DE102006049463A1 - Preparation of synthetic agents containing diorganomagnesium compounds and their mixtures with alkali metal salts, useful in e.g. synthetic chemistry, comprises reacting an alkali metal with a Grignard compound and an organic halo compound - Google Patents

Abstract

Preparation of synthetic agents containing diorganomagnesium compounds and their mixtures with alkali metal salts comprises reacting alkali metal or its mixtures or alloys with Grignard compounds (a) and organic halo compounds (b). Preparation of synthetic agents containing diorganomagnesium compounds and their mixtures with alkali metal salts comprises reacting an alkali metal or its mixtures or alloys with a Grignard compound (a) of formula (RMgX) or several Grignard compounds of formulae (R 1>MgX), (R 2>MgX) or (R 3>MgX) and an organic halo compound (b) of formula (RX) or several organic halide compounds of formulae (R 1>X), (R 2>X) or (R 3>X). R-R 3>H, optionally saturated, optionally functionalized aliphatic, cyclic, heterocyclic or aromatic 1-80C, preferably 1-20C organic fragments; and X : Cl, Br, I (all preferred), tosylate or triflate. An independent claim is included for the synthetic agent containing diorganomagensium compound of formula (R x 1>R y 2>Mg) as solution in an ether solvent comprising diorganomagensium compound in a mixture of lithium halo compound, Grignard compounds of formula (RMgX) and/or alkali metal organic compounds of formula (RM), where the molar ratio of the diorganomagnesium compound and lithium halo compounds is 1:0.1 to 1:2 and the molar ratio of the diorganomagnesium compound, Grignard compound and alkali metal organic compound is 1:0.15 to 1:4. x, y : 0-2 such that x+y = 2; and R-R 2>CH 3, C 2H 5, iso-propyl, n-propyl, n-butyl, iso-butyl, sec.butyl, tert.butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl.

Description

object The present invention is a process for the preparation of diorganomagnesium-containing synthesis agents and highly reactive magnesium, those obtainable by this method Synthesizers and their use.

Especially The present invention is a process for the preparation of mixtures of diorganomagnesiumhaltigen synthesis means with Alkali salts for use in organic and organometallic Synthetic chemistry, for example in halogen / metal exchange reactions or transmetalation reactions, or in metallation reactions.

Organomagnesium compounds have many applications in chemical synthesis (HG Richey, Jr., Grignard Reagents New Developments, John Wiley and Sons, 2000, GS Silverman, PE Rakita, Handbook of Grignard Reagents, Marcel Dekker Inc., 1996). Regarding the reactivity, Grignard compounds RMgX and diorganomagnesium compounds R ¹ R ² Mg are very similar (K. Nützel, Methods of Organic Chemistry, Organometallic Compounds (Houben-Weyl, Ed .: E. Muller, O. Bayer), Thieme Verlag Stuttgart, 1973 , Volume XIII / 2a, edition 4, p. 197 ff.). Mixtures of diorganomagnesium compounds with alkali metal organyls show in part a higher reactivity which is readily exploited in synthetic chemistry (K.Kitigawa, A. Inoue, H. Shinokubo, K. Oshima, Angew Chem 2000, 112, 2594, A. Inoue, K Kitagawa, H. Shinokubo, K. Oshima, J. Org. Chem., 2001, 66, 4333, A. Inoue, K. Kitagawa, H. Shinokubo, K. Oshima, Tetrahedron 2000, 56, 9601).

So include mixtures of Grignard or dialkylmagnesium compounds and lithium chloride LiCl as a highly potent reagent for halogen / metal exchange reactions disclosed. By reacting these mixtures with, for example Aryl halides are accessible to novel organomagnesium compounds, the above other methods are difficult or impossible to represent (P. Knochel et al., EP-A-04008081; P. Knochel et al., EP-A-1582524; P. Knochel et al., Angew. Chem. Int. Ed. 2003, 42, 4302; A. Krasovskiy et al., Angew. Chem. Int. Ed. 2004, 43, 3333; P. Knochel et al., Chem. Commun. 2004, 2288; P. Knochel et al., Org. Lett. 2004, 6, 4215; P. Knochel, Chem. Commun. 2005, 543; P. Knochel, Angew. Chem. Int. Ed. 2005 44, 1654; P. Knochel et al., Angew. Chem. Int. Ed. 2005, 44, 3133).

Of the Advantage of using these dialkylmagnesium / LiCl mixtures in Halogen / metal exchange reactions with mixtures of alkylmagnesium halides and lithium chloride is that the conversion rate clearly increased is, non-activated organic compounds can be implemented and also only half must be used on dialkylmagnesium compound, since both alkyl substituents involved in the exchange reaction. By using dialkylmagnesium / LiCl mixtures So can the economy of a halogen / metal exchange reaction be increased significantly. The application of this method, however, continues the availability a diorganomagnesium compound and its mixture with a lithium salt ahead.

The Preparation of diorganomagnesium-containing synthesis agents on the one hand and their mixtures with alkali metal salts, on the other hand but consuming according to the prior art.

The known methods for the preparation of diorganomagnesiumhaltigen Synthesizers are described below.

By transmetalation of diorgano-mercury compounds with magnesium arise diorganomagnesium compounds, as in 1 shown. However, this process requires the preparation and availability of a diorgano-mercury compound. These mercury compounds are also extremely toxic (HC Holtkamp et al., J. Organomet Chem. 1969, 19, 279).

Figure 1: Transmetalation reaction for the preparation of R ₂ Mg compounds:

By reaction of organolithium compounds with organomagnesium halides, diorganomagnesium compounds are formed to form lithium halides, as in 2 (CW Kamienski et al., J. Organomet. Chem., 1967, 8, 542). By using an excess of organolithium compounds or Grignard compounds form mixtures of diorganomagnesium compounds with organolithium or Grignard compounds.

Figure 2: Reaction of Grignard compounds with lithium organyls:

• R = organic fragment, X = halogen, M = alkali metal

These Method sets the availability a corresponding organolithium compound. Lots However, organolithium compounds are in aprotic organic solvents or in ether-containing aprotic organic solvent mixtures either not available or only conditionally stable. By applying the above Diorganomagnesiumhaltige synthesis means are usually in ether-containing solvent mixtures which, in further reactions, the selectivity of a Impair reaction can or even the reactivity of the diorganomagnesium-containing synthesis agent can. In some cases The ether can, depending on the coordination strength by adding higher boiling hydrocarbons be removed completely by distillation. This succeeds, for example in the production of dibutyl (2) magnesium. However, during the Continuously feed hydrocarbon. A production of diorganomagnesium compounds in only one solvent consumes accordingly much solvent and is therefore uneconomical.

A Preparation of, for example, mixtures of di- (2) -butylmagnesium with lithium chloride for use in halogen / metal exchange reactions by reaction of 2-butylmagnesium chloride with 2-butyllithium using technically available dilute solutions of 2-butyllithium (12% in cyclohexane) and 2-butylmagnesium chloride (25% in tetrahydrofuran (THF)) not directly possible, since the lithium chloride formed in the cyclohexane-rich solvent mixture fails and thus no longer to accelerate exchange reactions to disposal stands. If THF is added to this suspension, for example formed lithium chloride in solution, however, they are so extremely diluted Di- (2) -butylmagesium / LiCl mixtures get what an application in exchange reactions uneconomical power. Although it may be a more concentrated solution of 2-butyllithium in For example, cyclohexane can be used directly to the desired Di- (2) -butylmagnesium / LiCl mixtures to get, but these are Concentrates pyrophoric, only conditionally stable and difficult to handle. In the presence of ethers, moreover, even at lower temperatures Ether cleavage observed, resulting in undesirable byproducts and Loss of yield leads.

As in 3 Organomagnesium halides in solution according to W. Schlenk are present in the following equilibrium (Schlenk, W. et al, Berichte 1929, 62, 920, W Schlenk, Berichte 1931, 64, 734):

Figure 3: Schlenk equilibrium:

• 2 RMgX ⇌ R ₂ Mg × MgX ₂
• R ₂ Mg × MgX ₂ ⇌ R ₂ Mg + MgX ₂ ↓
• R = organic fragment, X = halogen

By adding special solvents such as pyridine, crown ether, dioxane, tetramethylethylenediamine (TMEDA) or dimethyl ether (DME), the equilibrium is shifted towards the diorganomagnesium compound. After separation of the precipitated sparingly soluble magnesium halide thus Diorganomagnesiumverbindungen or mixtures thereof with Grignard compounds can be obtained, as in 4 shown:

Figure 4: Diorganomagnesium compound via shift of the Schlenk equilibrium:

• R = organic fragment, X = halogen

It However, it is known that the shift of the balance is strong dependent is of the choice of the solvent, the temperature, the time of exposure of the solvent to the Grignard compound and the concentration of the solution. An almost complete one precipitation of the magnesium halide is difficult. It is therefore technical demanding to obtain reproducibly defined products. moreover this process requires the use of exotic solvents, which are rarely used technically, and which are partially toxic or are carcinogenic.

Diorganomagnesium compounds can also be prepared by reacting magnesium hydride MgH ₂ with alkenes containing activated double bonds, as described in U.S. Pat 5 shown:

Figure 5: Reaction of MgH ₂ with alkenes:

The Yields of diorganomagnesium compounds prepared therefrom Method, are low. In addition, this method requires high pressures and Temperatures. As a result, side reactions take place and the crude product must be cleaned technically consuming.

Another method is described in EP-B-0285374. Reaction of an alkyl halide with a mixture of, for example, lithium and magnesium in hydrocarbons containing from 0.05 to 2 molar equivalents of a Lewis base per mole of organometallic compound results in mixtures of organolithium and diorganomagnesium compounds as described in US Pat 6 shown.

Figure 6: Mixtures of lithium organyls and diorganomagnesium compounds:

• R = organic fragment, X = halogen x> 2, y = 1

This Process has the disadvantage that in mixtures of hydrocarbons and Lewis bases, for example THF. The product So it is in a solvent mixture in front. This often has a detrimental effect in synthetic chemistry, because, for example, changed selectivities or reactivities to be obtained. In addition, it is known that under or over a defined amount of Lewis base worse yields, for example due to side reactions such as ether cleavage. by virtue of the higher one Reactivity of lithium in comparison to magnesium accumulates mainly Start of the reaction an organolithium compound in the reaction mixture at. However, it is known that many organolithium compounds, such as sec-butyllithium, in solvents, the Lewis bases contain only limited stability and react with the Lewis base. Thereby arise unwanted By-products and the yield decreases accordingly. The method is therefore only conditionally applicable.

In addition, will by this method due to the poor solubility of lithium salts in solvents, containing only small amounts of Lewis base, only low-lithium or -free diorganomagnesium-containing synthesis agents obtained for use in, for example, halogen / metal exchange reactions are not suitable.

Another method is disclosed in US-A-5171467. Again, the reaction takes place in solvent mixtures of hydrocarbons and ethers. The procedure is based on 7 exemplified.

