EP1056750A1 - Synthesis agents containing benzyl magnesium halogenides or allyl magnesium halogenides and method for producing same - Google Patents
Synthesis agents containing benzyl magnesium halogenides or allyl magnesium halogenides and method for producing sameInfo
- Publication number
- EP1056750A1 EP1056750A1 EP99907379A EP99907379A EP1056750A1 EP 1056750 A1 EP1056750 A1 EP 1056750A1 EP 99907379 A EP99907379 A EP 99907379A EP 99907379 A EP99907379 A EP 99907379A EP 1056750 A1 EP1056750 A1 EP 1056750A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- magnesium
- halide
- methyltetrahydrofuran
- thf
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- -1 allyl magnesium Chemical compound 0.000 title claims abstract description 40
- 239000011777 magnesium Substances 0.000 title claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 25
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- GUDBSTJKAWCJQP-UHFFFAOYSA-N [Mg]CC1=CC=CC=C1 Chemical compound [Mg]CC1=CC=CC=C1 GUDBSTJKAWCJQP-UHFFFAOYSA-N 0.000 title claims abstract 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000011877 solvent mixture Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 16
- 150000004795 grignard reagents Chemical class 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- UAWVMPOAIVZWFQ-UHFFFAOYSA-N 1-(chloromethyl)-2-methoxybenzene Chemical compound COC1=CC=CC=C1CCl UAWVMPOAIVZWFQ-UHFFFAOYSA-N 0.000 description 1
- VQRBXYBBGHOGFT-UHFFFAOYSA-N 1-(chloromethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CCl VQRBXYBBGHOGFT-UHFFFAOYSA-N 0.000 description 1
- IZXWCDITFDNEBY-UHFFFAOYSA-N 1-(chloromethyl)-4-fluorobenzene Chemical compound FC1=CC=C(CCl)C=C1 IZXWCDITFDNEBY-UHFFFAOYSA-N 0.000 description 1
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 description 1
- MPCHQYWZAVTABQ-UHFFFAOYSA-N 2-(chloromethyl)naphthalene Chemical compound C1=CC=CC2=CC(CCl)=CC=C21 MPCHQYWZAVTABQ-UHFFFAOYSA-N 0.000 description 1
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- FDDVGEFFNYETAN-UHFFFAOYSA-N 6-(chloromethyl)-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(CCl)=CC=C21 FDDVGEFFNYETAN-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical class CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B49/00—Grignard reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
Definitions
- the invention relates to benzylmagnesium halides and allylmagnesium halides containing synthetic agents and a process for their preparation.
- Document EP 0 415 247 A2 discloses a process for the preparation of arylmethyl magnesium halides with tert-butyl ethers, preferably at least 2.5 moles of magnesium per mole of arylmethyl halide. It is also known from document WO 93/12121
- Arylmethyl magnesium halides have the disadvantage that the organomagnesium compounds formed are only poorly soluble and therefore form suspensions.
- DE 44 39 003 Cl and WO 93/02086 describe a process for the preparation of benzyl magnesium halide in a solvent of the general formula III
- R 2 / x OR 4 or in a solvent mixture containing a corresponding solvent, where R 1 and R 2 are independently a hydrogen, methyl or ethyl radical and R 3 and R 4 are a methyl and / or ethyl radical.
- Diethoxymethane in particular is listed as an advantageous example of III because this solvent is only slightly water-miscible, which is relevant in the aqueous work-up of a reaction mixture occurring in a Grignard reaction.
- a disadvantage of the synthetic agent containing benzyl magnesium halide thus produced is the poor stability of the solvent diethoxymethane against strong mineral acids, which are often used in the work-up of the reaction mixtures resulting from Grignard syntheses.
- the invention is therefore based on the object of creating a benzylmagnesium halide or allylmagnesium halide-containing synthetic agent which eliminates the disadvantages of the prior art, the solvent of which is, in particular, only slightly water-miscible and, at the same time, stable to mineral acids and which advantageously is only a trace of the by-product as a clear solution contains formed diaryl compound or diallyl compound.
- the object on which the invention is based is achieved by a synthesis agent containing benzyl magnesium halide or allyl magnesium halide, which is characterized in that the solvent is 2-methyl-THF or a solvent containing 2-methyl-THF.
- 2-methyl-THF is not water-miscible and has good solubility for many organic substances. Loss of solvent or product is reduced when using the synthetic agent according to the invention and the recovery of the solvent is simplified. Costs for the solvent can also be reduced by the fact that the inventive Synthesizing agent contains a solvent mixture of 2-methyl-THF and an aromatic solvent. Also, when using 2-methyl-THF it is not necessary to work with magnesium powder (magnesium chips are sufficient) and not at low temperatures to achieve good yields (the reaction temperatures are from -10 ° C. to 100 ° C.).
