separation of the phases and submission to the resulting cyclopentadienide To (Na) dissolved in aqueous DMSO, iron containing salts of hydrochloric acid (chloride iron chloride tetrahydrate iron) in a solution of dimethylsulfoxide.

The content in DMSO of 5.0-10.0 wt.% water enhances the heterogeneity of the phases at the stage of obtaining the intermediate product - cyclopentadienide potassium (sodium), better stabilization and full separation.

Separated pentalateral phase (with excess JRC) direct filing of ferric chloride carried out at ordinary temperature with stirring under inert atmosphere (N2). Use 15-30% solution of JRS in n-pentane (wt.).

The molar ratio of the JRC:KOH (NaOH) is 1.2 to 1.4:1.0 in.

The molar ratio cyclopentadienide To (Na) to Fel2(FeCl24H2O) is 2.0:1.0 in.

The concentration of KOH (NaOH) in DMSO 8,0-9,0 wt.%.

The selection of ferrocene carried out with known methods, for example using vacuum distillation DMSO with water vapor with the introduction of the reaction mixture of interning, such as oxypropylene (lapola) with subsequent supply after distillation DMSO any organic solvent ferrocene, for example, toluene, methyl tert-butyl ether (MTBE).

In order to secure a full selection from a mixture of DMSO and KCl (NaCl) with stirring differential mixer, water is supplied at the rate of 30-35 wt.% from remaining in a mixture of DMSO. This option, as shown, is energetically more favorable than a complete distillation of DMSO in the Stripping apparatus. Formed by the interaction of KOH (NaOH) with JRC chloride (Na) remains in the aqueous DMSO and easily separated from the hydrocarbon phase.

After stratification of the mixture in the sump is separated aq is with commodity product. The choice of solvent due to the requirements of the consumer.

If necessary, obtain crystalline ferrocene solvent is distilled off.

Get crystal product light, dark orange color with a melting point of 173,8-of 174.4oWith that do not contain iron impurities, moisture, cyclopentadiene resins and organic solvents. The yield of the target product of 97.8-to 98.4 wt. %. Coolant and diluent (for example, Laprol) and DMSO after appropriate treatment (drying) recyclery in the process of obtaining ferrocene. The effect is the absence cyclopentadienylsodium resins in the reaction mixture, and the target product is explained by the fact that when applying the JRC in a solution of n-pentane its interaction with the hydroxide (Na) occurs at the phase boundary: solvent - antibacterial (dimethylsulfoxide with dissolved hydroxide (Na) and formed cyclopentadienide To (Na) - pentane with dissolved JRC). When this is present in the JRS due to the reversibility of the equilibrium

ZPDCPG

the Dicyclopentadiene remains in the hydrocarbon phase, which upon termination of the reaction and sludge are removed from the remaining excess JRS.

In the known method, in contrast salaamgarage sublimation of ferrocene and DMSO thermal polymerization with the formation of oligomers JRS.

Almost the inventive method is carried out according to the scheme shown in the drawing.

In the mixer 1 serves dimethyl sulfoxide (DMSO) containing 5-10 wt.% water and solid KOH (NaOH) at the rate of 8.0, and 9.0 wt.% its content in DMSO.

Under stirring (current N2) serves 15-30% (wt.) the solution JRS in pentane at a molar ratio of the JRS and KOH (NaOH), is 1.2-1.4:1.0 in.

The mixture is stirred at ordinary temperature in a stream of nitrogen for 1-2 hours at a rotation speed of the stirrer 900-1200 rpm

The timing of all stages of the process specified on the basis of 100 l of the initial volume of DMSO and relevant amounts of other components.

Upon completion of the reaction obtain cyclopentadienide To (Na) mixture advocate for 0.5-1.0 hour. Then the upper hydrocarbon layer completely drain thoroughly and serve in recycling, and the remaining reaction mass - solution cyclopentadienide To (Na) in DMSO containing water at a speed of mixing 1200-1500 rpm slowly served 9,0-12,0% solution of FeCl2(or 13.5-18,0% solution of FeCl24H2O) in dimethyl sulfoxide.

