DE2254342A1 - USE OF AN ORGANIC METAL COMPLEX FOR MOLECULE ACTIVATION - Google Patents

Description

Dr. Hans-Heinridi Willrath

Dr. Dieter Weber Diploma in Phys. Klaus Seiifert

.PATENT ADVOCATES

Z - 62 WIESBADEN 3rd Nov. "1972 PostfaA 1327

Gustav-Frey Tag-Stra6e 25 II / Wh

<& (06121) 372720
Telegram terrace: WILLPATENT

7000-943

Allied Chemical Corporation, Morristown, Nev. 7 Jersey 07 960, USA

Use of an organometallic complex to activate molecules

Priority; Serial No. 196 94 $ 4 - dated November 9, 1971 in USA

Addition to patent application P 22 43 664.2

The invention relates to the activation of molecules such as hydrogen ,. Nitrogen, carbon monoxide, carbamates, aldehydes, ketones, aromatic hydrocarbons and saturated and unsaturated aliphatic and alicyclic hydrocarbons to make various addition products, rearrangements and chemical Cause reactions.

ORIGtNAi i

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Post office: Frankfurt / Main 6763 Bank: Dresdner Bank AG. Wiesbaden. Account no. 276 807

Certain molecules, such as hydrogen, nitrogen, carbon monoxide, Carbamates, aldehydes, ketones, aromatic hydrocarbons and saturated and unsaturated aliphatic and alicyclic hydrocarbons / v / earth brought into direct intimate contact with an organometallic complex described in the German patent application P 22 43 664.2 is described, whereby catalytically numerous chemical reactions, such as hydrogenations, hydropolymerizations, Amonolysis, isorrization, synthesis, decarbonylation and hydroformylation can be effected.

It has now been found that certain useful chemical reactions and transformations of certain molecules can be brought about by activating such molecules by bringing them into contact with certain metal-organic compounds with sterically exposed metal-metal bonds . More specifically, the organometallic complexes that have been found to be very effective in catalysis of these reactions and molecular misalignments are those that have the general structural formula R M444M'R, where R is a ligand that carries one or more carbon, hydrogen, oxygen -, nitrogen, sulfur or phosphoratoine, η denotes an integer from 1 to 3, M and M ^{1 can be} identical or different and denote transition metals and the symbol 444 denotes at least a sterically exposed or unhindered and unsaturated metal-metal bond .

Some of these activators are:

a) bis (dicyclopentadienyltitanium II) - / Jc ₅ U ₅ ) ₂ Tί? ₂

b) bis (tltan-II-pinacolate) - / ^ β ^ΙΙ ₁ 2 ^Ο 2 ^τ ^ 2 ι

309820/1076 ORIGINAL BATHROOM

c) Bis- (trinethylsilylmethyl) -titanium-II-dimer -

d) Bis-idicyclopentadienylzircon-II) - / Tc ₅ K ₅ ) ₂ Zr7 ₂

e) Bis- (zircon-II-pinacolate) - / C ^ -H ₁₂ O ₂ ZrZ ₂ and ¹

f) Bis- (dicyclopentadienylmolybdenum-II) - / Τ ^ ςΗ-.) ₂ Mo / ₂

These organometallic complexes are very reactive towards molecules such as hydrogen, nitrogen, carbon monoxide, carbamates, Aldehydes, ketones, aromatic hydrocarbons and saturated and unsaturated aliphatic and alicyclic Hydrocarbons.

Although there is no intention here to rely on any theory for the subject matter of the invention, it is assumed that these molecules are activated, as shown by the reversible reaction equations below, where for Purposes of explanation as an organometallic complex bis (dicyclopentadienyltitanium-II) is taken.

1. / Tc ₅ H ₅ J ₂ TV ₂ + N ₂ - ^ / Tc ₅ Hg) ₂ Ti-N = M-Ti (C ₅ IIg) ₂ /

2. ZTc ₅ V ₂ TiZ ₂ + H ₂ ^ ZTc ₅ E ₅ ) ₂ Ti ^> i (C ₅ H ₅ ) ₂ _7

3. ZTc ₅ K ₅ ) ₂ Ti7 ₂ + nH ₂ ^ / Tc ₅ H ₅ ) ₂ Ti-H-Ti (C ₅ F ₅ ) ₂ -H? _n

n = 1, 2, 3, 4, 5 etc.