- the solvent 2-methyl-THF used according to the invention is stable to strong mineral acids when working up a reaction mixture obtained in a Grignard reaction carried out with the synthetic agent according to the invention, which greatly simplifies the working up of such a reaction mixture.
- the synthetic agents according to the invention allow a higher concentration of active C-Mg bond than with the solvent THF and prove to be more crystallization stable than benzyl magnesium halides or allyl magnesium halides produced in THF solutions.
- X Cl
- the synthesis agent according to the invention is obtained after the insoluble magnesium chloride (MgCl 2 ) formed in the reaction has been separated off as a clear solution which contains only traces of the diaryl compound or diallyl compound formed as a by-product.
- the benzylmagnesium halide-containing or allyl magnesium halide-containing synthesis agents according to the invention can carry one or more of the following substituents in the phenyl or allyl group:
- benzyl chloride examples of corresponding starting compounds which are of particular importance with regard to their use for organic syntheses in the fields of crop protection agents, pharmaceuticals and dyes are benzyl chloride, benzyl bromide, 2-chlorobenzyl chloride, 2-methoxybenzyl chloride, 4-fluorobenzyl chloride, 4-methylbenzyl chloride, 2.5-
- the synthesis agent according to the invention is further characterized in that it contains benzyl or allyl magnesium halide and dibenzyl or diallyl magnesium in a molar ratio of 1: 0 to 0: 1.
- the stoichiometry typical of Grignard compounds according to the formula R-Mg-X is not present in the synthetic agent according to the invention.
- the synthetic agent is to be understood as a mixture of benzyl or allyl magnesium halide and dibenzyl or diallyl magnesium, the molar ratio of the aforementioned compounds depending on the respective substituent, the desired concentration of the solution and the type of halogen.
- the chloride content of the solutions can be reduced as a result. This leads to lower waste quantities for the user after using the synthetic agent according to the invention.
- the synthetic agent according to the invention is produced in such a way that
- Dispersed solvent mixture which contains 2-methyltetrahydrofuran and metered in a benzyl or allyl halide, b) the reaction temperature is kept in the range from -10 to + 100 ° C, preferably 0 to + 40 ° C, and c) the magnesium halide formed and precipitated during the reaction is separated off.
- the overall yield is 97.8%.
- R-MgX R 2 Mg molar ratio in the benzyl- and allylmagnesium halide-containing synthesis agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to synthesis agents containing benzyl magnesium halogenides and allyl magnesium halogenides (Grignard reagents) with 2-methyl-tetrahydrofuran as solvent, and to a method for producing same.
Description
Benzylmagnesiumhalogenide oder Allylmagnesiumhalogenide enthaltende Synthesemittel und Verfahren zu deren HerstellungSynthesis agents containing benzyl magnesium halides or allyl magnesium halides and process for their preparation
Beschreibungdescription
Die Erfindung betrifft Benzylmagnesiumhalogenide und Allylmagnesiumhalogenide enthaltende Synthesemittel sowie ein Verfahren zu deren Herstellung.The invention relates to benzylmagnesium halides and allylmagnesium halides containing synthetic agents and a process for their preparation.
BenzylmagnesiumhalogenideBenzyl magnesium halides
MgXMgX
L J
oder AllylmagnesiumhalogenideLJ or allyl magnesium halides
^ ^MgX^ ^ MgX
(X = Cl, Br, I) sind unter dem Begriff Gngnard-Reagenzien wohlbekannte Synthesehilfsmittel der praparativen organischen Chemie. Bisher wurden die Benzylmagnesiumhalogenide oder Allylmagnesiumhalogenide m etheπschen Losungsmitteln, wie Diethylether oder Tetrahydrofuran (THF) , hergestellt. Diethylether wird aufgrund seiner leichten Fluchtigkeit sowie seines niedrigen Flammpunktes nur ungern für technische Zwecke eingesetzt; die Herstellung der Benzylmagnesiumhalogenide m THF ist von einer unerwünschten Dimerisierung des Benzylrestes begleitet. Die Bildung der DiarylVerbindung erhöht den Verbrauch von Magnesium und verschlechtert die Ausbeute.(X = Cl, Br, I) are well-known synthesis aids of preparative organic chemistry under the term Gngnard reagents. So far, the benzylmagnesium halides or allylmagnesiumhalogenide have been produced using ethical solvents, such as diethyl ether or tetrahydrofuran (THF). Due to its slight volatility and its low flash point, diethyl ether is reluctant to use for technical purposes; the production of the benzyl magnesium halides m THF is accompanied by an undesirable dimerization of the benzyl radical. The formation of the diaryl compound increases the consumption of magnesium and worsens the yield.