The molar ratio of cyclopentadiene To (Na) and FeCl2is 2.0:1.0 in.

Padasuka FeCl2(FeCl24H2O). After the filing of ferric chloride the reaction mixture, the pH of which is 7.0, stirred for 1-2 hours, then fed to a Stripping apparatus 2 equipped with a reflux condenser vertical type.

Cube apparatus serves as intraining Laprol in the number 25,0-50,0% vol. to the reaction mixture.

While the total volumetric content of the reaction mixture in the cube does not exceed 30-35% of its volume.

The temperature in the cube of the apparatus is reduced to 60-70oAnd intensive circulation of the reaction mixture in Cuba, when submitting to the office of water vapor and low pressure raises the temperature in the cube apparatus to 148-150oC.

The steam flow is adjusted so that the distillation of DMSO was held for 1.5-2.0 hours.

The residual vacuum in the apparatus with distilled DMSO is 5-6 mm RT.article.

After evaporation of DMSO (distilled 85-90% of its amount in the mixture) the temperature of the cube is reduced to 40-45oWith, remove the vacuum and through the reflux condenser serves organic solvent ferrocene, for example, toluene, methyl tert-butyl ether (MTBE), which washes away when submitting crystals of ferrocene from the walls of the reflux condenser. The solvent is supplied from the calculation of receipt of 15.0-18,0% of rustically through collection 3 for 0.5-1.0 hour under stirring served through a filter to separate the iron hydroxide in the case of education in violation of the technology process) in the diaphragm mixer 4, in which water is supplied at the rate of 30-35% vol. from the remaining mixture in the amount of DMSO.

From the mixer 4, the mixture is fed to the settling tank 5, where the stratification of the phases. The top layer is a solution of ferrocene in solvent - or sent to the warehouse as a commercial product, or served in the reaction column 6 for removal of the solvent.

Get crystalline ferrocene light, dark orange color with a melting temperature (topl. ) 173,8-of 174.4oC that do not contain iron impurities, moisture, cyclopentadiene resins and organic solvents.

The yield of the target product is of 97.8-to 98.4 wt.%. The selectivity of the process and 99.8 to 99.9 wt.%.

The bottom two layers - Laprol and aqueous DMSO and KCl - share the sink and after appropriate treatment ( including azeotropic dehydration DMSO with benzene in column 7) are sent to recycling.

As waste in the process of getting ferrocene receive only an aqueous solution of KCl (NaCl).

Thus, the inventive method of obtaining ferrocene allows for the expense of carrying out the first stage of the process - get cyclopentadienide To (Na) in collaboration hydroxide (Na) with JRS in the two-phase system is to avoid the formation of oligomers JRS n the promotional mix entering the distillation of DMSO, do not contain iron impurities. The lower output of the target product of 97.8-98.4 per cent due to its losses at the stage of allocation at the expense of some volatility crystalline ferrocene and technological losses.

The following are examples of practical obtain ferrocene claimed and the known methods.

Example 1.

In the mixer serves 100 l of DMSO containing 5 kg (5 wt.%) water and 9 kg of solid KOH.

With stirring in a stream of nitrogen serves a 15% solution of JRC (of 12.73 kg) 115,2 l of pentane. The molar ratio of the JRC:the CON is 1.2:1.0 in.

The mixture is stirred at a temperature of 15oWith the mixer rotation speed of 1200 rpm for 1 hour.

The mixture is then defend for 0.5 hours.

After settling, the upper layer (pentane with the remaining JRC) carefully decant.

To the remaining reaction mixture containing cyclopentadienyl potassium in water-DMSO, under stirring (1200 rpm) slowly served 9,0% solution of FeCl2in dimethyl sulfoxide (DMSO) (10,26 kg FeCl2in 102,7 l DMSO). controlling the pH of the mixture in the range of 7.1 to 7.2. The molar ratio of C5H5K: FeCl2is 2.0:1.0 in.