4. / Tc ₅ H ₅ ) TV ₂ + C ₂ II ₄ - ^ / Tc ₅ H ₅ ) ₂ Ti7 ₂ C ₂ H ₄

5. / Tc ₅ H ₅ ) TV ₂ + C ₆ II ₆ ^ / Tc ₅ H ₅ ), TiZ ₂ C ₆ H ₆

6. / Tc ₅ II ₅ ) ₂ Ti7 ₂ + H ₂ C = CH-C _n H _{2n + L} ^ ±

7. / Tc ₅ II ₅ ) ₂ Ti7 _? + 2ZH ₂ C = CH-CH = CH ₂ _7 TII ₅ ) ₂ Ti (H ₂ C = CH-Cn = CH ₂ ) /

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An apparatus in which most of the chemical reactions can be carried out is shown schematically in the enclosed Drawing shown.

Reference numeral 1 denotes a reaction vessel equipped with a stirrer. Un the sample of a poem To avoid this, it can optionally be actuated magnetically, as shown, with a drive magnet 2 and a driven magnet 3 will. This boiler is able to withstand several atmospheres of pressure and can also work under reduced pressure to be able to.

A storage boiler 4, which also serves as a distillation plant, is with stopcocks and lines for distilling liquid raw materials and / or diluents contained therein a molecular sieve chamber 5 is connected to the reactor 1.

The container 6, which holds material distilled from the reactor 1, and the kettles 1, 4 and 6 are immersed in cooling baths 7, 8 and 9, respectively, which can optionally be lowered slightly to allow the fetters to spontaneously reach ambient temperature warm or can be warmed by an additional wire. These cooling baths can contain liquid nitrogen in order to bring the contents of the immersed kettle to -19 ° C. cool. However, the temperature is not critical. Dry ice baths can be used, or even higher temperatures than those produced by such baths. Obviously, however, it is important to keep the temperature of a fepsel acting as a receiving vessel below that of a connecting kettle that acts as a distillation device

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one of the reactants is an easily liquefiable gas or is readily liquefiable vapor, it is also generally preferred operate at a temperature sufficiently low to ensure that the reactant is in the liquid State is maintained.

In addition, the temperature must be sufficiently low to ensure that the material contained in the storage kettle does not significantly boil away or during the time in which the Varratskessel in connection with a diffusion pump or a other ^ vacuum device is, evaporates.

The gas container 10, which preferably has a larger capacity, as the reactor, can be a vessel as shown, or it can also be a relatively bulky vacuum line, their Capacity exceeds that of the reactor by a noticeable degree. In the case of the present examples, this has Chamber or conduit more than 12 times the volume of that of reactor 1. The ratio of the volumes is but not at all critical, but if the volume of these chambers is relatively small, becomes the 3 number of reaction cycles and therefore the associated one Response time increased.

The kettle 12 is a gas cylinder which comes to an end ; if.

as

one of the reaction partners / a compressed or liquefied one Gas receives. If a liquefied gas is present and also if it is not from. is of sufficient test quality, it can be "distilled" through the molecular sieve chamber 13 in order to ensure an absolutely dry reactant.

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To better understand the process of performing chemical Reactions, rearrangements and polymerizations can be the reference to serve on the drawing.

Hydrogenations, hydrodecyclopolymerizations, ammonolyses and
Ilydroformylations can be carried out in a very similar manner, as can be seen from Examples 1, 2, 4, 5, 9, 11, 12 and 14.

The dry catalyst that has been selected is introduced into the reactor through inlet 14. The majority of these organometallic catalysts are very active and sensitive to air.
They must therefore be added in a vacuum or in an inert atmosphere such as dry argon. The dry catalyst
is less reactive than when wetted with liquid reactant or diluent. When dry it is not noticeably reactive to nitrogen gas at ambient temperature, but it is very reactive to it when it is
is damp. Rs 10 moles of catalyst per Itoi primary reactant were used in practice, but this means one
large excess, and satisfactory results can be expected with much less, such as with catalyst in the order of 20% of this amount.