Aus dem Dokument EP 0 415 247 A2 ist ein Verfahren zur Herstellung von Arylmethylmagnesiumhalogeniden m tert.- Butylethern bekannt, wobei vorzugsweise mindestens 2,5 Mol Magnesium je Mol Arylmethylhalogenid eingesetzt werden. Weiterhin ist aus dem Dokument WO 93/12121 bekannt,Document EP 0 415 247 A2 discloses a process for the preparation of arylmethyl magnesium halides with tert-butyl ethers, preferably at least 2.5 moles of magnesium per mole of arylmethyl halide. It is also known from document WO 93/12121
Arylmethylmagnesiumhalogenid in Methyl-tert . -Butylether (MTBE) bei Reaktionstemperaturen oberhalb von 45°C herzustellen, wobei das Molverhaltnis von Magnesium zu Arylmethylhalogenid 1 : 1 bis 2 : 1 betragt. Die im MTBE hergestelltenArylmethyl magnesium halide in methyl tert. -Butyl ether (MTBE) at reaction temperatures above 45 ° C, the molar ratio of magnesium to aryl methyl halide is 1: 1 to 2: 1. The manufactured in the MTBE
Arylmethylmagnesiu halogenide weisen den Nachteil auf, daß die entstehenden Organomagnesiumverbmdungen nur schlecht löslich sind und deshalb Suspensionen bilden. DE 44 39 003 Cl und WO 93/02086 beschreiben ein Verfahren zur Herstellung von Benzylmagnesiumhalogenid in einem Losungsmittel der allgemeinen Formel IIIArylmethyl magnesium halides have the disadvantage that the organomagnesium compounds formed are only poorly soluble and therefore form suspensions. DE 44 39 003 Cl and WO 93/02086 describe a process for the preparation of benzyl magnesium halide in a solvent of the general formula III
R1\ OR3 R 1 \ OR 3
V inV in
R2/ xOR4
oder in einem ein entsprechendes Lösungsmittel enthaltenden Lösungsmittelgemisch, wobei R1 und R2 unabhängig voneinander ein Wasserstoff-, Methyl- oder Ξthylrest und R3 sowie R4 ein Methyl- und/oder Ethylrest sind. Als vorteilhaftes Beispiel für III ist insbesondere Diethoxymethan aufgeführt, weil dieses Lösungsmittel nur wenig wassermischbar ist, was bei der wässrigen Aufarbeitung eines bei einer Grignardrea tion anfallenden Reaktionsgemisches relevant ist. Als Nachteil des so hergestellten Benzyl agnesiumhalogenid enthaltenden Synthesemittels erweist sich die mangelhafte Stabilität des Lösungsmittels Diethoxymethan gegenüber starken Mineralsäuren, die häufig bei der Aufarbeitung der bei Grignardsynthesen anfallenden Reaktionsgemische eingesetzt werden.R 2 / x OR 4 or in a solvent mixture containing a corresponding solvent, where R 1 and R 2 are independently a hydrogen, methyl or ethyl radical and R 3 and R 4 are a methyl and / or ethyl radical. Diethoxymethane in particular is listed as an advantageous example of III because this solvent is only slightly water-miscible, which is relevant in the aqueous work-up of a reaction mixture occurring in a Grignard reaction. A disadvantage of the synthetic agent containing benzyl magnesium halide thus produced is the poor stability of the solvent diethoxymethane against strong mineral acids, which are often used in the work-up of the reaction mixtures resulting from Grignard syntheses.
Der Erfindung liegt daher die Aufgabe zugrunde, ein Benzylmagnesiumhalogenid oder Allylmagnesiumhalogenid enthaltendes Synthesemittel zu schaffen, das die Nachteile aus dem Stand der Technik beseitigt, dessen Lösungsmittel insbesondere nur wenig wassermischbar und gleichzeitig stabil gegenüber Mineralsäuren ist und das vorteilhafterweise als klare Lösung nur Spuren der als Nebenprodukt gebildeten DiarylVerbindung bzw. DiallylVerbindung enthält.The invention is therefore based on the object of creating a benzylmagnesium halide or allylmagnesium halide-containing synthetic agent which eliminates the disadvantages of the prior art, the solvent of which is, in particular, only slightly water-miscible and, at the same time, stable to mineral acids and which advantageously is only a trace of the by-product as a clear solution contains formed diaryl compound or diallyl compound.
Die der Erfindung zugrunde liegende Aufgabe wird durch ein Benzylmagnesiumhalogenid oder Allylmagnesiumhalogenid enthaltendes Synthesemittel gelöst, welches dadurch gekennzeichnet ist, daß als Lösungsmittel 2 -Methyl -THF oder ein 2-Methyl-THF enthaltendes Lösungsmittel vorliegt.The object on which the invention is based is achieved by a synthesis agent containing benzyl magnesium halide or allyl magnesium halide, which is characterized in that the solvent is 2-methyl-THF or a solvent containing 2-methyl-THF.