Figure 7: Preparation of diorganomagnesium compounds via magnesium halides:

As the synthesis results intermediately in an organolithium compound, the following reacted with magnesium chloride. In the synthesis must therefore anhydrous Magnesium chloride can be used to partial hydrolysis of to prevent organo-lithium compound, resulting in a loss of yield to lead would. Anhydrous magnesium chloride must be technically elaborated in situ be dried or at high temperatures for a long time. Both have a detrimental effect on the economics of this method out. A pure Diorganomagnesiumverbindung can also only when using a surplus be obtained on dry magnesium halide. Become magnesium halides in stoichiometric Used quantities, forms a mixture of a Diorganomagnesiumverbindung and a lithium organyl.

As already described above, it is known that many lithium organyls in ether-containing solvent mixtures are only partially stable due to ether cleavage. There are side reactions instead of being too unwanted By-products and inferior yields lead. The procedure is therefore only conditionally applicable. Magnesium chloride is in mixtures of hydrocarbons and ethers are difficultly soluble, resulting in a slower reaction of the organolithium compound with magnesium chloride. Long reaction times are needed which favors side reactions, such as ether cleavage. In addition, according to this method also only low-lithium or -free diorganomagnesium-containing synthesis agents obtained as described are limited.

In addition to these methods, there are other, but are suitable only for the synthesis of specific organomagnesium compounds. A direct production of organomagnesium compounds from magnesium and organic halides is possible only in rare cases. For example, in the case of di- (2) -butylmagnesium, butylethylmagnesium, butyloctylmagnesium, n-butyl-sec-butylmagnesium, this is possible. However, the preparation of these compounds is only to be carried out under energetically very unfavorable conditions. Thus, the alkyl halides used for synthesis must be partially metered under high pressure to the boiling suspension of solvent and finest magnesium powder. Since side reactions also take place at the very high reaction temperatures, gaseous alkenes from β-N elimination reactions are also always released into the environment. Thus, it is known that in the synthesis of dibutylmagnesium larger amounts of butene are formed. It is also known that the dialkylmagnesium compounds prepared in this way sometimes have a low solubility in the solvent used. Therefore, whenever possible, octyl chloride must always be added to form octyl-containing dialkylmagnesium compounds. In this way, on the one hand, the solubility of the compound is increased, on the other hand, no defined product can be produced in this way. It is also known that solutions of the dialkylmagnesium compounds thus prepared by the formation of coordination polymers, always have a very high viscosity, so that in principle aids such as aluminum alkyls must be added to reduce the viscosity. However, this significantly affects the purity. In addition, due to the in 8th slow oxidative addition of both necessary equivalents of alkyl halide to magnesium requires long reaction times (Magnesium alkyls from Akzo Nobel, 1999: Metal alkyls from Akzo Nobel, 2003; M. de Vries, Stamicarbon NV 1969, US-A-3737393; GW Knight, L. Jackson, DE Mach, Dow Chemical Comp. 1975, US-A-4213880; SiOR ₄ Addition: Akzo Nobel 1997, WO-A-99/09035; GaR3, InR3, RLi: LW Fannin, DB Malpass , R. Sanchez, Texas Alkyls 1980, US-A-4299781, CW Kamiensky, BJ McElroy, RO Bach, Lithium Corp. of America 1976 US-A-4069267, LW Fannin, DB Malpass, Texas Alkyls 1977, US-A 4127507, DB Malpass, DW Webb, Texas Alkyls 1984, US-A-4547477).

Figure 8: Synthesis of R ₂ Mg compounds from magnesium and organic halides exemplified by di- (2) -butylmagnesium:

Mixtures of diorganomagnesium compounds and alkali metal organyls are prepared according to 9 by reacting diorganomagnesium compounds with alkali metals (DB Malpass, JF Eastham, J. Org. Chem. 1973, 21, 3718).

Figure 9: Blends from diorganomagnesium compounds and alkali metal organyls:

• 3R ₂ Mg + 2M → 2R ₃ MgM + Mg 2R ₂ Mg + 2RM
• 5 (sec-Bu) ₂ Mg + 6Li → 2 (sec-Bu) ₃ MgLi ₅ + 3Mg ≡ 2 (sec-Bu) ₂ Mg + 6 ec-BuLi
• R = organic fragment, M = alkali metal

This However, method sets the availability preceded by a diorganomagnesium compound. As shown, designed the preparation of these compounds by methods of the prior art However, the technique is difficult.

The Speed of halogen / metal exchange reactions may be due Use of, for example, mixtures of Grignard compounds or diorganomagnesium compounds with lithium salts are drastically increased. By adding lithium salts to the compounds described above can Reagents are produced by other methods due to from side reactions or long reaction times technically not or difficult to represent. In all depictions described above of diorganomagnesium compounds other than lithium organyls or lithium metal, therefore, must in a further process step a lithium salt, for example, lithium chloride may be added. Due to the poor solubility the lithium salt in the solvent or solvent mixture used must partially in addition a solvent exchange respectively.

Become organomagnesium compounds via lithium organyls or under Made using lithium metal, a lithium salt is formed in situ. However, because of the feasibility in the described methods methods, lack of stability or lack of solubility of the resulting lithium organyl in hydrocarbons or in Ether / hydrocarbon mixtures must be worked, falls greater Part of the lithium salt formed. By adding polar solvents while this may be back in solution be brought, however, thereby arise dilute solutions, their use in the Synthetic chemistry is uneconomical. To still lithiumsalzhaltige To obtain mixtures is also here in a further process step a solvent exchange necessary. In addition, partly the availability and stability assuming an organolithium compound.

lithium chloride is very hygroscopic, which is a subsequent introduction into organomagnesium compounds difficult. Will be hydrated or slightly moist lithium chloride used, so finds a partial hydrolysis of organomagnesium Connections take place. This creates unwanted by-products and the Yield of organomagnesium compounds is reduced corresponding.

All listed Process for the preparation of diorganomagnesium-containing synthesis agents or their mixtures with alkali metal salts are either expensive, require the handling of pyrophoric or even toxic compounds, go from partly non-commercially available organometallic Compound or only partially stable organometallic compounds resulting in several process steps, leading to the formation of undesirable By-products or are limited. The task, a technical feasible, efficient, simple and inexpensive Process for the preparation of diorganomagnesium-containing synthesis agents and to show their mixtures with alkali salts, so far unsolved.

task It is therefore the object of the present invention to provide a process for the preparation to provide diorganomagnesium-containing synthesis agents, the overcomes the disadvantages of the prior art.

Especially The object of the present invention is to provide a method the same or differently substituted diorganomagnesiumhaltige Synthesis agent in only one defined solvent or in defined Solvent mixtures, and the directly Alkalisalzhaltige solutions but also Alkalimetallsalzarme or -free solutions of diorganomagnesium-containing synthesis agents in defined solvents or Solvent mixtures supplies.

According to the invention Task surprisingly solved by the features of the main claim. Preferably embodiments can be found in the subclaims.

The inventive method allows surprisingly the preparation of a variety of diorganomagnesium compounds, such as dialkyl, dialkenyl, dialkynyl, diaryl, diheteroaryl, Alkylalkenyl, alkylalkynyl, alkylaryl, alkylheteroaryl, alkenylalkynyl, Alkenylaryl, alkenylheteroaryl, alkynylaryl or alkynylheteroarylmagnesium compounds or mixtures thereof with alkali metal organyls or Grignard compounds or mixtures with alkali metal salts in only one defined solvent or in defined solvent mixtures.

Eben case possible it is with the method according to the invention also directly alkaline salt solutions of diorganomagnesium-containing synthesis agents or alkali metal salt-poor or -free solutions manufacture. The inventively produced diorganomagnesiumhaltige synthesis agent or mixtures thereof with Alkali metal salts can for the production of numerous partially highly functionalized substances, such as pharmaceuticals, natural product derivatives, polymer materials, agrochemicals, specialties and catalysts, for example in halogen / metal exchange reactions or metallation reactions, for example ortho-metallation reactions or transmetallation reactions, for example for the preparation of diorganozinc compounds or organozinc halides.

It has surprisingly been found that by reaction of a Grignard compound RMgX or several Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX, the desired diorganomagnesium-containing synthesis agents or their mixtures with alkali metal salts and additionally highly reactive magnesium are formed directly with alkali metal. The inventive method is characterized by the general reaction formula in 10 explained without limiting the invention thereto.

alkali metal For the purposes of the invention, the pure alkali metal is as well as its Mixtures or alloys with other alkali metals. As alkali metal is preferably lithium or mixtures or alloys of lithium and another alkali metal, preferably sodium. Of the Content of lithium in the mixtures or alloys is between 50 and 99.99 wt .-%, preferably between 80 and 99.99 wt .-%, further preferably between 90 and 99.99% by weight. However, other alkali metals can also be used become.

According to another embodiment of the invention, the process of the invention surprisingly provides a magnesium metal grade which is more reactive than untreated or prior art activated magnesium metal. Highly reactive magnesium in the sense of the present invention means that the magnesium is comparable with respect to its reactivity with ^Rieke® magnesium. The magnesium prepared by the process according to the invention enables the direct preparation of a wide range of diorganomagnesium-containing synthesis agents, such as, for example, dialkyl, dialkenyl, dialkinyl, diaryl, diheteroaryl, alkylalkenyl, alkylalkynyl, alkylaryl, alkylheteroaryl, alkenylalkynyl, Alkenylaryl, alkenylheteroaryl, alkynylaryl or alkynylheteroarymagnesium compounds, alkyl, alkenyl, alkynyl, aryl, heteroaryl-Grignard compounds and / or mixtures thereof with alkali metal salts and / or alkali metal organyls RM.

The process according to the invention is explained in more detail using the example of the formula below (Figure 10):

• R = organic fragment, X = halogen, tosylate or triflate fragment, M = alkali metal
• RMgX = Grignard compound or mixture of x * R ¹ MgX, y * R ² MgX and z * R ³ MgX Grignard compounds, where x + y + z = p and x and y and z are independently selected between 0 and p

How out 10 , is found in situ highly reactive magnesium is formed. Highly reactive magnesium is required for the preparation of special Grignard compounds that can not be prepared by oxidative addition of technically available magnesium grades to organic halides (Fürstner, Active Metals, VCH, Weinheim, New York, 1996, and citations therein). Highly reactive magnesium can, for example, Rieke by reduction of anhydrous magnesium salts by alkali metals in the presence of egg electron carrier, for example naphthalene, according to 11 can be generated: Figure 11: Rieke ^® Magnesium:

The high reactivity from Rieke®Magnesium is explained by that it is characterized by in situ formation in finely divided form with typical Particle sizes between 1 and 2 μm up to the nanometer range and that in the reaction an additional alkali metal salts Activation effect.

The process according to the invention is generally carried out as follows:
According to the invention, the alkali metal is initially charged in solid form or as a suspension in an aprotic organic solvent or solvent mixture. By adding a Grignard compound RMgX - or several Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - arise the corresponding diorganomagnesiumhaltigen synthesis agent or mixtures thereof with alkali metal salts. Compounds of the general formula RMgX, R ¹ MgX, R ² MgX and R ³ MgX are preferably added dissolved in an aprotic organic solvent or solvent mixture, more preferably in the solvent or solvent mixture in which the alkali metal is suspended.

In a further embodiment according to the invention, a Grignard compound RMgX or several Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX is initially charged in an aprotic organic solvent or solvent mixture and the alkali metal is added as solid or suspension in an aprotic organic solvent or solvent mixture. If the alkali metal is added as a suspension, it is preferable to use the solvent or the solvent mixture in which the compounds of the general formula RMgX, R ¹ MgX, R ² MgX and R ³ MgX are dissolved or suspended.