At the end of the hearth is ebunny reflux of the upright type, the volume of the cube of the device is 750 DM3. However, the reflux condenser is chosen so that between it and the walls of the apparatus remained a significant gap, otherwise this space in the process of distillation, DMSO may be completely covered with crystals of ferrocene.

The volume of the reaction mixture in Cuba apparatus does not exceed 30-35%.

Cube apparatus as coolant serves 55 l of oxypropylene (lapola) in a volume ratio to the reaction mixture of 0.25:1.00 each.

The temperature in the cube of the apparatus was raised to 60oAnd intensive circulation of the reaction mixture in Cuba, when the steam creates a vacuum and raise the temperature. Steam is carried out so that the DMSO Argonauts for 1.5-2.0 hours. The distillation of DMSO is carried out at a temperature of cube 150oWith a residual vacuum of 6 mm RT.article.

In this first Argonauts with water vapor part of ferrocene, which is deposited on the walls of the reflux condenser. Then Argonauts DMSO.

After distillation 175 l DMSO (within 1.5 hours) the temperature of the cube is reduced to 40oWith, remove the vacuum and in the reflux condenser serves 120 l of methyl tert-butyl ether (MTBE), while washing the crystalline ferrocene from the walls of the reflux condenser to the cube of the device.

The mixture peremeshivaete, send diaphragm in the mixer 4, which serves to 6.5 l of water (30% of the remaining DMSO).

From the mixer 4, the reaction mixture is fed to the sump 5. The top layer is a solution of ferrocene in MTBE - served in the distillation column 6 for MTBE distillation and separation of ferrocene. MTBE direct recycle to the process.

Get 14,6 kg ferrocene crystals which are orange in color without foreign inclusions.

The output of the ferrocene of 97.8 wt. % of theoretical. Melting point 174,0oC.

Ferrocene does not contain iron impurities, moisture, organic solvents and cyclopentadiene resins.

Example 2.

In the mixer 1 serves 100 l of dimethyl sulfoxide containing 10,1 kg (10 wt.%) water and 9.9 kg of solid NaOH.

With stirring in a stream of nitrogen serves a 30% solution of JRS in pentane (22,87 kg JRS 86 l pentane).

The molar ratio of the JRC: NaOH is 1.4:1.0 in.

The mixture is stirred at 25oC for 2 hours with rotation speed of the mixer 900 Rev/min the mixture is Then assert within 1 hour. After settling, the top layer is poured.

To the remaining mixture with the speed of rotation of the agitator 1400 rpm, when the pH of the mixture 7,1-7,2 slowly serves a 12% solution FeC CLASS="ptx2">

The mixture (pH 7) is stirred for 1.5 hours under stirring served in the Stripping apparatus 2.

Cube apparatus serves 120 l lapola in a volume ratio to the reaction mixture of 0.5:1.0, the temperature of the cube up to 70oAnd intensive circulation of the reaction mixture in Cuba, the supply of water vapor and residual vacuum of 5 mm RT.article distilled DMSO, the temperature of the cube while 148oC.

After distillation of about 180 l of DMSO (within 2 hours) the temperature of the cube is reduced to 45oWith the vacuum off, and a reflux condenser serves 170 l of toluene.

The mixture is stirred for 30 minutes at circulation through the collector 3, and then through the filter is directed to a diaphragm mixer 4, which serves 8.5 l of water (35% of the remaining DMSO). On the filter is installed after the collector 3, the hydroxide of iron is missing.

From the mixer 4, the reaction mixture is poured into tank 5.

Spend the allocation of ferrocene and recyclorama lapola, toluene, DMSO in example 1. Get 22.5 kg of ferrocene with access 98,0 wt.%. The selectivity of the process is and 99.8 wt.%.

Crystals of ferrocene orange without foreign inclusions, the melting temperature (topl.) 173,8oC.

