EP2142556A1 - Préparation et utilisation d'amides de magnésium - Google Patents

Préparation et utilisation d'amides de magnésium

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Publication number
EP2142556A1
EP2142556A1 EP08701246A EP08701246A EP2142556A1 EP 2142556 A1 EP2142556 A1 EP 2142556A1 EP 08701246 A EP08701246 A EP 08701246A EP 08701246 A EP08701246 A EP 08701246A EP 2142556 A1 EP2142556 A1 EP 2142556A1
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EP
European Patent Office
Prior art keywords
cyclic
substituted
general formula
amides
thf
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EP08701246A
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German (de)
English (en)
Inventor
Giuliano Cesar Clososki
Christoph Josef Rohbogner
Paul Knochel
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Ludwig Maximilians Universitaet Muenchen LMU
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Ludwig Maximilians Universitaet Muenchen LMU
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Priority claimed from PCT/EP2007/050492 external-priority patent/WO2007082911A1/fr
Application filed by Ludwig Maximilians Universitaet Muenchen LMU filed Critical Ludwig Maximilians Universitaet Muenchen LMU
Priority to EP08701246A priority Critical patent/EP2142556A1/fr
Publication of EP2142556A1 publication Critical patent/EP2142556A1/fr
Withdrawn legal-status Critical Current

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Definitions

  • the present application relates to magnesium amides, a method for the preparation of magnesium amides and the use of these amides.
  • the reactivity of the Grignard reagents can be increased by forming a magnesiate intermediate. These Grignard reagents then show a higher reactivity and selectivity due to the formation of a magnesiate intermediate.
  • a further object of the present invention is to provide a magnesium base showing a high kinetic activity and a high selectivity.
  • mixed magnesium and lithium amides of type R 1 R 2 N-MgX-ZLiY (I) can be prepared by reacting an amine R 1 R 2 NH with a Grignard reagent R'MgX in the presence of LiY or with R'MgX-zLiY in a solvent.
  • R , R and R' independently are selected from substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, and, for R 1 and R 2 only, the silyl derivatives thereof.
  • R 1 and R 2 may be H; or R 1 and R 2 together can be part of a cyclic or polymeric structure.
  • X and Y may be identical or different. In the above given context, z > 0.
  • the amides of formula I can also be prepared in an alternative way by reacting a lithium amide of the formula R 1 R 2 NLi with a magnesium salt of the form MgX 2 or Mg XY. This reaction is preferably carried out in a solvent. In order to achieve a compound of formula I, the magnesium salt and the lithium amide are reacted in approximately equimolar ratio. Thus, the ratio of lithium amide to magnesium salt is usually in the range of 1:0.8-1.2, preferably in the range of 1:0.9-1.1, and most preferably in the range of 1:0.95-1.05.
  • the amides of formula I are not part of the present invention.
  • R 1 , R 2 , R 3 , and R 4 are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R 1 and R 2 together, and/or R 3 and R 4 together can be part of a cyclic or polymeric structure; and wherein at least one of R 1 and R 2 and at least one of R 3 and R 4 is other than H.
  • the bisamides of the general formula II can be prepared from the monoamides of formula I.
  • a bisamide of formula II is formed.
  • This reaction is equivalent to a reaction of a generally known Grignard reagent R 'MgX in the presence of an amine R 1 R 2 NH, and subsequently with R 3 R 4 NLi.
  • the lithium may also be added as a lithium salt in the form LiY, especially when the Grignard reagent or the monoamide are not complexed with a lithium salt.
  • the reagent may also be of the form R R N-MgX-zLiY, wherein a lithium salt is already present with the monoamide. In this way, bisamides may be prepared, wherein the two amides are different. However, the two amides may also be the same.
  • the two amides are different, i.e. R 1 R 2 N is not the same as R R N.
  • the reactivity and selectivity of the mixed magnesium lithium amides strongly depends on the one of the two amides. If both amides are identical, the difference in reactivity and selectivity can not be seen. However, if both amides differ, one of the two amides is responsible for the reactivity of the complex compound. In such a case, one of the two amide functions may be a cheap and easily introducible amide, and the other amide function may be selected for the good reactivity and selectivity.
