SU722915A1 - Method of preparing metal-carbonyls derivatives - Google Patents

Description

The invention relates to the synthesis of metal-organic compounds, namely, to a process for the preparation of metal carbonyl derivatives of the general formula (I) where R is an unsaturated cyclic hydrocarbon radical containing from 5 to 13 carbon atoms;

M - transition metal U-U11 group;

X - - 2-4, 10 which are used as catalysts for fuel combustion, hydrogenation and isomerization of unsaturated compounds to obtain metal coatings and finely dispersed metal powders 15.

A known method of obtaining derivatives of carbonyl metals of the General formula

RMCCO) _X , where R is an unsaturated cyclic hydrocarbon radical having from 5 to 19 or more carbon atoms;

M - metal U-UP groups (V, Nb. Τα, Μη);

χ - 2-4,. consisting in the fact that, for example, solid vanadocene is treated with carbon monoxide under pressure for 15 hours. The yield of vanadocene is 50% W, however, the synthesis of the starting vanadocene from vanadium and cyclopentadienyl sodium halides is difficult due to its high sensitivity to atmospheric oxygen.

A known method for producing derivatives of metal carbonyls> UE groups, in particular cyclopentadieiyltricarbonyl manganese (CTM). The synthesis of CTM is carried out by reacting C ₅ H ₅ N _o ic manganese pentacarbonyl bromide in an organic solvent while boiling the reaction mixture for 1-3 hours. The yield of the target product by this method reaches 80–85% for manganese pentacarbonyl bromide 121.

The disadvantage of this method is multi-stage. For the synthesis of DTM on this

7229 the method requires dimarganeddecacarbo-nyl [Mn _g (C0) _<o ] and its derivatives - manganesepentacarbonyl, which are currently inaccessible.

In a similar way, 5 identical tricarbonyl manganese C ^ H was obtained. ₇ MniC (^ with a yield of 56% [h].

Closest to the invention in technical essence and the achieved result is a method for producing ¹⁰ derivatives of metal carbonyls of the general formula I, which consists in the fact that the sodium or lithium derivative of the corresponding cyclic hydrocarbon is reacted with ¹⁵ transition metal salt and carbon monoxide in high-pressure apparatuses, at 80 -250 ° and a pressure of 60–31 atm in an inert atmosphere in tetrahydrofuran. Yield 40% (counting ²⁰ per MnBr ^). The reaction takes 18-20 hours [4).

Disadvantages of this process - the frequency and duration of the process, besides the long high-temperature processes lead to significant decomposition of the reaction mixture and resinification and therefore a low yield of the desired product, and the resulting resin during the reaction impede transport of the reaction mass in the piping ^30, the wires separating apparatuses and the allocation of target products.

All these factors make this method inefficient and uneconomical.

The purpose of the invention is to increase the yield of ^{35 of the} target product and the intensification of the process.

This goal is achieved by the fact that the sodium or lithium derivative of the corresponding cyclic hydrocarbon is reacted with a transition metal salt and carbon monoxide at 80-170 ° C in an inert atmosphere under a pressure of 30-280 atm in tetrahydrofuran medium under the influence of ultrasound with a frequency of 4 to 22 kHz The yield of the target product is 60-86%. The reaction takes 1-4 hours .. '

PRI me R 1. Synthesis of cyclopentadienium tricarbonyl manganese (CTM).

A thin suspension of anhydrous Mn (13 parts) in benzene (100 parts) HC ₉ H ₅ Na (18.2 parts) in absolute THF (50 parts) is introduced into a 0.5 L reactor equipped with an ultrasonic transducer and purged with nitrogen using vacuum. give an initial pressure of CO of 30-50 atmospheres, include ultrasound and heating of the reactor. Bring the temperature

4 ao 100 -170 ° С. The reaction mixture is kept at this temperature for 1-3 hours. The reactor is cooled, the residual pressure of CO is released, purged with nitrogen and the reaction mixture is drained through a valve into a distillation apparatus. The selection of DTM is carried out by steam distillation. The yield is 80–86%. DTM - yellow crystals, so pl. 75-76 ° C.

Without opening the reactor spend 17 experiments without reducing the yield of the target product.

PRI me R 2. Synthesis of methylpiclopentadienyltricarbonylmanganese.

Carried out according to the method described in example 1, only methyl cyclopentadiene is used instead of cyclopentadiene.

'Product yield 65% based on MpSSySN ^ SdNdMn ^ SS ^ light yellow liquid, b.p. 106.5 ° C, 12 mm, n ^Z ° = 1.5873.