Ferrocene not when SS="ptx2">

In the mixer 1 serves 100 l of dimethyl sulfoxide containing 8.1 kg of water (8 wt. %), and 9.3 kg of solid KOH. With stirring in a stream of nitrogen serves 20% solution JRC (of 14.25 kg JRC) in 91,0 l of pentane. The molar ratio of the JRC: the CON is 1.3:1.0 in.

The mixture is stirred at 20oC for 1.5 hours at speed mixer of 1000 rpm the mixture is Then defend for 40 minutes.

After settling, the top layer is poured. To the remaining mixture with stirring (1500 rpm) slowly (pH of the mixture 7,1-7,2) serves 18,0% solution of chloride tetrahydrate iron FeCl24H2O in dimethyl sulfoxide (16,52 kg FeCl24H2O l 74,5 DMSO).

The molar ratio of cyclopentadienide potassium and FeCl2is 2.0:1.0 in.

The mixture is stirred for 1.2 hours (pH 7.0) and with stirring after the filing of FeCl24H2O is directed to the Stripping apparatus 2.

Cube apparatus serves 85 l lapola at a volume ratio to the reaction mixture of 0.4:1.0 in.

In the conditions of example 1 for 2 hours, evaporated to about 145 l DMSO, reduce the temperature of the cube 45oWith, remove the vacuum and in the reflux apparatus serves 135 l MTBE.

The mixture circulating through the collector 3 for 45 minutes, then through portfolio-4, which serves to 7.5 l of water (35% of the remaining amount of DMSO).

The selection of ferrocene, lapola and DMSO carried out as in example 1. Get 15,2 kg of crystalline ferrocene orange color with a melting point of 174.4oC. Yield of ferrocene is to 98.4 wt.%. The selectivity of 99.9 wt.%.

Traces of iron, moisture, cyclopentadiene resins and organic solvents in the resulting product are not available.

Example 4.

In the mixer 1 serves 100 l of dimethyl sulfoxide containing 7,1 kg of water (7.0 wt%) and 8.8 kg of solid KOH. Under stirring at a temperature of 15oWith the speed of the mixer 900 rpm serves 20% solution of JRS in pentane (14,52 kg JRS in 92.8 l pentane). The molar ratio of the JRC to CON equal to 1.4: 1.0 in.

The mixture is stirred for 1 hour, then defend for 40 minutes and after sludge is drained upper hydrocarbon layer.

To the remaining mixture with stirring with a speed of 1400 rpm serves a 13.5% solution of FeCl24H2O in DMSO (15,63 kg FeCl24H2O 99,2 l DMSO).

The molar ratio of C5H5To:FeCl2is 2.0:1.0 in.

The selection of ferrocene and recyclorama in the process of Laprol, MTBE and DMSO carried out as in example 1. In eflector apparatus 2 after distillation of about 165 l DMSO served 110 l MTBE, and in the mixer 5 add 9 liters of water. Get 14,34 kg ferrocene crystals which do not contain extraneous inclusions. Melting point 173,8oC. the Yield of ferrocene was 98.2 wt.%. The selectivity of 99.9 wt.%.

The obtained product does not contain iron impurities, moisture. cyclopentadiene resins and organic solvents.

Example 5.

In the mixer 1 serves 100 l of dimethyl sulfoxide containing 8.1 kg of water (8 wt. %) and 9.0 kg of solid KOH. With stirring in a stream of nitrogen serves a 25% solution of JRS in pentane (of 12.73 kg JRS 61 l of pentane). The molar ratio of the JRC:the CON is 1.2:1.0 in.

The mixture is stirred for 1 hour, defend 0.5 hours, poured the upper hydrocarbon layer. To the remaining solution cyclopentadienide potassium5H5To slowly add a 15.5% solution of FeCl24H2O in DMSO (15,99 kg FeCl24H2O 86,4 l DMSO).

The molar ratio of C5H5To:FeCl24H2O is 2.0:1.0 in.