The storage tank 4 contains the material that is to be subjected to one or more of the following processes: 1. Hydrogenation,
2. hydrodecyclopolymerization, 3. ammonolysis, 4. hydroformylation or other processing methods within the capacity of the selected catalyst. Preferably this material is

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very pure and absolutely anhydrous. To ensure drought, it is desirable to store the solvent over a molecular sieve. The reactor 1, the storage tank 4 and the receptacle 6 are cooled by immersion in cooling baths 7, 8 and 9. These cooling baths preferably contain liquid nitrogen, so that the immersed kettle is cooled to about -196 ° C. The total system including the distribution line 15, the gas container 10, the receiving container 6, the reactor and the storage container 4 are then evacuated by the Stop cocks 16, 17, 18, 19, 20, 22, 23, 24, 25 and then the stop cock 26 opens to the vacuum source. Although it is preferred to use the system to a high degree (about 10 to 10 mm Mercury), the degree of evacuation is not critical. A high degree of vacuum ensures quick removal of traces of moisture and oxygen, but has a lower one Vacuum degree only has the effect of extending the time required for the removal of such traces and possibly reduce the overall effectiveness of the catalyst somewhat.

All taps are now closed, with the exception of the shut-off taps 23 and 27. The cooling bath is removed from the storage container 4, which then warms up spontaneously to ambient temperature, and the desired amount of the reactant in the storage container 4 now distills into reactor 1.

In the event that this reactant is not absolutely dry is, and if he does not have anir. Molecular sieve has been stored, it is preferred to distill it through a molecular sieve 5, while the then to the cooled reactor 1 to a condensate

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tion directed \> / ird. In the case of some high-boiling reactants, it may be necessary to add a small amount of heat to the Supply reservoir 4 to effect the distillation.

When the reactor contains the desired amount, valves 23 and 27 are closed.

The storage tank 4 can now with a suitable diluent, such as normal heptane or tetrahydrofuran, are charged, or a second storage tank that holds the diluent can be used instead of the storage tank 4.

This diluent acts in the same way as the reactant treated. It is anhydrous, of high purity and is preferably stored over a molecular sieve. Of the Kettle is cooled as above, evacuated, and a quantity similarly distilled into the reactor. The crowd is not critical. Preferably the amount distilled is between about 1.5 and 5 times the amount of the first reactant in the reactor.

The gas, which represents the second reactant, is discharged from the cylinder 12, preferably at a pressure of about 1 at absolute, into the evacuated gas container 10 by turning the taps 16, 17 and the valve 29 are opened.

The nature of this gas will of course vary with the one to be carried out Reaction. It consists of hydrogen for hydrogenations and Ilydrodecyclonolymerizations, a mixture of hydrogen and nitrogen in a volume ratio of about 3: 1 for the Production of ammonia, from ammonia gas for ammonolysis and

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preferably from approximately equal parts by volume of carbon monoxide and hydrogen for hydroformylation reactions. When the reaction partner gases not of the highest purity and anhydrous, they are / should be passed through a molecular sieve on the way to the gas container 10 13 are directed.

The valve 29 and the cock 16 are closed, the cock 17 remains open, and a connection between the gas container 10 and the reactor 1 is established by additional opening of the taps. 19, 20 and 24 manufactured.

The contents of the reactor 1 are stirred and left with the Gas react until the pressure in the system drops below about 200 mm Hg. The selected pressure that marks the end of a reaction cycle indicates is not critical at all and varies somewhat with the ratio of the volumes of the interconnected boilers. ■

The gas flow to the reactor is interrupted by closing the taps 1.0 and / or 20, and the gas container is switched on again connected to cylinder 12, valve 29 and tub 16 open in order to restore the original pressure in the gas container 10.

The gas container is brought back into connection with the reactor, and the cycle is repeated until a substantially static gas pressure in the Fys'tem equilibrium and the Indicates completion of the reaction.

When reaction ^{1 has} essentially ended, the connection to the gas container is interrupted by closing taps 19 and 24. The container 6 is' with the aid of a cooling bath 9

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cools. Taps 20 and 30 have been opened and the product is ready distilled from the reactor to the container, taking it from the Diluent is separated.

The optimal temperatures and pressures that something rit the reactants and the catalysts chosen, are represented by the following information:

Hydrogenations can be carried out at about -20 to 200 ° C., with a range from 15 to 60 ° C. being preferred, 0.2 to 53 at absolute, with a Range of 1 to 5 at is preferred, and in 1 to 50 td. per circuit, with a range from 10 to 30 hours. preferred per cycle is to be carried out.

can (ydrodecycloOolyitierisierunrren at -? 9 to 200 C, a range from 30 to 80 ° C is preferred, at 1 to 50 at absolute, a range of 10 to 20 atm is preferred, and for 1 to 50 hours per cycle, with at about 10 to 30 hours per cycle are preferred, carried out v / ground. Monolysis can be carried out at 0 to 200 ° C, preferably at 15 to 100 ° C are, at 0.2 to 50 at absolute, with a range from 1 to 2 at is preferred, and for 1 to 50 hours per cycle, with about 10 to 30 hours before. Hydroformylations can take place at 20 to 250 ° C, with a range from 15 to 30 ° C is preferred, at 0.2 to 50 at absolute, with a range from 1 to 10 at is preferred, and during 1 to 50 Hours per cycle, with a range from 10 to 30 hours per cycle being preferred.