For the preparation of diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, the molar ratio of the amount of a Grignard compound RMgX - or the molar ratio of the total amount of several Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - to the total amount of alkali metal p / n, where p and n are independently selected from a range between 0.1 and 10, preferably between 0.5 and 6.

In one for the preparation of mixtures of diorganomagnesium compounds and Grignard compounds and mixtures thereof with alkali metal salts preferred embodiment is n ≤ p and in one for preparing mixtures of diorganomagnesium compounds and alkali metal organyls and mixtures thereof with alkali metal salts preferred embodiment is n ≥ p.

In an embodiment preferred for the preparation of diorganomagnesium compounds and their mixtures with alkali metal salts according to the invention, the molar ratio of the total amount of Grignard compounds RMgX, R ¹ MgX, R ² MgX and R ³ MgX and the total amount of alkali metal is between 1: 0.7 and 1: 2 , particularly preferred is a ratio of 1: 0.8 to 1: 1.5.

In a preferred embodiment for the preparation of highly reactive magnesium is the molar ratio the total amount of Grignard compounds RMgX and the amount of alkali metal between 1.0: 1 and 6: 1, more preferably a ratio of 1.1: 1 to 4: 1.

In a preferred according to the invention embodiment for the preparation of similarly substituted diorganomagnesiumhaltigen Synthesizers and their mixtures with alkali metal salts a compound of the general formula RMgX used.

In a preferred embodiment for producing differently substituted diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, x.R ¹ MgX, y.R ² MgX and z.R ³ MgX Grignard compounds are used, where x + y + z = p and x, y and z are independently selected from the range between 0 and p.

In a further embodiment of the invention, the reaction suspension - obtained by reaction of Grignard compounds RMgX with alkali metal - an organic halide RX - or several organic halides R ¹ X, R ² X and R ³ X - fed. This results in Grignard compounds of the general composition RMgX - or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - or their mixture with an alkali metal salt. These can be used according to the invention for the preparation of diorganomagnesium-containing synthesis agents or mixtures of diorganomagnesium-containing synthesis agents with alkali metal salts. As a result, concentrated product solutions are obtained, which increases the space-time yield and minimizes the amount of waste products produced. This process according to 12 is repeated several times in a further preferred embodiment, preferably it is repeated 1 to 20 times.

In a further preferred embodiment of the invention, the reaction residue - formed by reaction of Grignard compounds RMgX with alkali metal - separated and immediately after the reaction or after drying, or after washing and drying in an aprotic solvent or solvent mixture or suspended in a solution of one or more Grignard and used by adding organic halides RX for the synthesis of Grignard compounds of the general composition RMgX. The solution thus prepared can in turn be used according to the invention for the synthesis of diorganomagnesium-containing synthesis agents or mixtures thereof with alkali metal salts. This creates a cycle according to 12 which minimizes the accumulation of waste.

Diorganomesium-containing synthesis agents in the context of the invention are diorganomagnesium compounds R ₂ Mg or R _x ¹ R _y ² Mg and mixtures thereof with z Grignard compounds RMgX or R ³ MgX or z alkali metal organyls RM or R ³ M. The molar mixing ratio with Grignard compounds or alkali metal organyls z is in the range between 0 and 100, preferably between 0 and 4. The coefficients x and y result in the sum of 2 and lie independently in the range between 0 and 2. R, R ¹ , R ² and R ³ are independently selected and defined as below.

ever after used solvent or solvent mixture are mixtures of diorganomagnesium-containing synthesis agents and alkali salt halides which are in the ratio of Alkaline salt and organomagnesium compound differ.

lithium or lithium-containing mixtures or alloys are preferred used in the form of metal powder, metal dispersion or metal granules, particularly preferably in the form of metal powder or metal dispersion.

Prefers Grignard compounds RMgX become a suspension of the alkali metal dosed in an aprotic organic solvent.

organic Halides RX are preferred to a suspension of highly reactive Magnesium in an aprotic organic solvent or solvent mixture dosed, wherein the suspension also inventively diorganomagnesiumhaltige Synthesizers or Grignard compounds may contain.

to Synthesis of diorganomagnesium-containing synthesis agents and their Mixtures with alkali metal salts in solvent mixtures of ethers and hydrocarbons are used in another embodiment one or more different Grignard compounds RMgX in ethers or preferably used in mixtures of ethers and hydrocarbons. Furthermore, the alkali metal is preferably in an aromatic or aliphatic hydrocarbon suspended. The used ethers after implementation by methods of the prior art be removed, for example by distillation at atmospheric pressure, at reduced pressure, by vacuum distillation or by evaporation. Thus arise alkali metal salt-poor or -free solutions of diorganomagnesiumhaltigen Synthesis means.

to Synthesis of diorganomagnesium containing alkali metal salt Synthetic agents, for example for use in halogen / metal exchange reactions or metallation reactions, in a preferred embodiment ethereal solvents used, preferably cyclic ethers, more preferably THF and 2-methyl-THF.

Prefers becomes the process for the production of diorganomagnesiumhaltigen Synthesizers performed in the absence of air and moisture, preferably in an inert gas atmosphere, particularly preferably in a nitrogen or argon atmosphere.

The inventive method can at temperatures between -100 ° C and the boiling point of Reaction suspension are carried out, is preferably carried out in a temperature range between -15 ° C and the boiling point of the reaction suspension, more preferably between 0 ° C and 60 ° C.

The Diorganomagnesiumhaltige invention Synthesis agent is formed in addition to solids, which in a preferred embodiment be separated by methods of the prior art. Methods of State of the art, for example, decantation, filtration or centrifugation. The resulting solutions of diorganomagnesiumhaltigen Synthesizers are depending on the solvent or solvent mixture alkali metal salt-free or -containing and can be directly in the organic or organometallic synthetic chemistry.

• – R, R¹, R² und R³ können gleich oder unterschiedlich ausgewählt sein aus H, gesättigten, ungesättigten, verzweigten, unverzweigten, funktionalisierten, unfunktionalisierten, aliphatischen, cyclischen, heterozyklischen oder aromatischen organischen Fragmenten ausgewählt, R, R¹, R² und R³ können gleich oder unterschiedlich ausgewählt sein aus H, gesättigten, ungesättigten, verzweigten, unverzweigten, funktionalisierten, unfunktionalisierten, aliphatischen, cyclischen, heterozyklischen oder aromatischen organischen Fragmenten, bevorzugt Fragmenten mit 1 bis 80, besonders bevorzugt mit 1 bis 40, ganz besonders bevorzugt mit 1 bis 20 Kohlenstoffatomen, und
• – R verallgemeinernd auch für R¹, R² und R³ stehen kann, und
• – X ausgewählt ist aus Chlor, Brom, Iod, Tosylat oder Triflat, bevorzugt aus Chlor, Brom und Iod, und
• – M ein Alkalimetall ist.

In the Grignard compounds of the general composition RMgX, R ¹ MgX, R ² MgX and R ³ MgX and the organic halides RX, R ¹ X, R ² X and R ³ X and the Diorganomagnesiumverbindindungen R ₂ Mg and R _x ¹ R _y ² Mg and mixtures thereof with alkali metal organyls RM and R ³ M or Grignard compounds RMgX and R ³ MgX:

• R, R ¹ , R ² and R ³ may be the same or different selected from H, saturated, unsaturated, branched, unbranched, functionalized, unfunctionalized, aliphatic, cyclic, heterocyclic or aromatic organic fragments, R, R ¹ , R ² and R ³ may be the same or different selected from H, saturated, unsaturated, branched, unbranched, functionalized, unfunctionalized, aliphatic, cyclic, heterocyclic or aromatic organic fragments, preferably fragments of 1 to 80, particularly preferably 1 to 40, especially preferably having 1 to 20 carbon atoms, and
• - R can be generalized for R ¹ , R ² and R ³ , and
• X is selected from chlorine, bromine, iodine, tosylate or triflate, preferably from chlorine, bromine and iodine, and
• - M is an alkali metal.

In particular, R, R ¹ , R ² and R ^{3 may be the} same or different selected from methyl, ethyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl and heteroaryl fragments and branched and unbranched propyl, butyl, pentyl , Hexyl, heptyl, octyl fragments.

When aprotic, organic solvents preferred are aliphatic or aromatic hydrocarbons, Heterocycles, ethers, amines, nitriles or mixtures thereof.

Under The term aliphatic hydrocarbons fall within the meaning of Invention cyclic, saturated, unsaturated, branched and unbranched hydrocarbons. To be favoured saturated or cyclic, branched or unbranched hydrocarbons with 5 to 20 carbon atoms, particularly preferably n-pentane, n-hexane, n-heptane, n-octane or their isomers, cyclopentane, cyclohexane and methylcyclohexane.

Under For the purposes of the invention, the term ethers covers acyclic, cyclic, saturated, unsaturated, branched, unbranched, similarly substituted and differently substituted Ether having at least one oxygen atom, preferably one to four oxygen atoms. Further preferred as ethers are dimethyl ether, Diethyl ether, dibutyl ether, dimethoxyethane, diethoxymethane, polyethylene glycol, Methyl tert-butyl ether, cyclopentyl methyl ether, dioxane, tetrahydrofuran and 2-methyltetrahydrofuran, and particularly preferable are THF and 2-methyl-THF.

Under The term amines fall within the meaning of the invention acyclic, cyclic, saturated, unsaturated, branched, unbranched, similarly substituted and differently substituted Amines having at least one nitrogen atom, preferably one to four nitrogen atoms, preferred is N, N-tetramethylethylenediamine.

Under The term aromatic hydrocarbons fall within the meaning of the invention unsubstituted, monosubstituted and polysubstituted aromatic compounds. Preference is given to using benzene, toluene, Etylbenzene, cumene and xylene, and their isomers.

Under Heterocycles are for the purposes of the invention substituted, unsubstituted, aromatic, saturated and unsaturated to understand cyclic compound in the cycle of at least four carbon atoms and at least one atom from the group the heteroatoms oxygen, sulfur and nitrogen are preferred are four to six carbon atoms and one to three heteroatoms, particularly preferred are pyridine, THF and 2-methyltetrahydrofuran.

• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei eine Grignardverbindung RMgX – oder mehrere Grignardverbindungen R¹MgX, R²MgX und R³MgX – und ein Alkalimetall verwendet werden;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei die diorganomagnesiumhaltigen Synthesemittel unmittelbar aus den zugegebenen Reagenzien entstehen;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei das hochreaktive Magnesium unmittelbar aus den zugegebenen Reagenzien entsteht;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei unter Alkalimetall Lithium oder Mischungen oder Legierungen, bestehend aus Lithium und einem anderen Alkalimetall, vorzugsweise Natrium zu verstehen sind, wobei der Anteil an Lithium in den Mischungen oder Legierungen zwischen 50 und 99,99 Gew.-%, bevorzugt zwischen 80 und 99,99 Gew-%, weiterhin bevorzugt zwischen 90 und 99,99 Gew.-% beträgt;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei das Alkalimetall in einem aprotischen organischen Lösemittel oder Lösemittelgemisch vorgelegt wird und eine Grignardverbindung RMgX – oder mehrere Grignardverbindungen R¹MgX, R²MgX und R³MgX – zugegeben werden;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei eine Grignardverbindung RMgX – oder mehrere Grignardverbindungen R¹MgX, R²MgX und R³MgX – in einem aprotischen organischen Lösemittel oder Lösemittelgemisch vorgelegt werden und das Alkalimetall als Feststoff oder Suspension in einem aprotischen organischen Lösemittel oder Lösemittelgemisch zugegeben wird;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei Verbindungen der allgemeinen Formel RMgX, R¹MgX, R²MgX und R³MgX bevorzugt gelöst in dem Lösemittel oder Lösemittelgemisch zugegeben werden, in dem das Alkalimetall suspendiert ist;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei das Alkalimetall bevorzugt suspendiert in dem Lösemittel oder Lösemittelgemisch zugegeben wird, in dem Verbindungen der allgemeinen Formel RMgX, R¹MgX, R²MgX und R³MgX gelöst sind;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei das molare Verhältnis der Menge einer Grignardverbindung RMgX – oder das molare Verhältnis der Gesamtmenge mehrerer Grignardverbindungen R¹MgX, R²MgX und R³MgX – zur Gesamtmenge an Alkalimetall p/n ist, wobei p und n unabhängig voneinander gewählt sind aus einem Bereich zwischen 0,1 und 10, bevorzugt zwischen 0,5 und 6;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei n ≤ p, wobei Mischungen aus Diorganomagnesiumverbindungen und Grignardverbindungen oder deren Mischungen mit Alkalimetallsalzen entstehen;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei n ≥ p, wobei Mischungen aus Diorganomagnesiumverbindungen und Alkalimetallorganylen oder deren Mischungen mit Alkalimetallsalzen entstehen;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei zur Herstellung von Diorganomagnesiumverbindungen und deren Mischungen mit Alkalimetallsalzen das molare Verhältnis der Gesamtmenge an Grignardverbindungen RMgX, R¹MgX, R²MgX und R³MgX und der Gesamtmenge an Alkalimetall zwischen 1 : 0,7 und 1 : 2 ist, besonders bevorzugt von 1 : 0,8 bis 1 : 1,5;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium, wobei das molare Verhältnis der Gesamtmenge an Grignardverbindungen R¹MgX, R²MgX, R³MgX und der Menge an Alkalimetall von 1,0 : 1 bis 6 : 1, besonders bevorzugt von 1,1 : 1 bis 4 : 1 beträgt;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei zur Herstellung von gleichartig substituierten diorganomagnesiumhaltigen Synthesemitteln eine Verbindung der allgemeinen Formel RMgX verwendet wird;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei zur Herstellung von unterschiedlich substituierten diorganomagnesiumhaltigen Synthesemitteln x·R¹MgX, y·R²MgX und z·R³MgX Grignardverbindungen verwendet werden, wobei x + y + z = p und x, y und z unabhängig voneinander aus dem Bereich zwischen 0 und p gewählt sind;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei das Alkalimetall in Form von Metallpulver, Metalldispersion oder Metallgranulat verwendet wird, bevorzugt in Form von Metallpulver oder Metalldispersion;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei Grignardverbindungen bevorzugt zu einer Suspension des Alkalimetalls in einem aprotischen organischen Lösemittel dosiert werden;
• – ein Verfahren zur Herstellung von Grignardverbindungen oder diorganomagnesiumhaltigen Synthesemitteln aus erfindungsgemäß hergestelltem hochreaktiven Magnesium, wobei die organischen Halogenide RX bevorzugt zu einer Suspension des hochreaktiven Magnesiums in einem aprotischen organischen Lösemittel oder Lösemittelgemisch dosiert werden und wobei die Suspension auch erfindungsgemäß hergestellte diorganomagensiumhaltige Synthesemittel und/oder Grignardverbindungen enthalten kann;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei der Reaktionssuspension – erhalten durch Umsetzung von Grignardverbindungen RMgX mit Alkalimetall – ein organisches Halogenid RX – oder mehrere organische Halogenide R¹X, R²X und R³X – zugeführt werden, wobei Grignardverbindungen der allgemeinen Zusammensetzung RMgX – oder mehrere Grignardverbindungen R¹MgX, R²MgX und R³MgX – oder deren Mischung mit einem Alkalimetallsalz entstehen, wobei diese Mischungen in einem erfindungsgemäßen Verfahren zur Herstellung von diorganomagnesiumhaltigen Synthesemitteln oder deren Mischungen mit Alkalimetallsalzen verwendet werden können und dieser Vorgang mehrmals, bevorzugt 1 bis 20 mal wiederholt wird;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei der Reaktionsrückstand abgetrennt und unmittelbar nach der Umsetzung oder nach Trocknung, oder nach Waschung und Trocknung in einem aprotischen Lösemittel oder Lösemittelgemisch oder in einer Lösung einer oder mehrerer Grignardverbindungen suspendiert wird und durch Zugabe organischer Halogenide RX zur Synthese von Grignardverbindungen der allgemeinen
• Zusammensetzung RMgX verwendet wird, wobei die so dargestellte Lösung wiederum erfindungsgemäß zur Synthese von diorganomagensiumhaltigen Synthesemitteln oder deren Mischungen mit Alkalimetallsalzen eingesetzt werden kann;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen in Lösemittelgemischen aus Ethern und Kohlenwasserstoffen, wobei zur Synthese eine oder mehrere verschiedene Grignardverbindungen RMgX in Ethern oder bevorzugt in Gemischen aus Ethern und Kohlenwasserstoffen verwendet werden und wobei das Alkalimetall bevorzugt in einem aromatischen oder aliphatischen Kohlenwasserstoff, suspendiert vorgelegt wird, und wobei die verwendeten Ether nach erfolgter Umsetzung durch Methoden des Standes der Technik entfernt werden können, beispielsweise durch Destillation bei Normaldruck, bei Unterdruck, durch Vakuumdestillation oder durch Eindampfung, und wobei alkalimetallsalzarme oder -freie Lösungen von magnesiumorganischen Verbindungen entstehen;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei zur Herstellung von alkalimetallsalzhaltigen diorganomagnesiumhaltigen Synthesemitteln, beispielsweise zur Anwendung in Halogen/Metallaustauschreaktionen oder Metallierungsreaktionen, etherische Lösemittel eingesetzt werden, wobei bevorzugt cyclische Ether und besonders bevorzugt THF und 2-Methyl-THF eingesetzt werden;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei die Verfahren unter Ausschluss von Luft und Feuchtigkeit, bevorzugt in einer Inertgasatmosphäre, besonders bevorzugt in einer Stickstoff- oder Argonatmosphäre, durchgeführt werden;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei das erfindungsgemäße Verfahren bei Temperaturen zwischen –100°C und dem Siedepunkt der Reaktionssuspension durchgeführt werden, bevorzugt bei Temperaturen zwischen –15°C und dem Siedepunkt der Reaktionssuspension, besonders bevorzugt zwischen 0°C und 60°C;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei die entsprechenden diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalimetallsalzen von ausgefallenen Feststoffen durch Methoden des Standes der Technik, bevorzugt Dekantation, Filtration oder Zentrifugation, abgetrennt werden;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei R, R¹, R² und R³ für alle Fälle unabhängig voneinander aus H, gesättigten, ungesättigten, verzweigten, unverzweigten, funktionalisierten, unfunktionalisierten, aliphatischen, cyclischen, heterozyklischen oder aromatischen organischen Fragmenten ausgewählt, wobei gesättigte, ungesättigte, verzweigte, unverzweigte, funktionalisierte, unfunktionalisierte, aliphatische, cyclische, heterozyklische oder aromatische organische Fragmente mit 1 bis 80 Kohlenstoffatomen bevorzugt sind, wobei insbesondere gesättigte, ungesättigte, verzweigte, unverzweigte, funktionalisierte, unfunktionalisierte, aliphatische, cyclische, heterozyklische oder aromatische organische Fragmente mit 1 bis 40 Kohlenstoffatomen bevorzugt sind, wobei gesättigte, ungesättigte, verzweigte, unverzweigte, funktionalisierte, unfunktionalisierte, aliphatische, cyclische, heterozyklische oder aromatische organische Fragmente mit 1 bis 20 Kohlenstoffatomen besonders bevorzugt sind und wobei verzweigte und unverzweigte Methyl-, Ethyl-, Propyl-, Butyl-, Pentyl-, Hexyl-, Heptyl-, Octyl-, Cyclopropyl, Cyclopentyl, Cyclohexyl, Phenyl, Benzyl und Heteroaryl-Fragmente besonders bevorzugt sind, und X gewählt ist aus Chlor, Brom, Iod, Tosylat oder Triflat, bevorzugt aus Chlor, Brom und Iod;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei aprotische, organische Lösemittel verwendet werden;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei aliphatische oder aromatische Kohlenwasserstoffe, Heterozyklen, Ether, Amine, Nitrile oder Mischungen daraus verwendet werden;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei als aliphatische Kohlenwasserstoffe cyclische, gesättigte, ungesättigte, verzweigte und unverzweigte Kohlenwasserstoffe, bevorzugt gesättigte oder cyclische, verzweigte oder unverzweigte Kohlenwasserstoffe mit 5–20 Kohlenstoffatomen eingesetzt werden, besonders bevorzugt n-Pentan, n-Hexan, n-Heptan, n-Octan oder deren Isomere, Cyclopentan, Cyclohexan und Methylcyclohexan;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei, als Ether cyclische, gesättigte, ungesättigte, verzweigte, unverzweigte, gleichartig substituierte und unterschiedlich substituierte Ether mit mindestens einem Sauerstoffatom eingesetzt werden, bevorzugt mit einem bis vier Sauerstoffatomen, besonders bevorzugt Dimethylether, Diethylether, Dibutylether, Dimethoxyethan, Diethoxymethan, Methyl-tert-butylether, Polyethylenglykol, Cyclopentylmethylether, Dioxan, Tetrahydrofuran und 2-Methyltetrahydrofuran;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei als Amine cyclische, aliphatische, gesättigte, ungesättigte, verzweigte, unverzweigte, gleichartig substituierte und unterschiedlich substituierte Amine mit mindestens einem Stickstoffatom, bevorzugt mit einem bis vier Stickstoffatomen, eingesetzt werden, besonders bevorzugt ist N,N-Tetramethylethylendiamin;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei als aromatische Kohlenwasserstoffe unsubstituierte, einfach substituierte und mehrfach substituierte aromatische Verbindungen eingesetzt werden, bevorzugt Benzol, Toluol, Ethylbenzol, Cumol und/oder Xylole oder deren Isomere;