Vorteilhaft ist die Verwendung von 2-Methyl-THF als Lösungsmittel, da 2 -Methyl-THF im Gegensatz zu THF nicht wassermischbar ist und ein gutes Lösungsvermögen für viele organische Substanzen aufweist. Lösungsmittel- oder Produktverluste werden beim Einsatz des erfindungsgemäßen Synthesemittels reduziert und die Rückgewinnung des Lösungsmittels wird vereinfacht. Kosten für das Lösungsmittel können auch dadurch gesenkt werden, daß das erfindungsgemäße
Synthesemittel ein Lösungsmittelgemisch aus 2 -Methyl-THF und einem aromatischen Lösungsmittel enthält. Auch muß bei Verwendung von 2-Methyl-THF zum Erzielen guter Ausbeuten nicht mit Magnesiumpulver (es genügen Magnesiumspäne) und nicht bei tiefen Temperaturen gearbeitet werden (die Reaktionstemperaturen liegen bei -10 °C bis 100 °C) .It is advantageous to use 2-methyl-THF as a solvent since, in contrast to THF, 2-methyl-THF is not water-miscible and has good solubility for many organic substances. Loss of solvent or product is reduced when using the synthetic agent according to the invention and the recovery of the solvent is simplified. Costs for the solvent can also be reduced by the fact that the inventive Synthesizing agent contains a solvent mixture of 2-methyl-THF and an aromatic solvent. Also, when using 2-methyl-THF it is not necessary to work with magnesium powder (magnesium chips are sufficient) and not at low temperatures to achieve good yields (the reaction temperatures are from -10 ° C. to 100 ° C.).
Insbesondere ist das erfindungsgemäß eingesetzte Lösungsmittel 2- Methyl-THF bei der Aufarbeitung eines bei einer mit dem erfindungsgemäßen Synthesemittel durchgeführten Grignardreaktion anfallenden Reaktionsgemisches stabil gegenüber starken Mineralsäuren, was die Aufarbeitung eines solchen Reaktionsgemisches sehr vereinfacht.In particular, the solvent 2-methyl-THF used according to the invention is stable to strong mineral acids when working up a reaction mixture obtained in a Grignard reaction carried out with the synthetic agent according to the invention, which greatly simplifies the working up of such a reaction mixture.
Weiterhin vorteilhaft ist, daß die erfindungsgemäßen Synthesemittel eine höhere Konzentration an aktiver C-Mg-Bindung als beim Lösungsmittel THF erlauben und sich als kristallisationsstabiler gegenüber in THF-Lösungen hergestellten Benzylmagnesiumhalogeniden bzw. Allylmagnesiumhalogeniden erweisen. Im Fall, daß X = Cl ist, erhält man das erfindungsgemäße Synthesemittel nach der Abtrennung des bei der Reaktion gebildeten unlöslichen Magnesiumchlorids (MgCl2) als klare Lösung, die nur Spuren der als Nebenprodukt gebildeten DiarylVerbindung bzw. DiallylVerbindung enthält.It is also advantageous that the synthetic agents according to the invention allow a higher concentration of active C-Mg bond than with the solvent THF and prove to be more crystallization stable than benzyl magnesium halides or allyl magnesium halides produced in THF solutions. If X = Cl, the synthesis agent according to the invention is obtained after the insoluble magnesium chloride (MgCl 2 ) formed in the reaction has been separated off as a clear solution which contains only traces of the diaryl compound or diallyl compound formed as a by-product.
Die erfindungsgemäßen benzylmagnesiumhalogenidhaltigen bzw. allylmagnesiumhalogenidhaltigen Synthesemittel können in der Phenyl- bzw. Allylgruppe einen oder mehrere der folgenden Substituenten tragen:The benzylmagnesium halide-containing or allyl magnesium halide-containing synthesis agents according to the invention can carry one or more of the following substituents in the phenyl or allyl group:
- Fluor, Chlor, Brom,- fluorine, chlorine, bromine,
- Cλ- bis C8-Alkylgruppen- C λ to C 8 alkyl groups
- Cx- bis Cg-Halogenalkylgruppen mit Fluor und/oder Chlor als Halogenatom,C x to Cg haloalkyl groups with fluorine and / or chlorine as the halogen atom,
- Cx- bis C6-Alkoxygruppen,C x to C 6 alkoxy groups,
- Cx- bis C6-Halogenalkoxygruppen mit Fluor und/oder Chlor als Halogenatom,
- C - bis C6-Alkenylgruppen,C x to C 6 haloalkoxy groups with fluorine and / or chlorine as halogen atom, - C - to C 6 -alkenyl groups,
- C3- bis C6-Cycloalkylgruppen,C 3 to C 6 cycloalkyl groups,
- die Trimethylsilylgruppe und- The trimethylsilyl group and
- die Phenylgruppe oder die Phenoxygruppe, die ihrerseits die vorgenannten Substituenten tragen können.- The phenyl group or the phenoxy group, which in turn can carry the aforementioned substituents.