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In the polymerization of olefins as described in Example 3 are explained, and in the catalytic isomerizations or molecular rearrangements, as illustrated by Example 5, the way of working is on the whole the same as explained above, but simpler since there are no second reaction partners, like the gases required in the above procedures. The catalyst is fed into the reactor, and the reaction partner and the diluent are from the reservoir 4 to the Reactor 1 is distilled using the same methods and precautions described above. When the reactant is itself a gas, such as ethylene, it is better supplied from a cylinder than from the storage tank 4.

Polymerizations can be carried out using the following conditions be performed:

Polymerization temperature: -20 to 150 ° C / being a range of 50 to 80 ° C is preferred, polymer pressure: 0.5 to 25 at absolute, with a range from 1 to 10 atm being preferred, and total polymerization time: 1 to 50 hours, with 4 to 8 hours being preferred are.

Isomerizations can take place at temperatures between about 0 and 100 ° C, with a range from 1β to 80 ° C being preferred Pressures between 0.5 and 50 at absolute, with 1 to 10 at are preferred, and for a time of 1 to 100 hours, with 10 up to 30 hours are preferred.

In certain reactions, such as in the synthesis of methylamine from hydrogen and a metal cvanide, which is illustrated in Example 6, and. in the decarbonylation of a carbamate, as in

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As illustrated in Example 7, the first reactant is a solid rather than a liquid. But it will be the same apparatus and used essentially the same method as above. The solid carbaraate or cyanide flows directly through the insertion opening 14 was introduced into the reactor as was done with the catalyst. In both cases the selected diluent is Tetrahydrofuran. The reaction conditions are as follows:

Methylamine from II ~ and KCN (it can be the cyanide of any alkali metal, Alkaline earth metal or transition metal can be used). Temperature range: -20 to 200 ° C, preferably 10 to 25 C, pressure: 0.5 to 50 at absolute, preferably 1 to 10 at, reaction time: 1 to 50 hours per cycle, preferably 10 to 20 Hours per cycle.

Decarbonylation of carbamates: temperature range: 0 to 150 ° C., preferably 25 to 50 ° C., pressure: 0.1 to 1.0 at absolute, preferably 0.4 to 0.6 at, reaction time: 1 to 100 hours, preferably 20 to 30 hours

The following examples illustrate the methods according to the present invention Invention, wherein various molecules are activated in such a way that they molecular rearrangements, polymerizations and chemical Produce reactions which lead to the production of numerous useful products.

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example 1

Catalytic ^ hydrogenation of cyclohexene under

Formation of cyclohexane

A glass reactor with a volume of 35 ecm, equipped with a magnetic stirrer, is mixed with 36 mg of dry bis- (dicyclopentadienyltitanium-II) charged, which is carried out in an argon atmosphere in a dry box. The reactor is then equipped with a Vacuum manifold connected, which has a volume of 500 ecm, and with which he closed because of an intermediate Stopcock is not in communication.

A storage round bottom flask containing a quantity of pure, dry, oxygen-free cyclohexene, which in the presence of a Molecular sieve is stored in a similar manner with a closed stopcock between the supply flask and connected to the manifold. The storage flask is then cooled to -196 ° C in liquid nitrogen, the distribution line is evacuated to 10 to 10 mm of mercury, and both boilers are in connection with the distribution line and with each other by opening the stop cocks mentioned above.

The distribution line is now shut off from the vacuum source, with the distribution line and the associated boiler being evacuated stay. The reactor is cooled with liquid nitrogen while the stock flask, which serves as a distillation flask, is allowed to warm to ambient temperature so that Cyclohexene is distilled into the reactor with the catalyst. The distillation continues until 8.2 g of cyclohexene enters the reactor are distilled. The supply piston is locked and unlocked

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ORtGtKAi INSPECTED. .

removed, the reactor still remaining under reduced pressure. Now there is a storage flask, the pure, dry normal heptane which has also been stored in contact with a molecular sieve to ensure absolute dryness with the Manifold connected, cooled in liquid nitrogen, evacuated and the reactor via the manifold in the same Manner as described for the cyclohexene flask connected. The flask is allowed to warm to ambient temperature, and 10 g of n-heptane are distilled into the reactor as a diluent.