• – ein Verfahren zur Herstellung von hochreaktivem Magnesium und diorganomagnesiumhaltigen Synthesemitteln und deren Mischungen mit Alkalimetallsalzen, wobei als Heterozyklen substituierte, unsubstituierte, aromatische, gesättigte und ungesättigte cyclische Verbindung eingesetzt werden, die im Zyklus aus mindestens vier Kohlenstoffatomen, bevorzugt vier bis sechs Kohlenstoffatome, und mindestens einem Atom; bevorzugt ein bis drei Atome, aus der Gruppe der Heteroatome Sauerstoff, Schwefel und Stickstoff bestehen, wobei besonders bevorzugt sind THF, 2-Methyl-THF und Pyridin;
• – ein Verfahren zur Herstellung von gleichartig oder unterschiedlich substituierten Dialkyl-, Dialkenyl-, Dialkinyl-, Diaryl-, Diheteroaryl-, Alkylalkenyl-, Alkylalkinyl-, Alkylaryl-, Alkylheteroaryl-, Alkenylalkinyl-, Alkenylaryl-, Alkenylheteroaryl-, Alkinylaryl- oder Alkinylheteroarymagnesiumverbindungen oder deren Mischungen mit Alkalisalzen, Grignardverbindungen RMgX oder lithiumorganischen Verbindungen RLi;
• – ein Verfahren zur Herstellung von gleichartig oder unterschiedlich substituierten Di-n-Alkyl-, Di-sec-Alkyl-, Di-iso-Alkyl-, Di-tert-Alkyl-, Di-cycloalkyl-, Di-aryl- und Di heteroaryl-magnesiumverbindungen oder deren Mischungen mit Alkalisalzen, Grignardverbindungen RMgX oder lithiumorganischen Verbindungen RLi;
• – ein Verfahren zur Herstellung von Dimethylmagnesium, Diethylmagnesium, Di-iso-propylmagnesium, Di-n-propylmagnesium, Di-n-Butylmagnesium, Di-secbutylmagnesium, Di-iso-Butylmagnesium, Di-tert-Butylmagnesium, Di-cyclo-propylmagnesium, Di-cyclo-pentylmagnesium, Di-cyclo-hexylmagnesium, Di-n-pentylmagnesium, Di-n-hexylmagnesium, Diphenylmagnesium, Dibenzylmagnesium, n-Butyl-n-ocytlmagnesium, n-Butyl-ethylmagnesium, s-Butyl-ethylmagnesium oder s-Butyl-n-Butylmagnesium oder deren Mischungen mit Alkalisalzen, Grignardverbindungen RMgX oder lithiumorganischen Verbindungen RLi;
• – die Verwendung der erfindungsgemäß hergestellten diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalisalzen in der Synthesechemie;
• – die Verwendung der erfindungsgemäß hergestellten diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalisalzen in der organischen Chemie und metallorganischen Chemie;
• – die Verwendung der erfindungsgemäß hergestellten diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalisalzen in Halogen/Metall-Austauschreaktionen;
• – die Verwendung der erfindungsgemäß hergestellten diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalisalzen in Metallierungsreaktionen, bevorzugt in ortho-Metallierungsreaktionen;
• – die Verwendung der erfindungsgemäß hergestellten diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalisalzen in Transmetallierungsreaktionen;
• – die Verwendung der erfindungsgemäß hergestellten diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalisalzen zur Herstellung von Organozinkhalogeniden oder Diorganozinkverbindungen;
• – die Verwendung der erfindungsgemäß hergestellten diorganomagnesiumhaltigen Synthesemittel und deren Mischungen mit Alkalisalzen zur Herstellung von Magnesiumalkoholaten und Magnesiumhalogeniden;
• – die Verwendung von erfindungsgemäß hergestelltem hochreaktiven Magnesium in der Synthesechemie;
• – die Verwendung von erfindungsgemäß hergestelltem hochreaktiven Magnesium in der organischen Chemie und metallorganischen Chemie;
• – die Verwendung von erfindungsgemäß hergestelltem hochreaktiven Magnesium zur Herstellung von Grignardverbindungen der allgemeinen Zusammensetzung RMgX;
• – die Verwendung von erfindungsgemäß hergestelltem hochreaktiven Magnesium zur Herstellung von Diorganomagnesiumverbindungen R¹R²Mg;
• – die Verwendung von erfindungsgemäß hergestelltem hochreaktiven Magnesium zur Synthese von Magnesiumhydrid MgH₂;
• – die Verwendung von erfindungsgemäß hergestelltem hochreaktiven Magnesium zur Herstellung von gleichartig oder unterschiedlich substituierten Dialkyl-, Dialkenyl-, Dialkinyl-, Diaryl-, Diheteroaryl-, Alkylalkenyl-, Alkylalkinyl-, Alkylaryl-, Alkylheteroaryl-, Alkenylalkinyl-, Alkenylaryl-, Alkenylheteroaryl, Alkinylaryl- oder Alkinylheteroarymagnesiumverbindungen, Alkyl-, Alkenyl-, Alkinyl-, Aryl-, Heteroaryl-Grignardverbindungen RMgX oder deren Mischungen mit Alkalisalzen;
• – hochreaktives Magnesium erhältlich aus Alkalimetallen und Grignardverbindungen RMgX;
• – eine Diorganomagnesiumverbindung R_x ¹R_y ²Mg als Lösung in einem etherhaltigen Lösemittel, wobei sie im Gemisch mit Lithiumhalogeniden und/oder Grignardverbidnungen RMgX und/oder Alkalimetallorganylen RM vorliegt und das Molverhältnis von Diorganomagnesiumverbindungen und Lithiumhalogenid zwischen 1 : 0,1 bis 1 : 2 beträgt und das molare Mischungsverhältnis von Diorganomagnesiumverbindung und Grignardverbindung bzw. Alkalimetallorganyl zwischen 1 : 0,15 und 1 : 4 beträgt und die Summe x + y = 2 ist und x und y unabhängig voneinander aus dem Bereich zwischen 0 und 2 gewählt sind;
• – eine Lösung von Diorganomagnesiumverbindungen R_x ¹R_y ²Mg und Lithiumhalogeniden, ausgewählt aus der Gruppe Lithiumchlorid, Lithiumbromid und Lithiumiodid, in einem tetrahydrofuran- oder 2-methyltetrahydrofuranhaltigen Lösemittel, und deren Mischungen mit Grignardverbindungen RMgX oder Alkalimetallorganylen RM, wobei R, R¹ und R² unabhängig voneinander aus sekundären Alkylgruppen gewählt ist, bevorzugt sec-butyl, iso-propyl, cyclopropyl, cyclopentyl, cyclohexyl und das Molverhältnis von R_x ¹R_Y ²Mg und dem Lithiumhalogenid im Bereich zwischen 1 : 0,1 und 1 : 2 liegt und das molare Mischungsverhältnis von Diorganomagnesiumverbindung und Grignardverbindung bzw. Alkalimetallorganyl zwischen 1 : 0,15 und 1 : 4 beträgt und die Summe x + y = 2 ist und x und y unabhängig voneinander aus dem Bereich zwischen 0 und 2 gewählt sind;
• – eine Lösung von Diorganomagnesiumverbindungen R_x ¹R_y ²Mg und Lithiumhalogeniden, ausgewählt aus der Gruppe Lithiumchlorid, Lithiumbromid und Lithiumiodid, in einem tetrahydrofuran- oder 2-methyltetrahydrofuranhaltigen Lösemittel, und deren Mischungen mit Grignardverbindungen RMgX oder Alkalimetallorganylen RM, wobei R, R¹ und R² unabhängig voneinander gewählt aus methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl und das Molverhältnis von R_x ¹R_y ²Mg und dem Lithiumhalogenid im Bereich zwischen 1 : 0,1 und 1 : 2 liegt und das molare Mischungsverhältnis von Diorganomagnesiumverbindung und Grignardverbindung bzw. Alkalimetallorganyl zwischen 1 : 0,15 und 1 : 4 beträgt und die Summe x + y = 2 ist und x und y unabhängig voneinander aus dem Bereich zwischen 0 und 2 gewählt sind;
• – eine Lösung von Diorganomagnesiumverbindungen R_x ¹R_y ²Mg und Lithiumhalogeniden, ausgewählt aus der Gruppe Lithiumchlorid, Lithiumbromid und Lithiumiodid, in Tetrahydrofuran oder 2-Methyltetrahydrofuran und deren Mischungen mit Grignardverbindungen RMgX oder Alkalimetallorganylen RM, wobei R, R¹ und R² unabhängig voneinander gewählt aus methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl und das Molverhältnis von x_x ¹R_y ²Mg und dem Lithiumhalogenid im Bereich zwischen 1 : 0,1 und 1 : 2 liegt und das molare Mischungsverhältnis von Diorganomagnesiumverbindung und Grignardverbindung bzw. Alkalimetallorganyl zwischen 1 : 0,15 und 1 : 4 beträgt und die Summe x + y = 2 ist und x und y unabhängig voneinander aus dem Bereich zwischen 0 und 2 gewählt sind;
• – eine Lösung von Diorganomagnesiumverbindungen R_x ¹R_y ²Mg und Lithiumhalogeniden, ausgewählt aus der Gruppe Lithiumchlorid, Lithiumbromid und Lithiumiodid, in Lösemittelgemischen aus Kohlenwasserstoffen und Ethern und deren Mischungen mit Grignardverbindungen RMgX oder Alkalimetallorganylen RM, wobei R, R¹ und R² unabhängig voneinander gewählt sind aus methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl und das Molverhältnis von R_x ¹R_y ²Mg und dem Lithiumhalogenid im Bereich zwischen 1 : 0,05 und 1 : 2 liegt und das molare Mischungsverhältnis von Diorganomagnesiumverbindung und Grignardverbindung bzw. Alkalimetallorganyl zwischen 1 : 0,05 und 1 : 4 beträgt und die Summe x + y = 2 ist und x und y unabhängig voneinander aus dem Bereich zwischen 0 und 2 gewählt sind und wobei das Molverhältnis von Ether zu Diorganomagnesiumverbindung zwischen 0,02 : 1 und 50 : 1 beträgt;
• – eine Lösung von Diorganomagnesiumverbindungen R_x ¹R_y ²Mg und Lithiumhalogeniden, ausgewählt aus der Gruppe Lithiumchlorid, Lithiumbromid und Lithiumiodid, in in Lösungsmittelgemischen aus Dimethylether, Diethylether, Dibutylether, Methyl-tert-Butylether, Cyclopentylmethylether, Tetrahydrofuran oder 2-Methyltetrahydrofuran und Toluol, Cumol, Xylole, Pentan, Hexan, Heptan, Octan, Cyclohexan oder Methylcyclohexan und deren Mischungen mit Grignardverbindungen RMgX oder Alkalimetallorganylen RM, wobei R, R¹ und R² unabhängig voneinander gewählt sind aus methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl und das Molverhältnis von R_x ¹R_y ²Mg und dem Lithiumhalogenid im Bereich zwischen 1 : 0,05 und 1 : 2 liegt und das molare Mischungsverhältnis von Diorganomagnesiumverbindung und Grignardverbindung bzw. Alkalimetallorganyl zwischen 1 : 0,05 und 1 : 4 beträgt und die Summe x + y = 2 ist und x und y unabhängig voneinander aus dem Bereich zwischen 0 und 2 gewählt sind und wobei das Molverhältnis von Ether zu Diorganomagnesiumverbindung zwischen 0,02 : 1 und 50 : 1 beträgt.