Example 3. Indenyltricarbonyl manganese.

A fine dispersion of sodium metal 2 g in 100 ml of THF and 5 g of indene in 15 ml of THF is introduced into a 0.5 L reactor equipped with an ultrasonic transducer, purged with nitrogen using nitrogen, and anhydrous MCPI 3.5 g) is introduced into the same mixture, and carbon monoxide at a pressure of 70 atm. (include ultrasound and reactor heating). The temperature of the reaction mixture was brought to 100-150 ° and kept at this temperature for 1-3 hours. The reactor was cooled, the residual pressure of CO was released, purged with nitrogen, and the reaction mixture was drained through a valve into a distillation apparatus. The isolation of indenyltricarbonyl manganese is carried out by steam distillation.

The yield of 60%, so pl. 50-52 S.

Example 4. Synthesis of fluorenyltricarbonplmanganese.

Carried out analogously to example 3, only instead of indene in the reaction introduced fluorene.

C _l5 HgMn (CO) _d 25% was _isolated , mp. 117-118 ° C. According to the known method, fluorenyltricarbonyl manganese is obtained in 11% yield.

PRI me R 5. Obtaining cyclopengadienyl tetracarbo nilva nadia.

To 8 hours of coarse metallic sodium at 60 hours of THF, 19 hours of cyclopentadiene in 50 parts of THF and 1.5 hours of Ge (CO) _{5 are} added. After hydrogen evolution through the valve in countercurrent

7229 inert gas injected VC (L ₃ (13 h) in

including benzene. The reactor is purged with carbon monoxide, a pressure of 180-200 atm, ultrasound and heating of the reactor are turned on, the temperature is brought to 130 ° C and at 5 this temperature the reaction mixture is kept for 2–4 hours. The reactor is cooled, the residual pressure is released, and the reaction mixture is drained through a valve. A dark red solution in a stream of inert gas is passed through a column with · The solvent is removed from the transparent solution in vacuo.

C ₅ HjV (C0) ₄ 70% is isolated in the form of dark red crystals with mp. ^fifteen

138-140 ° C.

Example Synthesis of cyclopentadienyl tetracarbonylniobium.

To cyclopentadienyl sodium prepared from 9 parts of sodium and 10 parts of cyclopentadiene in 100 parts of THF, 1 part of Fe (C0) ₅ and 11.7 parts of NaC & in 50 parts of benzene are gradually added. The reaction is carried out for 4 hours at 80 ° C and 280 atm. With. 25 After cooling the autoclave, the reaction mixture is poured in countercurrent argon into a receiver, the solvent is evaporated in vacuo. The dry residue was sublimated at 80 ° C, 0.1 mm. Yield C ₅ H ₅ Nb (CO) ₄ 30

60-65%, mp 144-145 ° C.

¹⁵ 6

Claims (2)