Select Ferreira and recyclorama lapola, MTBE and DMSO is carried out in the conditions of example 1. In the cube apparatus 2 before the distillation of DMSO added 55 l lapola (in proportion to the reaction mixture of 0.25:1.0) and in the reflux apparatus 2 after the distillation of 160 l DMSO-podracers melting 174,3oC. the Selectivity of the process and 99.8 wt.%.

The product does not contain iron impurities, moisture, cyclopentadiene resins and organic solvents.

Example 6 (the prototype).

In the mixer 1 serves 100 l of DMSO, and 9 kg of solid KOH.

With stirring in a stream of nitrogen serves of 12.73 kg JRS. The molar ratio of the JRC:the CON is 1.2:1.0 in.

Then to the mixture under stirring (1800 rpm) slowly added dropwise to 13.5% solution of FeCl24H2O in DMSO (15,99 kg FeCl24H2O 101.5 l DMSO). The molar ratio of cyclopentadienide potassium and FeCl24H2O is 2.0:1.0 in.

After the addition is tetrahydrate iron chloride the mixture is stirred for 1 hour.

The selection of ferrocene carried out as in example 1, adding cube Stripping apparatus 68 l lapola, after distillation 170 l DMSO for 1.5 hours in a reflux condenser serves 120 l of MTBE, and the diaphragm mixer serves 4 10 l of water.

However, in the study of reaction mixture in Cuba apparatus 2 after the distillation of DMSO in it visually detected white Guardia insoluble in organic solvents inclusions - oligomers JRS, some of them have been found on the walls of the column.

Mass offinalis bottom of the mixture of the apparatus 2 shows the presence in it to 0.63 wt.% in relation to the original JRC of trimers, 0.47 wt.% - tetramers JRS.

Received ferrocene has a melting point 175,5oWith and contains as impurities cyclopentadienylsodium oligomers JRCs number 0,018 wt.%.

The output of ferrocene is 14,58 kg (97,6% by weight per FeCl2). The selectivity of the process to 98.5 wt.%.

The target product does not contain iron impurities, moisture and organic solvents, the content cyclopentadiene resins in the product 0,018 wt.%, however, on the filter after collection of 3 found a thin white coating containing the hydroxide of iron.

Analysis of the results of practical receipt of ferrocene claimed and known methods shows that the inventive method eliminates formation of cyclopentadiene resin at the stage of selection of ferrocene due to the fact that the reaction mixture does not come free JRS containing DCPD, originating in a known method of thermal polymerization of the JRC with the formation of tar.

In addition, in the known method a small part of the lower oligomers JRS when the distillation is adjudged to be in crystalline ferrocene, reducing its quality. The melting temperature of ferrocene obtained by a known method, is 173.5 metricoC, at Saleem level.

The absence in the reaction mixture, the target product and the waste of iron-containing impurities, the high selectivity of the proposed method with respect to ferric chloride (and 99.8 to 99.9 wt.%) indicates the fullness of the interaction of the reactants and that the reduction of the yield of the target product is due to its losses at the stage of allocation.

However, in the description of examples of periodic receipt of ferrocene on the well-known and inventive ways.

The problem of education in the reaction mixture cyclopentadiene resins known in the way significantly exacerbated during the transition to the continuous production of ferrocene in industrial (and even, as has been shown, in experimental-industrial) scale. Through 200-250 cycles cube evaporator, the lower wall of the dephlegmator and pipelines resulted cyclopentadiene resins, and cleaning equipment from them is problematic, as in all cases, the formation of thermopolymeric diene hydrocarbons.

By the present method pilot plant runs for 2.5 months and the problem of education tempentity resin does not occur.

Working concentration of KOH (NaOH) in DMSO practical examples the operation of all components.

When the concentration of the JRC in pentane, exceeding 30 wt.%, observed cyclopentadiene resins in the cube evaporator 2, the concentration of the JRC is less than 15 wt.% impractical and would require undue excess of pentane in the process.