The subject of the invention is in detail:

• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, one Grignard compound RMgX or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX and an alkali metal being used;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, the diorganomagnesium-containing synthesis agents being formed directly from the added reagents;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, the highly reactive magnesium being formed directly from the added reagents;
• - A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein alkali metal lithium or mixtures or alloys consisting of lithium and another alkali metal, preferably sodium are to be understood, wherein the proportion of lithium in the mixtures or alloys between 50 and 99.99% by weight, preferably between 80 and 99.99% by weight, more preferably between 90 and 99.99% by weight;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and mixtures thereof with alkali metal salts, wherein the alkali metal is initially charged in an aprotic organic solvent or solvent mixture and a Grignard compound RMgX or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX added become;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and mixtures thereof with alkali metal salts, wherein a Grignard compound RMgX or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX are presented in an aprotic organic solvent or solvent mixture and the alkali metal as Solid or suspension in an aprotic organic solvent or solvent mixture is added;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, compounds of the general formula RMgX, R ¹ MgX, R ² MgX and R ³ MgX preferably being added dissolved in the solvent or solvent mixture in which the alkali metal is suspended is;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and mixtures thereof with alkali metal salts, wherein the alkali metal is preferably added suspended in the solvent or solvent mixture in which compounds of the general formula RMgX, R ¹ MgX, R ² MgX and R ³ MgX are dissolved are;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein the molar ratio of the amount of a Grignard compound RMgX - or the molar ratio of the total amount of several Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - to the total Alkali metal is p / n, wherein p and n are independently selected from a range between 0.1 and 10, preferably between 0.5 and 6;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, where n ≤ p, resulting in mixtures of diorganomagnesium compounds and Grignard compounds or mixtures thereof with alkali metal salts;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, where n ≥ p, resulting in mixtures of diorganomagnesium compounds and alkali metal organyls or mixtures thereof with alkali metal salts;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein for the preparation of Diorganomagnesiumverbindungen and their mixtures with alkali metal salts, the molar ratio of the total amount of Grignard compounds RMgX, R ¹ MgX, R ² MgX and R ³ MgX and the total of alkali metal is between 1: 0.7 and 1: 2, more preferably from 1: 0.8 to 1: 1.5;
• A process for producing highly reactive magnesium, wherein the molar ratio of the total amount of Grignard compounds R ¹ MgX, R ² MgX, R ³ MgX and the amount of alkali metal is from 1.0: 1 to 6: 1, more preferably from 1.1 : 1 to 4: 1;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, a compound of the general formula RMgX being used for the preparation of similarly substituted diorganomagnesium-containing synthesis agents;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein for the preparation of differently substituted diorganomagnesiumhaltigen synthesis means x · R ¹ MgX, y · R ² MgX and z · R ³ MgX Grignardverbindun where x + y + z = p and x, y and z are independently selected from the range between 0 and p;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein the alkali metal is used in the form of metal powder, metal dispersion or metal granules, preferably in the form of metal powder or metal dispersion;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein Grignard compounds are preferably dosed to a suspension of the alkali metal in an aprotic organic solvent;
• A process for the preparation of Grignard compounds or diorganomagnesium-containing synthesis agents from inventively prepared highly reactive magnesium, wherein the organic halides RX are preferably dosed to a suspension of highly reactive magnesium in an aprotic organic solvent or solvent mixture and wherein the suspension also prepared according to the invention diorganomagensiumhaltige synthesis agent and / or Grignard compounds may contain;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein the reaction suspension obtained by reaction of Grignard compounds RMgX with alkali metal - an organic halide RX - or more organic halides R ¹ X, R ² X and R ³ X - Are supplied, wherein Grignard compounds of the general composition RMgX - or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - or their mixture with an alkali metal salt, these mixtures in a process according to the invention for the preparation of diorganomagnesiumhaltigen synthesis agents or mixtures thereof with Alkali metal salts can be used and this process is repeated several times, preferably 1 to 20 times;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein the reaction residue is separated and suspended immediately after the reaction or after drying, or after washing and drying in an aprotic solvent or solvent mixture or in a solution of one or more Grignard compounds and by addition of organic halides RX for the synthesis of Grignard compounds of the general
• Composition RMgX is used, wherein the solution thus shown in turn according to the invention for the synthesis of diorganomagensiumhaltigen synthesis agents or mixtures thereof with alkali metal salts can be used;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts in solvent mixtures of ethers and hydrocarbons, wherein one or more different Grignard compounds RMgX in ethers or preferably in mixtures of ethers and hydrocarbons are used for the synthesis and wherein the alkali metal is preferably in an aromatic or aliphatic hydrocarbon, and the ethers used can be removed after the reaction by methods of the prior art, for example by distillation at atmospheric pressure, under reduced pressure, by vacuum distillation or by evaporation, and wherein alkali metal salt-poor or -freie solutions arise from organomagnesium compounds;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, ethereal solvents being used for the preparation of alkali metal salt-containing diorganomagnesium-containing synthesis agents, for example for use in halogen / metal exchange reactions or metallation reactions, preference being given to cyclic ethers and more preferably THF and 2 Methyl THF can be used;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, the processes being carried out in the absence of air and moisture, preferably in an inert gas atmosphere, more preferably in a nitrogen or argon atmosphere;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and mixtures thereof with alkali metal salts, the process according to the invention being carried out at temperatures between -100 ° C. and the boiling point of the reaction suspension, preferably at temperatures between -15 ° C. and the boiling point of the reaction suspension, more preferably between 0 ° C and 60 ° C;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein the corresponding diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts of precipitated solids are separated by methods of the prior art, preferably decantation, filtration or centrifugation;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein R, R ¹ , R ² and R ³ independently of H, saturated, unsaturated, branched, unbranched, functionalized, unfunctionalized, aliphatic, cyclic, heterocyclic or aromatic organic fragments are selected, wherein saturated, unsaturated, branched, unbranched, functionalized, unfunctionalized, aliphatic, cyclic, heterocyclic or aromatic organic fragments having 1 to 80 carbon atoms are preferred, in particular saturated, unsaturated, branched, unbranched, functionalized , unfunctionalized, aliphatic, cyclic, heterocyclic or aromatic organic fragments having 1 to 40 carbon atoms are preferred, wherein saturated, unsaturated, branched, unbranched, functionalized, unfunctionalized, aliphatis particularly preferred are che, cyclic, heterocyclic or aromatic organic fragments having 1 to 20 carbon atoms and where branched and unbranched methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclopentyl, Cyclohexyl, phenyl, benzyl and heteroaryl fragments are particularly preferred, and X is selected from chlorine, bromine, iodine, tosylate or triflate, preferably from chlorine, bromine and iodine;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, using aprotic organic solvents;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, using aliphatic or aromatic hydrocarbons, heterocycles, ethers, amines, nitriles or mixtures thereof;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein as aliphatic hydrocarbons cyclic, saturated, unsaturated, branched and unbranched hydrocarbons, preferably saturated or cyclic, branched or unbranched hydrocarbons having 5-20 carbon atoms are used, especially preferably n-pentane, n-hexane, n-heptane, n-octane or their isomers, cyclopentane, cyclohexane and methylcyclohexane;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein, as ether cyclic, saturated, unsaturated, branched, unbranched, similarly substituted and differently substituted ethers having at least one oxygen atom are used, preferably having one to four oxygen atoms dimethyl ethers, diethyl ether, dibutyl ether, dimethoxyethane, diethoxymethane, methyl tert-butyl ether, polyethylene glycol, cyclopentyl methyl ether, dioxane, tetrahydrofuran and 2-methyltetrahydrofuran;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, wherein as amines cyclic, aliphatic, saturated, unsaturated, branched, unbranched, similarly substituted and differently substituted amines having at least one nitrogen atom, preferably having one to four nitrogen atoms, N, N-tetramethylethylenediamine is particularly preferred;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, unsubstituted, monosubstituted and polysubstituted aromatic compounds being used as aromatic hydrocarbons, preferably benzene, toluene, ethylbenzene, cumene and / or xylenes or their isomers;
• A process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, substituted heterocycles, unsubstituted, aromatic, saturated and unsaturated cyclic compounds having in the cycle of at least four carbon atoms, preferably four to six carbon atoms, and at least an atom; preferably one to three atoms, from the group of heteroatoms oxygen, sulfur and nitrogen, with particular preference being THF, 2-methyl-THF and pyridine;
• A process for the preparation of identically or differently substituted dialkyl, dialkenyl, dialkinyl, diaryl, diheteroaryl, alkylalkenyl, alkylalkynyl, alkylaryl, alkylheteroaryl, alkenylalkynyl, alkenylaryl, alkenylheteroaryl, alkynylaryl or alkynylheteroarymagnesium compounds or mixtures thereof with alkali metal salts, Grignard compounds RMgX or organolithium compounds RLi;
• A process for the preparation of identically or differently substituted di-n-alkyl, di-sec-alkyl, di-iso-alkyl, di-tert-alkyl, di-cycloalkyl, di-aryl and di-heteroaryl magnesium compounds or their mixtures with alkali metal salts, Grignard compounds RMgX or organolithium compounds RLi;
• A process for the preparation of dimethylmagnesium, diethylmagnesium, di-isopropylmagnesium, di-n-propylmagnesium, di-n-butylmagnesium, di-sec-butylmagnesium, diisobutylmagnesium, di-tert-butylmagnesium, di-cyclopropylmagnesium, Di-cyclo-pentylmagnesium, di-cyclo-hexylmagnesium, di-n-pentylmagnesium, di-n-hexylmagnesium, diphenylmagnesium, dibenzylmagnesium, n-butyl-n-ocytlmagnesium, n-butyl-ethylmagnesium, s-butyl-ethylmagnesium or Butyl-n-butylmagnesium or mixtures thereof with alkali metal salts, Grignard compounds RMgX or organolithium compounds RLi;
• The use of the diorganomagnesium-containing synthesis agents prepared according to the invention and their mixtures with alkali metal salts in synthetic chemistry;
• The use of the diorganomagnesium-containing synthesis agents prepared according to the invention and mixtures thereof with alkali metal salts in organic chemistry and organometallic chemistry;
• The use of the diorganomagnesium-containing synthesis agents prepared according to the invention and mixtures thereof with alkali metal salts in halogen / metal exchange reactions;
• The use of the diorganomagnesium-containing synthesis agents prepared according to the invention and mixtures thereof with alkali salts in metallation reactions, preferably in ortho-metallation reactions;
• The use of the diorganomagnesium-containing synthesis agents prepared according to the invention and mixtures thereof with alkali metal salts in transmetalation reactions;
• The use of the diorganomagnesium-containing synthesis agents prepared according to the invention and mixtures thereof with alkali metal salts for the preparation of organozinc halides or diorganozinc compounds;
• The use of the diorganomagnesium-containing synthesis agents prepared according to the invention and their mixtures with alkali metal salts for the preparation of magnesium alcoholates and magnesium halides;
• The use of highly reactive magnesium produced in accordance with the invention in synthetic chemistry;
• The use of highly reactive magnesium produced in accordance with the invention in organic chemistry and organometallic chemistry;
• The use of highly reactive magnesium prepared according to the invention for the preparation of Grignard compounds of the general composition RMgX;
• The use of highly reactive magnesium prepared according to the invention for the preparation of diorganomagnesium compounds R ¹ R ² Mg;
• The use of highly reactive magnesium prepared according to the invention for the synthesis of magnesium hydride MgH ₂ ;
• The use of highly reactive magnesium prepared according to the invention for the preparation of identically or differently substituted dialkyl, dialkenyl, dialkinyl, diaryl, diheteroaryl, alkylalkenyl, alkylalkynyl, alkylaryl, alkylheteroaryl, alkenylalkynyl, alkenylaryl, alkenylheteroaryl, Alkynylaryl or alkynyl heteroarymagnesium compounds, alkyl, alkenyl, alkynyl, aryl, heteroaryl Grignard compounds RMgX or mixtures thereof with alkali metal salts;
• Highly reactive magnesium obtainable from alkali metals and Grignard compounds RMgX;
• A diorganomagnesium compound R _x ¹ R _y ² Mg as a solution in an ether-containing solvent, in admixture with lithium halides and / or Grignard compounds RMgX and / or alkali metal organyls RM and the molar ratio of diorganomagnesium compounds and lithium halide between 1: 0.1 to 1: Is 2 and the molar mixing ratio of diorganomagnesium compound and Grignard compound or alkali metal organyl is between 1: 0.15 and 1: 4 and the sum x + y = 2 and x and y are independently selected from the range between 0 and 2;
• A solution of diorganomagnesium compounds R _x ¹ R _y ² Mg and lithium halides selected from the group consisting of lithium chloride, lithium bromide and lithium iodide in a solvent containing tetrahydrofuran or 2-methyltetrahydrofuran and mixtures thereof with Grignard compounds RMgX or alkali metal organyls RM, where R, R ¹ and R ^{2 is} independently selected from secondary alkyl groups, preferably sec-butyl, iso-propyl, cyclopropyl, cyclopentyl, cyclohexyl and the molar ratio of R _x ¹ R _Y ² Mg and the lithium halide in the range between 1: 0.1 and 1: 2 and the molar mixing ratio of diorganomagnesium compound and Grignard compound or alkali metal organyl is between 1: 0.15 and 1: 4 and the sum x + y = 2 and x and y are independently selected from the range between 0 and 2;
• A solution of diorganomagnesium compounds R _x ¹ R _y ² Mg and lithium halides selected from the group consisting of lithium chloride, lithium bromide and lithium iodide in a solvent containing tetrahydrofuran or 2-methyltetrahydrofuran and mixtures thereof with Grignard compounds RMgX or alkali metal organyls RM, where R, R ¹ and R ² independently of one another are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl , cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl and the molar ratio of R _x ¹ R _y ² Mg and the lithium halide in the range between 1: 0.1 and 1: 2 and the molar mixing ratio of Diorganomagnesiumverbindung and Grignardverbindung or Alkalimetallorganyl between 1 Is 0.15 and 1: 4 and the sum x + y = 2 and x and y are independently selected from the range between 0 and 2;
• A solution of diorganomagnesium compounds R _x ¹ R _y ² Mg and lithium halides selected from the group consisting of lithium chloride, lithium bromide and lithium iodide in tetrahydrofuran or 2-methyltetrahydrofuran and mixtures thereof with Grignard compounds RMgX or alkali metal organyls RM, where R, R ¹ and R ^{2 are} independently selected from among methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl , cyclohexyl, phenyl, benzyl and the molar ratio of x _x ¹ R _y ² Mg and the lithium halide in the range between 1: 0.1 and 1: 2 and the molar mixing ratio of diorganomagnesium compound and Grignard compound or alkali metal organyl is between 1: 0.15 and 1: 4 and the sum x + y = 2 and x and y are independently selected from the range between 0 and 2;
• A solution of diorganomagnesium compounds R _x ¹ R _y ² Mg and lithium halides selected from the group lithium chloride, lithium bromide and lithium iodide, in solvent mixtures of hydrocarbons and ethers and mixtures thereof with Grignard compounds RMgX or alkali metal organyls RM, where R, R ¹ and R ^{2 are} independent are selected from among methyl, ethyl, iso-propyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl and the molar ratio of R _x ¹ R _y ² Mg and the lithium halide in the range between 1: 0.05 and 1: 2 and the molar mixing ratio of diorganomagnesium compound and Grignard compound or alkali metal organyl between 1: 0, 05 and 1: 4 and the sum x + y = 2 and x and y are independently selected from the range between 0 and 2 and wherein the molar ratio of ether to diorganomagnesium compound is between 0.02 : 1 and 50: 1;
• A solution of diorganomagnesium compounds R _x ¹ R _y ² Mg and lithium halides selected from the group consisting of lithium chloride, lithium bromide and lithium iodide in solvent mixtures of dimethyl ether, diethyl ether, dibutyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, tetrahydrofuran or 2-methyltetrahydrofuran and toluene , Cumene, xylenes, pentane, hexane, heptane, octane, cyclohexane or methylcyclohexane and mixtures thereof with Grignard compounds RMgX or alkali metal organyls RM, where R, R ¹ and R ^{2 are} independently selected from methyl, ethyl, iso-propyl, n-propyl , n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl and the molar ratio of R _x ¹ R _y ² Mg and the lithium halide in the range between 1: 0.05 and 1: 2 and the molar mixing ratio of diorganomagnesium compound and Grignard compound or alkali metal organyl between 1: 0.05 and 1: 4 bet and the sum x + y = 2 and x and y are independently selected from the range between 0 and 2, and wherein the molar ratio of ether to diorganomagnesium compound is between 0.02: 1 and 50: 1.