The vacuum manifold, which in this case comes from the gas container exists, is now charged with hydrogen of high fineness up to a pressure of 1 at. While the reactor continues to stir, becomes the distribution pipe or the gas container in connection with this and the reactor is allowed to reach ambient temperature. First, the pressure in the system drops to 700 Hg, da the reactor only under the vapor pressure of the hydrocarbon mixed stands. Stirring is continued, hydrogen becomes saturated due to the catalytic hydrogenation of cyclohexene Cyclohexane absorbed. The pressure is carefully controlled, and if it is below 200 mm I! G for a period of 20 hours has fallen, the manifold is shut off, refilled with hydrogen and the absorption cycle repeated. After the fourth cycle, there is no further hydrogen absorption I found what indicates that the system is in equilibrium is located. In total, 2.5 liters of IT ^ are measured under standard conditions of temperature and pressure (STP), consumed.

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A vacuum flask is now connected to the distribution pipe, but is not yet brought into open connection with it. The reactor and vessel are cooled with liquid nitrogen and then evacuated by placing them in open communication with the vacuum manifold. The manifold
is now shut off by the diffusion pump, which serves as a vacuum source, the reactor is allowed to warm to ambient temperature, and the product is thus distilled over into the receptacle.

7.5 g of cyclohexane product are obtained, corresponding to a yield of 89%. The product is determined by steam chromatography, infrared spectroscopy and nuclear magnetic resonance spectroscopy.

Example 2

Catalytic hydrodecyclopolymerization

from cyclohexene to paraffins

This example is done in exactly the same way as in Example 1, and carried out in a similar plant, with the exception that the vacuum manifold resp. the gas container is made of metal rather than glass and all parts are designed to withstand pressure. Of the The only difference when carrying out the process is the reaction temperature and the reaction pressure:

Catalyst: Fis- (dicyclopentadienyltitanium-II) 36 rag

Charge: Cyclohexene 8.2 g

Hydrogen (STP) 2.5 1

Diluent: heptane "10 g

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Reaction temperature: 65 ° C

Reaction pressure: autogenous

Response time (100 hours in total): 25 hours / cycle

Product: paraffins 0.82 σ

Yield: 10 %

Example 3

Catalytic polymerization of diolefins

with the formation of polyolefins

This example is in the same system as it was used in example 2, and practically in the same! ^<7 also carried out, but with the following differences:

No reaction partners are fed in, but only the butadiene to be polymerized, which brings about the polymerization Catalyst and a diluent. Since the butadiene is a gas, a butadiene cylinder is used instead of a storage flask used. The butadiene is taken directly from the cylinder through a molecular sieve absorber into the pre-cooled reactor with the temperature distilled from freely evaporating liquid nitrogen (-196 C). Less catalyst is used than in example 1, and a lower pressure is used for this polymerization than for the hydrodecyclopolymerization of Example 2.

Catalyst: Pis- (dicyclopentadienyltitanium-II) 30mg

Feed: Butadiene (STP) 2.5 1

Diluent: heptane 10 g

Reaction temperature: 65 ° C

Reaction pressure: autogenous

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- l7 "* '

Response time: 6.0 hours

Product: 'Polybutadiene 2.1 σ

Today: 35%

Example 4

Catalytic ammonolysis of ethylene

with formation of Xthylamine

This example is carried out in essentially the same plant and in the same way as in Example 1, although there is a difference in the handling of the gaseous ethylene. Instead of a storage flask, a gas cylinder with liquefied ethylene is used. The gas distilled from this over a molecular sieve moisture absorbers and condensed in DE-A pre-cooled reactor having a Tenoeratur of freely evaporating liquid ⁵ nitrogen (-196 ° C) -. ■ The reaction is carried out under relatively high pressure, because a le?. ta 11 reactor is used instead of an Ilas reactor.

Catalyst: / titanium H-pinacolate / ,, 34 mg

charge: "'ethylene gas 2.8 g

Anhydrous ammonia (liquid) 6.2 q

Reaction temperature: 60 C

Reaction pressure: 'autogenous

Response time: 50 hours

Product: ethylamine (yield 10 %) 0.45 g

By pearlizing nan can obtain higher yields.