  • one of the amides is TMP and the other is diisopropylamide.
  • the magnesium amides containing two amides are referred to as bisamides, irrespective of the fact that the two amides may also be different. In the latter case, i.e. when the two amides are different, these magnesium amides may also be referred to as magnesium diamides, or heteroamides. When the two amide functions are identical, the magnesium amide may be termed as homoamide.
  • the bisamides may be prepared by reacting two lithium amides R 1 R 2 NLi and R 3 R 4 NLi with a magnesium salt MgX 2 . If both lithium amides are identical, or a magnesium monoamide is reacted with a lithium amide of the same type, a bisamide of the general formula Mg(NR 'R 2 ) 2 -zLiY will result. For a higher solubility of the magnesium salt MgX 2 , this salt may be prepared in situ, for example as described below.
  • X is not present in formula II, it is defined above as it is used in the preparation of compounds of formula II.
  • X may be selected from the same group as Y and may be different or identical to Y.
  • the bisamides of the present invention show an increased solubility and a high reactivity.
  • the amides of the present invention are bases which will tolerate many functional groups, especially halogen substituents. This is due to the different nature of the nitrogen magnesium bond present in the amides of the present application in view of a carbon magnesium bond as in Grignard reagents.
  • the increase in reactivity of the Grignard reagents in the presence of a lithium salt is due to the formation of magnesiate intermediates. In contrast thereto, however, the lithium salt which is added to the amides according to the present application prevents the formation of aggregates.
  • the solvent is selected from cyclic, linear or branched mono or polyethers, thioethers, amines, phosphines, and derivatives thereof containing one or more additional heteroatoms selected from O, N, S and P, preferably tetrahydrofuran (THF), 2-methyltetrahydrofuran, dibutyl ether, diethyl ether, tert-butylmethyl ether, dimethoxyethane, dioxanes, preferably 1,4-dioxane, triethylamine, ethyldiisopropylamine, dimethylsulfide, dibutylsulfide; cyclic amides, preferably N-methyl-2- pyrrolidone (NMP), N- e
  • the process for the preparation of amides of formula I is carried out by reacting an amine R 1 R 2 NH with a Grignard reagent R'MgX in the presence of LiY or with R'MgX-zLiY in a solvent.
  • the materials are contacted preferably at room temperature for the minimum time necessary to provide the desired yield. Temperatures between O 0 C and 50 0 C are preferred, however, higher or lower reaction temperatures are also suitable.
  • the preparation of the bisamides of formula II is usually carried out at temperatures between -40 0 C and 5O 0 C, preferably in the range of ⁇ 20°C to 30 0 C and most preferred at around 0 0 C. A person skilled in the art will, however, be able to select a suitable temperature for the preparation of the amides of formula I or II by routine experimentation.
  • X and Y are independently or both Cl, Br or I, and preferably Cl.
  • the preparation of a compound of formula I is achieved by /PrMgCl-LiCl [5] .
  • This process is particularly preferred since iPrMgCl-LiCl is commercially available.
  • any Grignard reagent can be used to prepare the mixed Mg/Li-amides in the presence of any lithium salt. It is nevertheless preferred to use a Grignard reagent the side or by-products of which can easily be removed from the reaction mixture.
  • the presence of a lithium salt accelerates the exchange reaction compared to homoleptic reagents RMgX and R 2 Mg without the use of a lithium salt.
  • the present invention is directed to a mixed Mg/L ⁇ bisamide of the general formula R 1 R 2 N-MgNR 3 R 4 ZLiY (II), wherein R 1 , R 2 , R 3 , R 4 , Y and z are defined as above. It is to be understood that the adduct of a solvent is also comprised by any of these formulae.
  • a third aspect of the present invention is directed to a solution of the amide (II) in a solvent.
  • the solvent can be any suitable solvent capable of dissolving the amide.
  • Especially preferred solvents are the solvents listed above for the preparation of the amides.
  • the solvent used to dissolve the mixed amides or used for the solvent adduct of the mixed amides contains a Lewis base.
  • a Lewis base in the understanding of the present application is a molecule having an electron lone pair in a bonding orbital.
  • a specifically preferred Lewis base for the amides of the present invention is THF.