method requires dimarganepdekakarb NIL SMP2.CO), and and its derivatives - hectares of manganese pentacarbonyl | which are currently inaccessible. In a similar way, an identical tricarbopil manganese .MnCCQ was obtained with a yield of 56% s. The closest to the invention in its technical essence and the achieved result is a method for producing metal carbonyl derivatives of general formula I, which means that the sodium or lithium derivative of the corresponding cyclic hydrocarbon is reacted with a transition metal salt and carbon monoxide in high pressure apparatus. 250 and a pressure of 60-31 atm in an inert atmosphere in tetrahydrofuran medium. Output 4O% (calculated on MpVg.,). The reaction lasts 18-20 hours. 4 The disadvantages of this method are the periodicity and duration of the process, besides the long-term high-temperature processes lead to a significant release of the reaction mixture and its tarring and, consequently, to a low yield of the target product, and the resin formed during the reaction. it is difficult to transport the reaction masses through pipelines to separation devices and to isolate the desired products. All these factors make this method ineffective and uneconomical. The chain of the invention is to increase the yield of the target product and intensify the process. The goal is achieved by reacting the atrium or lithium derivative of the corresponding cyclic hydrocarbon with a transition metal salt and carbon monoxide at 80-170 in an inert atmosphere under the pressure of 30-atm in atmosphere of tetrahydrofuran under the influence of ultrasound frequency from 4 to 22 kHz. The yield of the target product 6O-86%. Rek .tsi goes 1-I1 h. Example. Synthesis of cyclopentadienyltricarbonyl manganese (DTM). Into a 0.5 liter reactor, equipped with an ultrasonic transducer, purged with nitrogen using vacuum, a thin suspension of anhydrous NnCt (13 parts) in benzene (1OO parts) and CsHsNci (18.2 parts) in absolute THF (5O parts) , give the initial pressure of CO 30-50 atm, include ultrasound and heating of the reactor. The temperatures are ao 100-170 ° C. The reaction mixture is held at this temperature for 1-3 hours. The reactor is cooled, the residual pressure of CO is released, purged with nitrogen and the reaction mixture is poured through a valve into a distillation apparatus. The separation of the DTM is carried out by steam distillation. Output 8O-86%. CTM - yellow crystals, so pl. 75-76 ° C. Without opening the reactor, 17 experiments were carried out without reducing the yield of the target product. Example: Synthesis of methyl cyclopentadienyl tricarbonyl manganese. Carried out according to the method described in Example 1, only methylcyclopentadiene is used instead of cyclopentadiene. Bbixoa product 65% in pacjiere at MnSaRdCiSsdNdMpsSSS) light yellow liquid, bp. 106.5 ° C, 12 mm, and ° 1.5873. PRI me R 3. Ikdeniltricarbonyl manganese. In a 0.5 liter reactor equipped with an ultrasonic transducer, purged with nitrogen using vacuum, fine grains of metallic sodium 2 g in 1OO ml THF and 5 g indene in 15 ml THF are introduced and anhydrous (3.5 g ) and carbon monoxide under pressure of 7O atm. (include ultrasound and reactor heating). The temperature of the reaction mixture is brought to 1OO-15O and held at this temperature for 1-3 hours. The reactor is cooled, the residual pressure of CO is released, purged with nitrogen and the reaction mixture is poured through a valve into a distillation apparatus. The selection of indenyl tri-carbonyl manganese is carried out by steam distillation. The product yield is 60%, so pl. 50-52 C. Example 4. Synthesis of fluorenyl tricarbonyl manganese. It is carried out analogously to Example 3, but instead of IVD, fluorene is introduced into the reaction. Entered With. NaMP (CO), 25%, m. Pl. 13 9 117-118 C. According to a known method, fluorenyl tricarbonyl manganese is obtained in a yield of 11%. PRI me R 5. Getting cyclopenadyl tetracarbo nilva nadi. To 8 hours of coarse metallic sodium at 60 hours. THF was added 19 hours of cyclopentadiene at 50 hours. THF (1.5 hours HESSO). After hydrogen was introduced through a valve in a countercurrent of inert gas 5, VC (l (13 h) in 6 oz of benzene was introduced. The reactor was flushed with carbon monoxide, pressure 18 o-2 oo atm, included ultrasound and heating of the reactor, temperature was adjusted to 13 o c and at At this temperature, the reaction mixture is held for 2-4 hours. The reactor is cooled, the residual pressure of CO is released, the reaction mixture is drained through a valve. The dark red solution in a stream of inertial gas is passed through a column with a clear solution in a vacuum to remove the solvent. ), 70% in the form of those 1g-red crystals with a melting point of 138-140 ° C. EXAMPLE 6 Synthesis of cyclopentadienyl tetracarbonylniobi. To cyclopentadienyl sodium, prepared from 9 h, sodium and 1O part of cyclopentadiene in 1OO h. THF gradually shed 1 h of Fe (CO ) 5 and 11.7 parts of NaC in 5O parts of benzene. The reaction is carried out for 4 hours at 8 ° C and 280 atm. C. After cooling the autoclave, the reaction mixture is poured in a countercurrent of argon into the receiver, the solvent is evaporated in vacuo. the residue is sublimated at 8 ° C, O, 1 mm. Output C HsNbCCO), 6O-65%, so pl. 144-14З p. 156 Claim 1. Instruction for the production of metal carbonyl derivatives of the general formula RMCco :), where R is an unsaturated cyclic hydrocarbon radical containing from 5 to 13 carbon atoms; M is a transition metal of the V-V11 group; X - 2-4 by the interaction of the sodium or lithium derivative of the corresponding cyclic hydrocarbon, the transition metal salt and carbon monoxide under pressure, when heated in an inert atmosphere, in tetrahydrofuran medium, so that, in order to increase the yield of the target product and the intensification of the process, the reaction is carried out under the influence of ultrasound frequency from 4 to 22 kPh. 2. The method according to claim 1, which is carried out with the fact that the process is carried out at 80-170 ° C. Sources of information taken into account in the examination of LZ / NoLtur-forsch gb 5О31, 1954. 2. Izv. Academy of Sciences of the USSR, ser. chemical 1963, p. 188O. 3.3.0rganomeiae..Chem: 23.527.197O. 4.3 3norg.nuct.Chem 1.165, 1955 (pyuotype).