Beispiele für entsprechende Ausgangsverbindungen, denen im Hinblick auf ihre Verwendung für organische Synthesen auf den Gebieten der Pflanzenschutzmittel, der Arzneimittel und der Farbstoffe besondere Bedeutung zukommen, sind Benzylchlorid, Benzylbromid, 2-Chlorbenzylchlorid, 2-Methoxybenzylchlorid, 4- Fluorbenzylchlorid, 4-Methylbenzylchlorid, 2,5-Examples of corresponding starting compounds which are of particular importance with regard to their use for organic syntheses in the fields of crop protection agents, pharmaceuticals and dyes are benzyl chloride, benzyl bromide, 2-chlorobenzyl chloride, 2-methoxybenzyl chloride, 4-fluorobenzyl chloride, 4-methylbenzyl chloride, 2.5-
Dimethylbenzylchlorid, 2 -Chlormethylnaphthalin und 2 -Chlormethyl - 5,6,7, 8-tetrahydronaphthalin.Dimethylbenzyl chloride, 2-chloromethylnaphthalene and 2-chloromethyl-5,6,7, 8-tetrahydronaphthalene.
Das erfindungsgemäße Synthesemittel ist weiterhin dadurch gekennzeichnet, daß Benzyl- bzw. Allylmagnesiumhalogenid und Dibenzyl- bzw. Diallylmagnesium im Molverhältnis von 1 : 0 bis 0 : 1 in ihm enthalten sind. Im erfindungsgemäßen Synthesemittel liegt nicht die für Grignard-Verbindungen typische Stöchiometrie gemäß der Formel R-Mg-X vor. Das Synthesemittel ist als Gemisch aus Benzyl- bzw. Allylmagnesiumhalogenid und Dibenzyl- bzw. Diallylmagnesium aufzufassen, wobei das Molverhältnis der vorgenannten Verbindungen vom jeweiligen Substituenten, von der angestrebten Konzentration der Lösung und der Art des Halogens abhängig ist. Der Chlorid-Gehalt der Lösungen kann dadurch erniedrigt sein. Das führt beim Anwender zu geringeren Abfallmengen nach dem Einsatz des erfindungsgemäßen Synthesemittels .The synthesis agent according to the invention is further characterized in that it contains benzyl or allyl magnesium halide and dibenzyl or diallyl magnesium in a molar ratio of 1: 0 to 0: 1. The stoichiometry typical of Grignard compounds according to the formula R-Mg-X is not present in the synthetic agent according to the invention. The synthetic agent is to be understood as a mixture of benzyl or allyl magnesium halide and dibenzyl or diallyl magnesium, the molar ratio of the aforementioned compounds depending on the respective substituent, the desired concentration of the solution and the type of halogen. The chloride content of the solutions can be reduced as a result. This leads to lower waste quantities for the user after using the synthetic agent according to the invention.
Das erfindungsgemäße Synthesemittel wird in der Weise hergestellt, daßThe synthetic agent according to the invention is produced in such a way that
a) Magnesium in 2-Methyltetrahydrofuran oder in einema) Magnesium in 2-methyltetrahydrofuran or in one
Lösungsmittelgemisch, welches 2-Methyltetrahydrofuran enthält, dispergiert und ein Benzyl- bzw. Allylhalogenid zudosiert wird,
b) die Reaktionstemperatur im Bereich von -10 bis +100°C, vorzugsweise 0 bis +40°C, gehalten wird und c) das bei der Reaktion gebildete und ausgefallene Magnesiumhalogenid abgetrennt wird.Dispersed solvent mixture which contains 2-methyltetrahydrofuran and metered in a benzyl or allyl halide, b) the reaction temperature is kept in the range from -10 to + 100 ° C, preferably 0 to + 40 ° C, and c) the magnesium halide formed and precipitated during the reaction is separated off.
In den nachfolgenden 3 Ausführungsbeispielen sowie in den 2 Tabellen wird der Gegenstand der Erfindung näher erläutert.The subject matter of the invention is explained in more detail in the following 3 exemplary embodiments and in the 2 tables.