  • Other preferred Lewis bases may be selected from 2-methyl THF, dioxane, mixtures of THF and/or 2-methyl THF with dioxane, mixtures of pentane and/or hexane with THF and/or 2-methyl THF, and any mixture of the compounds, selected from diethylether, diisopropylether, di-n-butyl ether, cyclopentylmethyl ether, methyl tert-butyl ether, THF and 2-methyl THF.
  • the Lewis base is present in an amount of 4-30 eq, preferably in an amount of 4.5-20 eq, even more preferably in an amount of 5-15 eq, and most preferably in an amount of 5-10 eq, in relation to the amount of Mg in the amide.
  • the present invention is related to the use of mixed Mg/Li amides (II).
  • the amides of the present invention can be used to remove acidic protons.
  • the deprotonated species can then subsequently be quenched with an electrophile.
  • electrophiles that are, for example, cited in the following references, but are not limited thereto:
  • the bis amides of the present invention combine a high reactivity at a high selectivity or tolerance towards other functional groups within a molecule. Especially, this effect can be seen with aromatic reagents substituted with sensitive functional groups. These aromatic, or heteroaromatics, need a highly reactive base to be deprotonated, and at the same time, the base has to tolerate other functional groups like esters or mtriles. Benzonitrile or benzoic acid esters are examples of such compounds. These aromatic compounds can be deprotonated with common bases like LDA, LiHMDS oder n-Buhi, however, the bases will not tolerate any other functional groups within the reagent.
  • magnesium monoamides like TMPMgCl-LiCl are too unreactive to deprotonate the aromatic reagent.
  • the base has to be added in a high surplus, needing a surplus of the electrophile.
  • the new bisamides of the present invention give a solution to this problem as these compounds combine a high reactivity at a high selectivity.
  • a preferred embodiment of the present invention refers to the use of magnesium bisamides of the present invention for the deprotonation of aromatics and heterocycles.
  • the aromatics or heterocycles are substituted with a phosphorodiamidate, more preferably with tetramethylphosphorodiamidate, Phosphorodiamidates can be used as directing metalation groups (DMG) and allow a substitution pattern of the aromatics or heterocyles which would otherwise not be possible.
  • DMG directing metalation groups
  • the final aspect of the invention relates to the product of the reaction of an electrophile with a substrate which has been deprotonated with a reagent of the general formula II.
  • z is preferably in the range of from 0.01-5, more preferably, z > 1, more preferably, z is in the range from 1 - 5, more preferably from 0.5 - 2.5, further more preferably from 1.5 to 2.5, even more preferably from 1.8 to 2.2, even further more preferably from 1.9 to 2.1, still even more preferably from 1.95 to 2.05, and most preferred about 2.
  • the inventors of the present invention surprisingly found that the lithium salt is most preferably used in an equal amount in relation to the amide function of the bisamide.
  • the amount of lithium salt is thus most preferably about 2, however, a slight deviation of this optimum value still leads to acceptable results.
  • the present invention is described in the following on the basis of specific examples. Especially, i-PrMgCl is used as Grignard reagent. However, it is to be understood that the present invention is not limited to such examples.
  • alkyl refers to linear, cyclic and branched, substituted and unsubstitued C 1 -C 2O compounds. Preferred ranges for these compounds are C 1 -Ci 0 , preferably C]-C 5 (lower alkyl) and C 2 -Ci 0 and preferably C 2 -C 5 , respectively, for alkenyl and alkynyl.
  • cycloalkyl generally refers to linear and branched, substituted and unsubstitued C 3 -C 2O cycloalkanes.
  • preferred ranges are C 3 - Ci5, more preferably C 3 -C 8 .
  • the subst ⁇ tuent may be selected by a person skilled in the art from any known substituent.
  • a person skilled in the art will select a possible substituent according to his knowledge and will be able to select a substituent which will not interfere with other substituents present in the molecule and which will not interfere or disturb possible reactions, especially the reactions described within this application.