BAD ORiOiNAL

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Example 5

Catalytic isomerization of Tlept-l-on uη tor formation of trans-Tcpt -? - eη

This example was in the same plant as used in Example 1 were carried out, but the method is ^l similar to that of Example 3 because only the catalyst and the llept-en 1, which should be isonerisiert, were fed. The isomerization time and temperature and the pressure under which the process was carried out are given below. '• ie in example 1 the charge was liquid and therefore became from the. The storage flask was distilled in the same manner as in Example 1 in a peactor.

Catalyst: bis (dicyclonentadienyltitanium II). Feed: 1-heptene
Diluent: n-heptane
Action temperature:
Reaction pressure:
Reaction time:
Product: trans-hept-2-en
yield

Example 6

Catalytic Synthesis of Methylamine from H ^ and KCN Using essentially the apparatus of Example 2, 6.5 grams of pure, dry calcium cyanide and 36 mg of dry bis (dicyclopentadienyltitanium II) were charged to a stirred metal reactor using the same method as that described at

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36 mg , 0 hours 9, 8 g 3 g 10 / O g % 20th ° C autogenous 15th 9, 95

of the feed used with the catalyst in Example 2 became. Instead of heptane as a diluent, 10 g of tetrahydrofuran were used used. Also, using the method of Example 2, a total of 7.5 liters of pure pulp in Fractions fed to your reactor by the manifold or the Gas container was filled 15 times, each time allowing the hydrogen to react with the potassium cyanide while the Mixture was stirred in the presence of the catalyst. The reaction was carried out under a pressure of 5 at at 20 ° C, which took 15 hours. The methylamine was removed as 0.16 g gas. Yield: 5%.

Example 7

Catalytic decarbonylation of urea with the formation of hydrazine

Using essentially the same apparatus and feeding method as shown in Example 6 7.0 g of pure, dry urea and 36 mg of dry ice (dicyclopentadienyltitan-II) was fed into a stirred glass reactor. 10 g of isopropanol were added as a diluent, and 2.5 1 H _{9 were} allowed to react with the urea in 5 portions of 500 ecm each, the IT _{7 being} fed into the distributor line, which was then connected to the reactor.

The reaction takes place at 40 ° C. under 0.5 at absolute. Every cycle Took about 15 hours to reach a Cleiehaawicht.

0.16 g of hydrazine was distilled off as a product from the Real'tor under vacuum. Yield: 5 %. .

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'-' ■■■■ '■ ■' ■ '■'< BAD

Example 0

Catalytic Aimonolysis of Chlorobenzene under

Formation of aniline

Using the apparatus of Example 2, 34 mg (titanium-II-pinacolate) 2 were placed as a catalyst in a reactor at -30 ° C fed in the absence of air, after which 11.2 g of pure, dry chlorobenzene were added. The latter became one Distilled storage flask into the reactor using the same method as described in Example 1. Likewise As in Example 1, 10 g of pure, dry normal heptane were distilled into the reactor. 100 g of pure anhydrous Ammonia gas were fed into the evacuated manifold, and the distributor pipe is brought into connection with the reactor, which was now warmed to 20 ° C, ura a conversion of the ammonia to allow with the stirred chlorobenzene until a total of 3.4 g of ammonia had been consumed.

Reaction temperature: 20 C

Reaction pressure: autogenous

Response time: (80 hours in total) 20 hours / cycle

Product: aniline 8.4 g

Yield 90%

Example 9

Catalytic decarbonylation of cyclohexanone to cyclopentane

This example was made in the same plant and on the oak tree Carried out as in Example 8, but with the exception

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that the cyclohexanone feed, which is a liquid and not a solid, is distilled into the reactor from a storage flask by keeping the cyclohexanone dry over a molecular sieve.

The amounts of the reactants and the temperatures and pressures used are summarized below.