Beispiel 1example 1
In einem Doppelmantelreaktor werden 360 g 2-Methyl-THF und 14,7 g (605 mol = 21% Überschuß) Magnesiumspäne unter Schutzgas vorgelegt. Unter Rühren werden innerhalb von 60 Minuten 63,2 g (500 mmol) Benzylchlorid zudosiert. Die Reaktionstemperatur der exothermen Reaktion wird durch Kühlung auf 25 bis 30 °C begrenzt. Zur Vervollständigung der Umsetzung wird noch 30 Minuten bei 20 °C gerührt. Der ausgefallene Feststoff und überschüssiges Magnesium werden durch Filtration abgetrennt . Analyse nach Hydrolyse des Filtrats :360 g of 2-methyl-THF and 14.7 g (605 mol = 21% excess) of magnesium shavings are placed under a protective gas in a double jacket reactor. 63.2 g (500 mmol) of benzyl chloride are metered in with stirring over the course of 60 minutes. The reaction temperature of the exothermic reaction is limited to 25 to 30 ° C. by cooling. To complete the reaction, the mixture is stirred at 20 ° C. for a further 30 minutes. The precipitated solid and excess magnesium are separated off by filtration. Analysis after hydrolysis of the filtrate:
OH" 1,48 mmol/gOH " 1.48 mmol / g
Cl" 0, 5 mmol/g Mg2+ 1,22 mmol/g Dibenzyl < 0 , 1 %Cl " 0.5 mmol / g Mg 2+ 1.22 mmol / g dibenzyl <0.1%
Die Analyse zeigt, daß das Schlenk-Gleichgewicht verschoben ist und sich teilweise die Diorganomagnesiumverbindung gebildet hat. Der Rückstand wird noch zwei mal mit 2-Methyl-THF gewaschen. Die Gesamtausbeute (berechnet über Gesamtbase) beträgt 99%. Der Frittenrückstand besteht aus MgCl2.
Beispiel 2The analysis shows that the Schlenk equilibrium has shifted and the diorganomagnesium compound has partially formed. The residue is washed two more times with 2-methyl-THF. The total yield (calculated over total base) is 99%. The frit residue consists of MgCl 2 . Example 2
Dieses Beispiel wird entsprechend Beispiel 1 ausgeführt, jedoch mit Benzylbromid als Benzylhalogenid. Aufgrund der besseren Löslichkeit von MgBr2 relativ zu MgCl2 in 2 -Methyl-THF tritt kein Niederschlag auf, es resultiert eine klare Lösung. Analyse nach Hydrolyse des Filtrats :This example is carried out in accordance with Example 1, but with benzyl bromide as the benzyl halide. Due to the better solubility of MgBr 2 relative to MgCl 2 in 2-methyl-THF, no precipitation occurs, a clear solution results. Analysis after hydrolysis of the filtrate:
OH" 1,22 mmol/gOH " 1.22 mmol / g
Br" 1,21 mmol/g Mg2* 1,22 mmol/gBr " 1.21 mmol / g Mg 2 * 1.22 mmol / g
Die Gesamtausbeute beträgt 97,8%.The overall yield is 97.8%.
Beispiel 3Example 3
In einem Doppelmantelreaktor werden 13 , 3 g (547 mmol = 20 % Überschuß) Magnesiumspäne in 260 g 2-Methyl-THF vorgelegt. 35 g (457 mmol) AllylChlorid werden innerhalb von 100 Minuten zudosiert. Die Reaktionstemperatur wird durch Kühlung auf 30 °C begrenzt. Während der Zugabe fällt ein weißer Niederschlag aus. Die Nachreaktionszeit beträgt 60 Minuten bei 25 °C. Nach Filtration erhält man eine Lösung mit folgender Analyse:13.3 g (547 mmol = 20% excess) of magnesium shavings in 260 g of 2-methyl-THF are placed in a double jacket reactor. 35 g (457 mmol) allyl chloride are added within 100 minutes. The reaction temperature is limited to 30 ° C. by cooling. A white precipitate precipitates out during the addition. The post-reaction time is 60 minutes at 25 ° C. After filtration, a solution is obtained with the following analysis:
OH" 1,53 mmolOH " 1.53 mmol
Cl" 0, 97 mmol Mg2t 1,24 mmolCl " 0.97 mmol Mg 2t 1.24 mmol
Der Rückstand, bestehend aus MgCl2, wird mit 2 -Methyl-THF gewaschen. Die Ausbeute beträgt 89%.