  • substituents include without limitation halogenes, preferably fluorine, chlorine, bromine and iodine; aliphatic, alicyclic, aromatic or heteroaromatic hydrocarbons, especially alkanes, alkylenes, arylenes, alkylidenes, arylidenes, heteroarylenes and heteroarylidenes; carbonxylic acids including the salts thereof; carboxylic acid halides; aliphatic, alicyclic, aromatic or heteroaromatic carboxylilc acid esters; aldehydes; aliphatic, alicyclic, aromatic or heteroaromatic ketones; alcohols and alcoholates, including a hydroxyl group; phenoles and phenol ates; aliphatic, alicyclic, aromatic or heteroaromatic ethers; aliphatic, alicyclic, aromatic or heteroaromatic peroxides; hydroperoxides; aliphatic, alicyclic, aromatic or heteroaromatic amides or amidines; nit
  • the substituents may be bound to the residues R 1 , R 2 , R 3 and/or R 4 via a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom.
  • the hetero atoms in any structure containing hetero atoms, as e.g. hetero arylenes or heteroaromatics, may preferably be N, O, S and P.
  • R 1 and R 2 , or R 3 and R 4 can be part of a cyclic structure
  • R 1 and R 2 together, or R 3 and R 4 together are a divalent saturated or unsaturated, linear or branched alkyl, alkenyl or alkynyl which forms in connection with the nitrogen atom of the amide a cyclic secondary amide.
  • An example of such a cyclic amide is the amide of TMPH.
  • the residues R 1 and R 2 , and/or R 3 and R 4 can be part of a polymeric structure.
  • the nitrogen atom of the amide is the connected to a polymeric backbone which may even contain more than one nitrogen atom for the formation of an amide according to the invention.
  • aryl refers to substituted or unsubstituted C 4 -C 24 aryl.
  • heteroaryl a substituted or unsubstituted C 3 -C 24 aryl, containing one or more heteroatoms as B, O, N, S, Se, P, is meant.
  • Preferred ranges for both are Q-C1 5 , more preferably C 4 -Q 0 and includes aryls and fused aryls with or without heteroatoms.
  • a preferred ring size comprises 5 or 6 ring atoms.
  • TMPH 2,2,6,6-tetramethylpiperidine
  • TMPMgCI-LiCI Traces TMP 2 Mg-2LiCi: 70 % s %
  • the activity of the amides (I) can be shown on the basis of the magnesiation of isoquinoline.
  • Diisopropylamido magnesium chloride-lithium chloride 5a leads to the magnesiated isoquinoline 6 after 12 h reaction time at 25°C and by using 2 equivalents of the base.
  • the iodoisoquinoline 7a is isolated in 88% yield (Scheme 2).
  • Even more active is the sterically more hindered and less aggregated 2,2,6,6-tetramethylpiperidino magnesium chloride-lithium chloride reagent 5b. It leads to a complete magnesiation within 2 h at 25°C.
  • the magnesiation of heterocycles bearing more acidic protons' 71 such as thiazole, thiophene, furan, benzothiophene or benzothiazole proceeds smoothly between 0 0 C and 25°C leading to the organomagnesium derivatives 14a-c and 16a-b. After trapping with standard electrophiles, the expected products 15a-c and 17a-b are obtained in 81-98% yield (entries 10-14 of Table 1).
  • the mixed magnesium-lithium amide 5b is also well suited for the regioselective metalation of polyfunctional aromatic systems.
  • the reaction of 2-phenylpyridine 27 in THF at 55°C with 5b (2.0 equiv.) for 24 h provides the Grignard reagent 28 showing a rare case where a phenyl ring is preferentially metalated compared to a pyridine ring.
  • the ortho- iodinated product 29 is obtained in 80% yield.
  • the metalation of polyfunctional aromatics such as the bromodiester 30 also succeeds using only the stoichiometric amount of base 5b (1.1 equiv.) in THF (-30 0 C, 0.5 h) leading regioselectively to the arylmagnesium species 31 which after iodolysis furnishes the polyfunctional aromatic derivative 32 in 88% yield.
  • TMPMgCl-LiCl A solution of TMPMgCl-LiCl can easily be prepared in THF due to its excellent solubility and it is stable for more than 6 months at 25°C.