Catalyst: bis (dicyclopentadienyltitanium II) 36 mg

Charge: Cyclohexanone ', 9.8 g

Diluent: ^s n-heptane 10.0 g

Reaction temperature: 20 C

Reaction pressure: autogenous

Response time: 40 hours

Product: Cyclopentane 0.70 g

,. Yield. 10 ΐ

Example IO

Catalytic hydroformylation with formation of 2-methylbutyraldehyde and / or valeraldehyde from 1-butene, carbon monoxide and

hydrogen

This example was carried out in the same system as example 2 and carried out essentially in the same manner as Example 4, with the exception that the reaction was carried out under 3 at pressure took place and the mixture of carbon monoxide and hydrogen took place Ammonia was used. A mixture of the isomers, 2-methylbuty-raldehyö and valeraldehyde, were obtained, as indicated above, but by varying the equilibrium constantan, as well as by changing it the reaction temperature and by selecting other cat-

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36 mg G 20th
/Cycle 5.6 1 G 2.5 1 G 2.5 C. 20 ° autogenous 4 χ
Hours. 0.22 0.22 51 "ό

lysers than the suggested, can be used as a product mainly one or the other of the two isomers can be obtained.

Catalyst: ^ is- (acetylacetonatonickel-I) Charge: 1-butene

Carbon monoxide

Hydrogen reaction temperature: .Reaction pressure: Response time: (80 hours in total)

Product: 2-methylbutyraldehyde Valeraldehyde yield

Example 11

Catalytic Hydrogenation of Benzene to Form Cyclohexane This example was carried out in essentially the same way as Example 1 except that higher pressures were required and therefore a metal reactor designed for high pressure as in Example 4, was used.

Catalyst: bis (dicyclopentadienyl-Ti-II) 36 mg

Cocatalyst: nickel powder 36 mg

Charge: Benzene 5 g

Hydrogen (in excess)

Reaction temperature: 20 C

Reaction pressure (absolute): 1.5 at

Response time per cycle: 10 hours

Yield: cyclohexane (20%) 1, OG g

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'- 23 -

The yield can be improved by cycling.

It can be seen that many different polymerizations, molecular rearrangements and chemical reactions are carried out can, if one uses the method of molecular activation and the catalytic Applying the effect of the invention without departing from the inventive concept.

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Claims (1)

Claims 1. Use of an organometallic complex according to patent (Patent application P 22 43 664.2) of the general structural formula R '. M'R, where R denotes a ligand which contains one or more carbon, hydrogen, oxygen, nitrogen, sulfur or phosphorus atoms, η is a whole number from 1 to 3, f and M ^{1 are} each identical or different transition metals and the symbol -ff for at least one sterically exposed "letall- ^ metal bond" means for activating hydrogen, nitrogen, carbon monoxide, carbamate, aldehyde, ketone, aromatic and saturated uncunsaturated aliphatic or alicyclic I Hydrogen molecules are formed by direct, intimate contact of these molecules with the organometallic complex. 2. Use of Ris- (dicyclopentadienyltitanium-II), (titanium-II-pinacolate) - ,, Bis- (trimethylsilylmethyltitanium-II) and / or bis- (acetylacetonatonickel-I) according to claim 1. 3. Use according to claim 1 and 2 with catalytic association of ammonia and an alkene with 1 to 12 carbon atoms an amine. 4. Use according to claim 1 and 2 with the catalytic combination of ammonia unc ¹ eim: s _{aromatics substituted by IJII 9} , Cl or CJ to form an aromatic amine. 5. Vorv.'cnduno according to claim 1 and 2 with catalytic association of hydrogen with an aliphatic unsaturated carbon 3 09820 / 107R hydrogen or an aromatic hydrocarbon
corresponding partially or fully saturated hydrocarbon. " β, use according to claim 5 with formation of cyclohexane from benzene and hydrogen. 7. Use according to claim 1 and 2 with Ilydropolyraerisierung an aliphatic alkene or alicyclic alkene with 2 to 12
Carbon atoms in the presence of i ^r on Hydrogen su higher molecular weight paraffins. 8. Use according to claim 1 and 2 with polymerization of diolefins with. 4 to 12 carbon atoms to a polymerized
Olefin product. D, Use according to claim 1 and 2 with isomerination of olefins having at least 4 to 12 carbon atoms by catalytically
induiorto migration of the Donnal binding. If), use according to claim 1 and 2 iinter catalytic association von ^ Ja ^ serstaff rat hydrogen cyanide s-lure odar a cy an id one Alkali metals, alkaline earth metals or transition metals to methylamine. 11. Use according to claim 1 and 2 with catalytic decarbonylation of a photon or aldehyde turned into a hydrocarbon. 12. Use according to claims 1 and 2 under catalytic hydroformy · " lation of hydrogen, carbon monoxide and an olefin into one ^ Idehyd. 309820 / 107R L e r s e i t e