Tabelle 1The residue, consisting of MgCl 2 , is washed with 2-methyl-THF. The yield is 89%. Table 1
Ausgangsverbindung Lösungsmittel mol Mg / Ausbeute % mol HalogenidStarting compound solvent mol Mg / yield% mol halide
Ph-CH2CI THF 2,00 80 - 90Ph-CH 2 CI THF 2.00 80-90
Ph-CH2CI 2-Methyl-THF 1 ,20 99Ph-CH 2 CI 2-methyl-THF 1, 20 99
Ph-CH2CI 2-Methyl-THF 1 ,05 98Ph-CH 2 CI 2-methyl-THF 1, 05 98
2-CH3-Ph-CH2CI THF 2,00 782-CH 3 -Ph-CH 2 CI THF 2.00 78
2-CH3-Ph-CH2CI 2- ethyl-THF 1 ,40 972-CH 3 -Ph-CH 2 CI 2-ethyl-THF 1, 40 97
2-CI-Ph-CH2CI THF 2,00 202-CI-Ph-CH 2 CI THF 2.00 20
2-CI-Ph-CH2CI 2-Methyl-THF 1 ,20 862-CI-Ph-CH 2 CI 2-methyl-THF 1, 20 86
Ph-CH2Br THF 1 ,50 73Ph-CH 2 Br THF 1, 50 73
Ph-CH2Br THF 2,00 83Ph-CH 2 Br THF 2.00 83
Ph-CH2Br 2-Methyl-THF 1 ,20 98Ph-CH 2 Br 2-methyl-THF 1, 20 98
Allyl-Cl THF 1 ,20 73Allyl-Cl THF 1, 20 73
Allyl-Cl 2-Methyl-THF 1 ,20 89
Allyl-Cl 2-methyl-THF 1, 20 89
Umsetzungen von Benzylchlorid (Ph-CH2CI), 2-Methyl-Benzylchlorid (2-CH3-Ph-CH2CI), 2-Chlor-Benzyichlorid (2-CI-Ph-CH2CI), Benzylbromid (Ph-CH2Br) und Allylchlorid mit Mg-Spänen.Reactions of benzyl chloride (Ph-CH 2 CI), 2-methyl-benzyl chloride (2-CH 3 -Ph-CH 2 CI), 2-chloro-benzyichloride (2-CI-Ph-CH 2 CI), benzyl bromide (Ph- CH 2 Br) and allyl chloride with Mg chips.
Umsetzungen mit THF sind nicht erfindungsgemäß und dienen zu Vergleichszwecken Umsetzungen mit 2-Methyl THF sind erfindungsgemäßReactions with THF are not according to the invention and are used for comparison purposes. Reactions with 2-methyl THF are according to the invention
Tabelle 2Table 2
Grignardverbindung Konzentration / Molverhältnis mmol / g R-MgX : R2MgGrignard compound concentration / molar ratio mmol / g R-MgX: R 2 Mg
Ph-CH2-MgCI 1 ,48 1 : 0,28Ph-CH 2 -MgCI 1, 48 1: 0.28
2-CH3-PhCH2-MgCI 1 ,53 1 : 0,362-CH 3 -PhCH 2 -MgCI 1.53 1: 0.36
2-CI-PhCH2-MgCI 1 ,29 1 : 0,672-CI-PhCH 2 -MgCI 1, 29 1: 0.67
Ph-CH2-MgBr 1 ,22 1 : 0Ph-CH 2 -MgBr 1, 22 1: 0
Allyl-MgCI 1 ,53 1 : 0,29
Allyl-MgCl 1.53 1: 0.29
Molverhältnis R-MgX : R2Mg in den benzyl- und allylmagnesiumhalogenidhaltigen Synthesemitteln
R-MgX: R 2 Mg molar ratio in the benzyl- and allylmagnesium halide-containing synthesis agents
Claims
1. Benzylmagnesiumhalogenide oder Allylmagnesiumhalogenide enthaltende Synthesemittel, dadurch gekennzeichnet, daß die Benzylmagnesiumhalogenide oder Allylmagnesiumhalogenide in 2 -Methyltetrahydrofuran oder in einem 2- Methyltetrahydrofuran enthaltenden Lösungsmittelgemisch vorliegen.1. Benzylmagnesiumhalogenide or Allylmagnesiumhalogenide containing synthetic agents, characterized in that the Benzylmagnesiumhalogenide or Allylmagnesiumhalogenide are present in 2-methyltetrahydrofuran or in a solvent mixture containing 2-methyltetrahydrofuran.
2. Synthesemittel nach Anspruch 1, dadurch gekennzeichnet, daß die Benzylmagnesiumhalogenide oder Allylmagnesiumhalogenide in einem Gemisch von 2-Methyltetrahydrofuran und einem aromatischen Lösungsmittel vorliegen.2. Synthesis agent according to claim 1, characterized in that the benzylmagnesium halides or allylmagnesium halides are present in a mixture of 2-methyltetrahydrofuran and an aromatic solvent.
3. Synthesemittel nach einem oder mehreren der Ansprüche 1 bis3. Synthesis agent according to one or more of claims 1 to
2, dadurch gekennzeichnet, daß die Phenylgruppe der Benzylmagnesiumverbindung oder die Allylmagnesiumverbindung einen oder mehrere der folgenden Substituenten trägt:2, characterized in that the phenyl group of the benzyl magnesium compound or the allyl magnesium compound carries one or more of the following substituents:
- Fluor, Chlor,- fluorine, chlorine,
- Cj^- bis C8-Alkylgruppen,- C j ^ to C 8 alkyl groups,
- C - bis C8-Halogenalkylgruppen mit Fluor und/oder Chlor als Halogenatom,C to C 8 haloalkyl groups with fluorine and / or chlorine as the halogen atom,
- Cx- bis C3-Alkoxygruppen,C x to C 3 alkoxy groups,
- Cx- bis C3-Halogenalkoxygruppen mit Fluor und/oder Chlor als Halogenatom,C x to C 3 haloalkoxy groups with fluorine and / or chlorine as the halogen atom,
- C2- bis C6-Alkenylgruppen, C3- bis C6-Cycloalkylgruppen,C 2 to C 6 alkenyl groups, C 3 to C 6 cycloalkyl groups,
- die Trimethylsilylgruppe und- The trimethylsilyl group and
- die Phenylgruppe oder die Phenoxygruppe , die ihrerseits die vorgenannten Substituenten tragen können.- The phenyl group or the phenoxy group, which in turn can carry the aforementioned substituents.