The Invention will be explained with reference to the following examples without to restrict it to it.

To illustrate the efficiency of the process for the preparation of diorganomagnesium-containing synthesis agent, the preparation of di-sec-butylmagnesium and its mixtures with sec-BuLi and sec-BuMgCl and LiCl was selected. A technical preparation of this compound, for example by oxidative addition of two equivalents of sec-butyl chloride to magnesium leads as described to β-H elimination and various by-products. In addition, high process temperatures and long reaction times are necessary. Experiments for the preparation of (sec-Bu) ₂ Mg by transmetallation with sec-BuLi lead to solvent mixtures. If it is desired to obtain lithium chloride-containing solutions directly by reacting sec-BuMgCl with sec-BuLi, it is necessary to work with only a relatively stable sec-BuLi concentrate, which is also pyrophoric. If the synthesis of sec-Bu ₂ Mg / LiCl mixtures with sec-BuMgCl and sec-BuLi concentrate in THF, for example, carried out at 0 ° C, also still THF cleavage is observed, so that the product solution is contaminated with impurities.

The advantages of the inventively obtained highly reactive magnesium in the production of Grignard compounds are illustrated by the preparation of t-BuMgCl. It is known that when using technical magnesium in the production of t-BuMgCl in THF, the product formed MgCl ₂ rich. It takes place as a side reaction a Wurtz coupling instead. Accordingly, the yields are low when using technical magnesium. Activation of the technical grade magnesium by methods of the prior art, such as addition of iodine or 1,2-dibromoethane, does not lead to optimal yields.

All Experiments were conducted in an argon atmosphere using Schlenk techniques. It technical raw materials were used. At sec-BuMgCl came different Batches as approx. 25% solutions used in THF. The exact content and composition of Batches were determined by wet analysis. Lithium became lithium metal used with different sodium content. The content of sodium is given in Table 1.

The Experimental parameters, analysis results and evaluations of the examples for the preparation according to the invention of diorganomagnesium-containing synthesis agents are in the tables 1 to 3 summarized. In the examples, R = sec-butyl. So far were stated during the reaction taken samples and analyzed by wet analysis. This was not taken into account in determining the yield, so that in case of samples the yields given in the tables depending on Number of samples lower.

The Experimental parameters, analysis results and evaluations of the examples for the preparation according to the invention of highly reactive magnesium, its use for the production of T-BuMgCl and Vergleichbesipsiele with technical magnesium are in Tables 4a and 4b.

The content of magnesium was determined by complexometry, the content of chloride argentometrically and the content of total base acidimetrisch after hydrolysis. The active base was determined according to Watson-Eastham with 2,2'-biquinoline as an indicator. GC / MS and ¹ H NMR measurements confirmed the identity of the isolated products.

Examples 1 to 5: organomagnesium compounds by reaction of alkali metal and sec-BuMgCl according to the in 10 represented general formula

General procedure explained with reference to Example 1:
In a 250 ml Schlenk flask with reflux condenser and dropping funnel, 700 mg (101 mmol) of lithium powder are suspended in about 8.0 g of THF. At a temperature between 30 and 40 ° C within 90 minutes 38.5 g (83.3 mmol) of a 25.3% solution of sec-butylmagnesium chloride in THF was added. After an hour of reaction time at 30 ° C, the reaction suspension is filtered and the residue washed with THF. The filter residue is dried under vacuum.
Yield: 50.3 g of a brownish clear solution.

Examples 2 to 5:

The Examples 2 to 5 are analogous to Example 1 according to the experimental parameters in Table 1. The results are summarized in Tables 2 and 3.

The Results in Table 2 show that the reaction residues consist of Examples 1 to 4 predominantly Made of magnesium metal. In addition, LiCl is still and not reacted lithium metal found. Lithium metal-free residues are by using a surplus to Grignard compound as shown in Example 7.

Example 6: Reaction of highly reactive magnesium (minimization of residues in the production of diorganomagnesiumhaltigen Synthesis means):

5.33 g of the residue from Example 2, consisting of [Cl] = 1.18 mmol / g, [Mg] = 32.3 mmol / g and [Li] = 6.3 mmol / g, are suspended in about 63 g of THF. Be at 30 ° C 16.9 g (182.6 mmol) of sec-butyl chloride dosed within 2 hours. After a post-reaction time of about one hour, the obtained Suspension filtered and the residue dried on a vacuum.

Yield: 70.1 g of a brown solution, corresponding to a yield of 96.0% with respect to used sec-butyl chloride. Analytical values: [OH] = 2.50 mmol / g; [Mg] = 2.33 mmol / g; [Li] = 0.30 mmol / g; [Cl] = 2.44 mmol / g. Due to the salary on metallic lithium in the residue used, the product solution contains low Amounts of di-sec-butylmagnesium and LiCl. The composition the product solution is found in Table 3.

Example 7: Preparation of highly reactive magnesium

5.0 g (720.5 mmol) of lithium (Na content 3.2% by weight) are dissolved in 400 g of THF suspended. At 30 ° C 404.2 g (864.6 mmol) of sec-BuMgCl (as a 25% solution in THF) within 2 hours. After an hour of after-reaction at 30 ° C the reaction suspension is filtered and the residue with 2 times 100 g of THF washed and dried in vacuo. There were 26.9 g of a black one Received precipitation. The analysis data show that it is this is magnesium, which still contains LiCl. Yield of magnesium: 98%

Example 8: Use of technical magnesium in the production of t-BuMgCl in THF

• a) 75 g (3.068 mol) of technical magnesium chips suspended in about 800 ml of THF. There are 2 ml of 1,2-dibromoethane to Activation of magnesium added and heated to 50 ° C. The dosage of t-butyl chloride (188.3 g, 2.034 mol) takes place within 3 hours at 50 to 66 ° C. To one hour of post-reaction is filtered. It will be 868.9 g one dark solution (yield: 87.1% based on OH).
• b) the remnants of magnesium turnings from example 8a and 86g (3.539 mol) of fresh technical Mg chips suspended in about 910 ml of THF. The dosage of 279.5 g (3.019 mol) t-BuCl takes place between 40 to 45 ° C within 3 hours. To 1 hour post-reaction is filtered. 1158.2 g of a dark solution are obtained (Yield 84.4% based on OH).