The concentration of water in DMSO in the range of 5-10 wt.% determined on the basis of possible stabilization of the formed phases, their best separation. When the water concentration is less than 5 wt.% in DMSO is not achieved the desired stability of the phases, there is leakage of the JRC in the reaction zone. The concentration of water is more than 10 wt.% may at the stage of filing FeCl2(FeCl24H2O) to the appearance of by-products, in particular of iron hydroxide.

The concentration of KOH and FeCl2(or FeCl24H2O) in DMSO in the selected limits allow to obtain the target product, not containing virtually impurities.

When the concentration of FeCl2(FeCl24H2O) in DMSO greater than 12.0 wt.% (respectively 18 wt.%) in the reaction mixture may form a local excess of FeCl2that is unacceptable from the point of view of the purity of the target product, attainable only in strict compliance with the molar ratio of C5H5K(Na): Fl2(FeCl24H2O) than to allow its excess. The concentration of FeCl2(FeCl24H2O) is less than 9.0 wt.% (13.5 wt. %) inappropriate, because they lead to a decrease in the intensity of the process, unjustified neither from the point of view of the purity of the product, nor its output.

The number of Laprol served as interning in the reaction mixture before distillation of DMSO in a volume ratio to it 0,25-0,50:1,0, allows to achieve a desired dilution of ferrocene in the distillation of DMSO and temperature stability of the cube Stripping apparatus in the process of distillation DMSO.

Toluene, MTBE served in ferrocene after the distillation of DMSO in amounts corresponding receiving 15-18% solutions of ferrocene, which is determined by the solubility of ferrocene and requirements of the consumer.

In the Stripping apparatus 2 is distilled 85-90% DMSO so that part of it remained as a solution containing KS1 (NaCl). adding to which 30-35% vol. water (DMSO), which ensures good separation of phases - ferrocene in a solvent, lapola and a mixture of DMSO, KCl (NaCl) and water. Used reception of incomplete distillation DMSO and adding water to the remaining amount of DMSO promotes better separation of the phases and total separation DMSO and KCl (NaCl).

Used in examples 1-5 n-pentane corresponds to THE 38.101.493-79, CON corresponds to GOST 9285-78, NaOH - GOST 2263-79, FeCl24H2O complies with GOST 4149-65, DMSO corresponds to THE 13-0279411-01-89, Laprol THE 6-05-2033-87, MTBE corresponds to THE 0000-412-05742686-95 with ISM. 1,2.

1. The method of obtaining ferrocene by reacting potassium hydroxide or sodium cyclopentadiene in the environment of dimethyl sulfoxide and then adding to the resulting cyclopentadienide potassium or sodium ferric chloride in dimethyl sulfoxide at a ratio cyclopentadienyl potassium or sodium to chloride of iron 2,0: 1,0 (a mole. and the selection of the target product, characterized in that at the stage of interaction of potassium hydroxide or sodium cyclopentadiene in dimethyl sulfoxide impose additional 5-10 wt. % of water, and the cyclopentadiene serves as 15-30% solution (wt. ) in n-pentane at a molar ratio to potassium hydroxide or sodium 1,2-1,4: 1,0.

2. The method according to p. 1, characterized in that as the use of ferric chloride chloride and iron chloride tetrahydrate iron.

 

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The invention relates to an improved process for the preparation of ferrocene used as additives for boiler and engine fuels

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The invention relates to the production of derivatives of ferrocene, in particular ortho-carboxyethylpyrrole or its salts, used as a medicinal product in the deficit of iron in the body

The invention relates to a new stable complex compound containing macrocyclic tetradentate ligand having the structure of formula I, where R1and R2have the same or different values are related or unrelated, and each is selected from the group consisting of hydrogen, halogen, methyl, CF3and, if they are connected, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, are spatial and confirmation difficult, so that the oxidative degradation of complex metal compound is limited, when the complex is in the presence of an oxidizing environment, Z represents a stable to oxidation atom, which metallocomplexes selected from nitrogen and oxygen, X represents an oxidation resistant functional group selected from O or NRswhere Rsrepresents a methyl, phenyl, hydroxyl, auxillou group, CF3or CH2CF3, R3, R4, R5represent fragments of connecting adjacent Z atoms containing structure described in the claims
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The invention relates to the field of chemical industry, in particular to a method of obtaining a new water-binding aluminosilicate dispersed systems

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: inorganic synthesis.