4. Synthesemittel nach einem oder mehreren der Ansprüche 1 bis4. Synthesis agent according to one or more of claims 1 to
3, dadurch gekennzeichnet, daß im Synthesemittel ein Benzylmagnesiumhalogenid und eine
103, characterized in that in the synthesis agent a benzyl magnesium halide and 10
Dibenzylmagnesiumverbindung im Molverhältnis von 1 : 0 bis 0 : 1 enthalten sind.Dibenzylmagnesiumverbindung in a molar ratio of 1: 0 to 0: 1 are included.
5. Verfahren zur Herstellung eines Synthesemittels gemäß einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß5. A method for producing a synthetic agent according to one or more of claims 1 to 4, characterized in that
a) Magnesium in 2-Methyltetrahydrofuran oder in einem Lösungsmittelgemisch, welches 2-Methyltetrahydrofuran enthält, dispergiert und ein Benzylmagnesiumhalogenid oder ein Allylmagnesiumhalogenid zudosiert wird,a) dispersing magnesium in 2-methyltetrahydrofuran or in a solvent mixture which contains 2-methyltetrahydrofuran and metering in a benzylmagnesium halide or an allylmagnesium halide,
b) die Reaktionstemperatur im Bereich von -10 bis +100°C, vorzugsweise 0 bis +40°C, gehalten wird undb) the reaction temperature is kept in the range from -10 to + 100 ° C, preferably 0 to + 40 ° C and
c) das bei der Reaktion gebildete und ausgefallene Magnesiumhalogenid abgetrennt wird.
c) the magnesium halide formed and precipitated during the reaction is separated off.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998108570 DE19808570C1 (en) | 1998-02-28 | 1998-02-28 | Synthesis reagent comprising benzyl-or allyl-magnesium halide |
| DE19808570 | 1998-02-28 | ||
| PCT/EP1999/000264 WO1999043684A1 (en) | 1998-02-28 | 1999-01-18 | Synthesis agents containing benzyl magnesium halogenides or allyl magnesium halogenides and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| EP1056750A1 true EP1056750A1 (en) | 2000-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99907379A Ceased EP1056750A1 (en) | 1998-02-28 | 1999-01-18 | Synthesis agents containing benzyl magnesium halogenides or allyl magnesium halogenides and method for producing same |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP1056750A1 (en) |
| DE (1) | DE19808570C1 (en) |
| WO (1) | WO1999043684A1 (en) |
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| CN101061087A (en) * | 2004-07-07 | 2007-10-24 | 意大利灵北医药有限公司 | Process for the synthesis and purification of (4-methoxybutyl)(4-trifluoromethylphenyl)methanone |
| US7205414B2 (en) | 2005-01-12 | 2007-04-17 | Honeywell International Inc. | Process for the Kumada coupling reaction |
| EP1994037A1 (en) | 2006-03-03 | 2008-11-26 | Chemetall GmbH | Organomagnesium synthesis agent |
| CN103755516B (en) * | 2013-12-27 | 2016-03-02 | 浙江工业大学 | Preparation method of 1, 1-diphenylethylene |
| CN106279216A (en) * | 2016-04-06 | 2017-01-04 | 海正化工南通股份有限公司 | A kind of synthesis way of o-chlorobenzyl magnesium chloride |
| AU2018411552B2 (en) * | 2018-03-06 | 2024-06-20 | Upl Ltd | Improved process for preparation of intermediates |
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| DE3928812A1 (en) * | 1989-08-31 | 1991-03-07 | Basf Ag | METHOD FOR PRODUCING ETHERIC SOLUTIONS OF ARYLMETHYL MAGNESIUM HALOGENIDES |
| GB9115246D0 (en) * | 1991-07-16 | 1991-08-28 | Ici Plc | Process for the preparation of arylmagnesium halides |
| GB9126339D0 (en) * | 1991-12-11 | 1992-02-12 | Ici Plc | Chemical process |
| DE4439003C1 (en) * | 1994-11-01 | 1996-02-22 | Metallgesellschaft Ag | Grignard reagents comprising benzyl-magnesium halide |
| US5747407A (en) * | 1996-08-29 | 1998-05-05 | Phillips Petroleum Company | Method of making a Ziegler-Natta olefin polymerization catalyst |
-
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- 1998-02-28 DE DE1998108570 patent/DE19808570C1/en not_active Expired - Fee Related
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