Example 9: Use of highly reactive magnesium in the production of t-BuMgCl in THF

20 g of the highly reactive magnesium-containing residue from Example 7 (316 mmol Mg) are suspended in about 122 mL THF. The dosage of 26.7 g (288 mmol) of t-BuCl is between 40 to 45 ° C within of 30 minutes. After 30 minutes post-reaction is filtered. It 133.2 g of a dark solution are obtained (Yield 97.1% based on OH).

The Experimental parameters, analysis data and production results of highly reactive magnesium and its reaction with t-BuCl, as well the comparative examples for the preparation of t-BuMgCl with technical Magnesium are shown in Table 4a and Table 4b.

Table 2: Analytical values of the reaction residues from Examples 1 to 4

Table 3: Composition of the product solutions in Examples 1 to 6

• ¹ as [Li]; ² as [Cl]; ³ calculated as [Cl] - [Li]; ⁴ calculated as [Mg] _Ges - [Mg] _RMgX ; ⁵ calculated as [Li] - [CI].

Claims (32)

Process for the preparation of highly reactive magnesium and diorganomagnesium-containing synthesis agents and their mixtures with alkali metal salts, characterized in that an alkali metal or mixtures or alloys of alkali metals, and a Grignard compounds of the general formula RMgX or more Grignard compounds of the general formulas R ¹ MgX, R ² MgX and R ³ MgX are reacted together, wherein: - R, R ¹ , R ² and R ³ may be the same or different selected from H, saturated, unsaturated, branched, unbranched, functionalized, unfunctionalized, aliphatic, cyclic, heterocyclic or aromatic organic Fragments, preferably fragments having 1 to 80, more preferably 1 to 40, most preferably 1 to 20 carbon atoms, and - X is selected from chlorine, bromine, iodine, tosylate or triflate, preferably from chlorine, bromine and iodine. A method according to claim 1 or 2, characterized in that R, R ¹ , R ² and R ³ may be the same or different selected from methyl, ethyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl and heteroaryl fragments and branched and unbranched propyl, butyl, pentyl, hexyl, heptyl, Oc tyl fragments. Method according to claim 1 or 2, characterized that the alkali metal is lithium or mixtures or alloys, consisting of lithium and another alkali metal, preferably Sodium, wherein the proportion of lithium in the mixtures or Alloys between 50 and 99.99 wt .-%, preferably between 80 and 99.99% by weight, more preferably between 90 and 99.99% by weight is. Method according to at least one of claims 1 to 3, characterized in that the alkali metal is initially charged in an aprotic organic solvent or solvent mixture and a Grignard compound RMgX - or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - are added. Method according to at least one of claims 1 to 4, characterized in that a Grignard compound RMgX - or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - are presented in an aprotic organic solvent or solvent mixture and the alkali metal as a solid or suspension in an aprotic organic solvent or solvent mixture is added. Method according to at least one of claims 1 to 5, characterized in that the compounds of the general formula RMgX, R ¹ MgX, R ² MgX and R ³ MgX are preferably added dissolved in the solvent or solvent mixture in which the alkali metal is suspended. Method according to at least one of claims 1 to 6, characterized in that the alkali metal is preferably added suspended in the solvent or solvent mixture in which compounds of the general formula RMgX, R ¹ MgX, R ² MgX and R ³ MgX are dissolved. A method according to any one of claims 1 to 7, characterized in that the molar ratio of the amount of a Grignard compound RMgX - or the molar ratio of the total amount of several Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - to the total amount of alkali metal p / n is, wherein p and n are independently selected from a range between 0.1 and 10, preferably between 0.5 and 6. Method according to at least one of claims 1 to 8, characterized in that mixtures of Diorganomagnesiumverbindungen and Grignard compounds or their mixtures with alkali metal salts arise when n ≤ p is. Method according to at least one of claims 1 to 8, characterized in that mixtures of Diorganomagnesiumverbindungen and alkali metal organyls or mixtures thereof with alkali metal salts arise when n ≥ p is. Process according to at least one of Claims 1 to 10, characterized in that, for the preparation of diorganomagnesium compounds and their mixtures with alkali metal salts, the molar ratio of the total amount of Grignard compounds RMgX, R ¹ MgX, R ² MgX and R ³ MgX and the total amount of alkali metal between 1 : 0.7 and 1: 2, more preferably from 1: 0.8 to 1: 1.5. Process according to at least one of Claims 1 to 10, characterized in that, for the preparation of highly reactive magnesium, the molar ratio of the total amount of Grignard compounds R ¹ MgX, R ² MgX, R ³ MgX and the amount of alkali metal is from 1.0: 1 to 6 : 1, more preferably from 1.1: 1 to 4: 1. Method according to at least one of claims 1 to 12, characterized in that for the production of similar substituted diorganomagnesiumhaltigen synthesis means a compound the general formula RMgX is used. Process according to at least one of Claims 1 to 13, characterized in that x · R ¹ MgX, y · R ² MgX and z · R ³ MgX Grignard compounds are used to prepare differently substituted diorganomagnesium-containing synthesis agents, where x + y + z = p and x, y and z are independently selected from the range between 0 and p. Method according to at least one of claims 1 to 14, characterized in that the alkali metal in the form of metal powder, Metal dispersion or metal granules is used, preferably in Form of metal powder or metal dispersion. Method according to at least one of claims 1 to 15, characterized in that the Grignard compounds are preferred to a suspension of the alkali metal in an aprotic organic solvent be dosed. Method according to at least one of claims 1 to 16, characterized in that the organic halides RX to a suspension of the highly reactive magnesium in an aprotic organic solvents or solvent mixture be dosed. Method according to at least one of claims 1 to 17, characterized in that suspension already diorganomagensiumhaltige dienganomagensiumhaltige May contain synthesis agents and / or Grignardverbindungen. A process according to at least one of claims 1 to 18, characterized in that the reaction suspension obtained by reaction of Grignard compounds RMgX with alkali metal is an organic halide RX - or more organic halides R ¹ X, R ² X and R ³ X - supplied, wherein Grignard compounds the general composition RMgX - or more Grignard compounds R ¹ MgX, R ² MgX and R ³ MgX - or their mixture with an alkali metal salt, these mixtures are in turn used to prepare diorganomagnesiumhaltigen synthesis agents or their mixtures with alkali metal salts and this process several times, preferably 1 to 20 times is repeated. Method according to at least one of claims 1 to 19, characterized in that the reaction residue separated and immediately after the reaction or after drying, or after washing and drying in an aprotic solvent or solvent mixture or in a solution one or more Grignard compounds is suspended and by Addition of organic halides RX for the synthesis of Grignard compounds the general composition RMgX is used, the so illustrated solution in turn according to the invention for synthesis of diorganomagensium-containing synthesis agents or mixtures thereof can be used with alkali metal salts. Method according to at least one of claims 1 to 20, characterized in that the reaction takes place in solvent mixtures of ethers and hydrocarbons, wherein one or more different Grignard compounds RMgX or R ¹ MgX, R ² MgX and / or R ³ MgX in ethers, preferably in Mixtures of ethers and hydrocarbons, are used and the alkali metal or the alkali metal and magnesium are preferably presented suspended in an aromatic or aliphatic hydrocarbon. Process according to at least one of Claims 1 to 21, characterized in that the reaction takes place exclusively in ethers, one or more different Grignard compounds RMgX or R ¹ MgX, R ² MgX and / or R ³ MgX in ethers being used for the preparation and Alkali metal or the alkali metal and magnesium are suspended in ethers. Method according to at least one of claims 1 to 22, characterized in that as the ether dimethyl ether, diethyl ether, Dibutyl ether, methyl tert-butyl ether, Cyclopentylmethyl ether, tetrahydrofuran or 2-methyltetrahydrofuran, preferably THF and / or 2-methyl-THF. Method according to at least one of claims 1 to 23, characterized in that as hydrocarbons aprotic, organic solvents, preferred Toluene, cumene, xylenes, pentane, hexane, heptane, octane, cyclohexane or methylcyclohexane. Method according to at least one of claims 1 to 24, characterized in that it is at temperatures between -100 ° C and the Boiling point of the reaction suspension, preferably at temperatures between -15 ° C and the Boiling point of the reaction suspension, more preferably between 0 ° C and 60 ° C is performed. Synthesis agent containing a Diorganomagnesiumverbindung R _x ¹ R _y ² Mg as a solution in an ether-containing solvent, preparable according to at least one of claims 1 to 25, characterized in that the Diorganomagnesiumverbindung in admixture with lithium halides and / or Grignard compounds RMgX and / or alkali metal organylene RM and the molar ratio of diorganomagnesium compound and Grignard compound or alkali metal organyl is between 1: 0.15 and 1: 4 and the sum x + y = 2 and x and y independently selected from the range between 0 and 2 are. Synthesis agent according to claim 26, characterized in that: - the lithium halides are selected from the group lithium chloride, lithium bromide and lithium iodide, - the solvent of dimethyl ether, diethyl ether, dibutyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, Cumene, xylenes, pentane, hexane, heptane, octane, cyclohexane or methylcyclohexane or any mixtures of at least two of these substances, and - R, R ¹ and R ^{2 are} independently selected from: methyl, ethyl, iso-propyl, n -propyl, n -butyl, iso -butyl, sec -butyl, tert -butyl, n -pentyl, n -hexyl, n -heptyl, n -octyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl. Synthesis agent according to claim 26 or 27, characterized characterized in that the solvent Contains tetrahydrofuran and / or 2-methyltetrahydrofuran or from tetrahydrofuran or 2-methyltetrahydrofuran or any Mixtures of these consists. Synthesis agent according to at least one of claims 26 to 28, characterized in that it is in the Diorganomagnesiumverbindung a dialkyl, dialkenyl, dialkinyl, diaryl, diheteroaryl, Alkylalkenyl, alkylalkynyl, alkylaryl, alkylheteroaryl, alkenylalkynyl, Alkenylaryl, alkenylheteroaryl, alkynylaryl or alkynylheteroarylmagnesium compound, preferably a di-n-alkyl, Di-sec-alkyl, di-iso-alkyl, di-tert-alkyl, di-cycloalkyl, di-aryl and diheteroaryl-magnesium compound, more preferably diethylmagnesium, Di-iso-propylmagnesium, di-n-propylmagnesium, di-n-butylmagnesium, Di-sec-butylmagnesium, Diisobutylmagnesium, di-tert-butylmagnesium, di-cyclopropylmagnesium, Di-cyclo-pentylmagnesium, di-cyclo-hexylmagnesium, di-n-pentylmagnesium, Di-n-hexylmagnesium, diphenylmagnesium, dibenzylmagnesium, n-butyl-n-ocytlmagnesium, n-butyl-ethylmagnesium, s-butyl-ethylmagnesium or s-butyl-n-butylmagnesium. Highly reactive magnesium, producible after one or more of the claims 1 to 25. Use of the synthesis agent according to at least one of the claims 26 to 29 in synthetic chemistry, preferably in organic chemistry and organometallic chemistry. Use according to claim 31, characterized that the synthesis agent in halogen / metal exchange reactions, in Metallation reactions, preferably in ortho-metallation reactions, in transmetalation reactions, for the preparation of organozinc halides or diorganozinc compounds, magnesium alcoholates or magnesium halides is used.