SUBSTANCE: invention provides heterometallic neodymium (III) and iron (III) malate having formula I:

appropriate for synthesis of mixed oxides with perovskite structure, which are used as catalysts in oxidative catalysis of unsaturated acyclic hydrocarbons and as materials used in microwave frequency technology and in computer memory materials. Preparation consists in electrolysis of concentrated aqueous solution of neodymium (III) chloride and malic acid at 1:3 ratio in presence of pyridine with pressed reduced iron anode and inert cathode at anode current density 1 A/cm2, followed by separating precipitate and washing it with organic solvent before drying.

EFFECT: enlarged assortment of oxidation catalysts.

2 cl, 1 dwg, 2 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for preparing acetic acid salts, in particular, anhydrous ferrous (II) acetate. Method for preparing anhydrous ferrous (II) acetate involves interaction of metallic iron with acetic acid in the presence of oxidizing agents of ferric oxide Fe2O3 or Fe3O4 and molecular iodine in the mole ratio acetic acid : acetic anhydride : iron oxide = 100:(6-20):(2-2.5), respectively, and in the mole ratio iron oxide : iodine = 100:6.3. The process is carried out at temperature 80°C in the beaded mill of vertical type with high-rotation blade mixer and reflux condenser in the mass ratio of glass beads and liquid phase in the charge = 1:1. The process is carried out with periodic taking off samples of the end product solid phase by filtering and the following recover filtrate and feeding with acetic acid and iron oxide. For compensation of components loss of liquid phase in filtering there are recovered into reactor to the repeated process that is carried out for four times at a time. All procedures of the basic process and filtration are carried out in nitrogen medium. Preferably, method involves using hematite, γ-oxide, iron minium, magnetite or Fe3O4 x 4 H2O as the iron oxide source. Invention provides possibility for preparing anhydrous ferrous (II) acetate and simplifying method due to excluding the evaporation stage in isolation of salt.

EFFECT: improved preparing method.

3 cl, 2 tbl, 8 ex

FIELD: industrial inorganic synthesis.

SUBSTANCE: implementation of the method comprises contacting iron in the form of iron powder or iron sidewall adjacent to a body with glacial acetic acid and air oxygen at 17-25°C and vigorous stirring effected by high-speed blade-type mechanical stirrer. Initial acetic acid-to-iron molar ratio is (224÷274):100. Acetic anhydride additive is preferably introduced in amount of 2% based on the initial concentration of acetic acid. When concentration of ferric salt in the mixture reaches 2.70-3.51 mole/kg, stirring is stopped and heavy unreacted iron particles are allowed to settle/ Major mass of product suspension is filtered off and thus obtained basic ferric acetate precipitate is dried. Filtrate, which is saturated acetic acid solution of basic ferric acetate, is returned into reactor to be reprocessed. Yield of desired product achieves 99.2-99.3%.

EFFECT: simplified process and improved economical efficiency due to utilization of inexpensive raw material and accessible oxidant.

2 ex

FIELD: inorganic syntheses.

SUBSTANCE: ferric acetate is prepared by interaction of metallic iron with acetic acid in presence of an oxidant. Process is carried out at ambient temperature in acetic acid/acetic anhydride medium (weight ratio 5:1) under nitrogen atmosphere. Molar ratio acetic acid/iron/basic ferric acetate is maintained the following: 10:8:1. Reaction mixture is thoroughly stirred with high-speed blade stirrer or shaken at shaking frequency 2 Hz. When consumption of basic ferric acetate is completed, suspension of ferrous acetate is separated by filtration from unreacted iron powder. Precipitate is dried and filtrate returned into the process.

EFFECT: simplified process due to selection of optimal oxidant.

2 ex

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