  • the use of TMPMgCl-LiCl allows for the regioselective functionalization of various aromatics and heteroaromatics. It gives access to new magnesium species not readily available via a Br/Mg-exchange reactions or by previously reported metalation procedures.
  • R 1 and R 2 are not limited to organic compounds.
  • R 1 and R 2 may also be silylated compounds like trimethylsilyl.
  • the preparation of the b ⁇ s(trimethylsilyl) amide 33 can be achieved by reacting bis(trimethylsilyl)amine with i-PrMgCl LiCl at room temperature (see Scheme 5). This base can efficiently be used to deprotonate ketones like e.g. cyclohexanone as can be seen from Scheme 5.
  • Scheme 5 Preparation and use of silylated magnesium amide
  • the Grignard reagents can also be used to prepare a polymeric base.
  • 2,2,6, 6-Tetramethyl piperidine (TMPH) is a well known base. It can be used to prepare the corresponding mixed Mg/Li amide TMPMgCl-LiCl 5b. This monomeric base is very reactive but also very expensive.
  • a corresponding polymeric base to TMPH is chimassorb 994, the structure of which is shown in Scheme 6.
  • Chimassorb 994 can be used to prepare the corresponding mixed Mg/Li amide by reacting chimassorb 994 with j-PrMgCl-LiCl at room temperature (see Scheme 5).
  • This base 34 is stable and soluble in THF before and after deprotonation. As being a polymeric base, it can be easily removed after completion of the reaction. Since chimassorb 994 is much cheaper than TMP, a corresponding base can be prepared at reduced costs.
  • the polymeric base 34 shows slightly lower activity than monomeric TMPMgCl-LiCl but is nevertheless very effective in deprotonating compounds with acidic protons like isoquinoline. A corresponding example is shown in Scheme 7.
  • the polymeric base can be used to deprotonate various substrates. For example, isoquinoline reacts at room temperature with the base 34 affording after quenching with iodine 1-iodoisoquinoline 7a.
  • TMP 2,2,6,6-tetramethylpiperidide
  • Scheme 10 gives an overview over examples of reactions of four different aromatic substances (41-44) with (TMP) 2 Mg- 2LiCl (40a) and TMPMgCl-LiCl (5b) under identical conditions. The respective yields are indicated for the products of each of the two amides 40a and 5b. This experiment clearly shows the even superior reactivity of the bisamides in view of the monoamides. All reactions are carried out at room temperature (rt) being at 25°C.
  • the unsymmetrical reagents 40e-40i are prepared from TMPMgCl LiCl, /-Pr 2 NMgCl-LiCl and (2- ethyl-hex Vl) 2 NMgCl -LiCl' 91 , respectively, and the corresponding lithium species of lH-benzotriazole (Bt), 5,6-dimethyl-lH-benzotriazole (DMBt) and carbazole (CBZ), respectively (Scheme 11).
  • the base 4Oe provides a far higher reactivity than TMPMgCl-LiCl (5b) and (TMP) 2 Mg- 2LiCl (40a) when using special directing metalation groups (DMG).
  • TMPMgCl LiCl provides full metalation of 44 in 90 minutes at 0°C
  • reagent 40a provides full metalation in 60 minutes.
  • the use of 4Oe provides full metalation at 0°C in only 10 minutes.
  • only 1.3 equivalents of the base 4Oe are used in contrast to 1.5 equivalents of TMPMgCl-LiCl.
  • the yield of 44a is higher compared to the use of TMPMgCl-LiCl (Scheme 12).
  • the regulating intermediates derived from (TMP)Mg(Bt)-2LiCl show good stability and tolerance to various substrates. They can be trapped with an electrophile like iodine to provide the corresponding functional ized derivatives in good yields. Examples are shown in Table 3.
  • the compounds of the present invention can also be used in connection with a phosphorodiamidate group on an aryl or heteroaryl. This effect will be shown in the following with the N,N,N',N'-tetramethylphosphorodiamidate ((Me 2 N) 2 P(O)O-) group, but is not limited to this specific group. As a person skilled in the art will recognize immediately, other directing metalation groups can also be used, especially other phosphorodiamidate groups.
  • Ortho-ditect ⁇ d metalation is an important method for the functionalization of various aromatics and heterocycles.
  • Various DMG directed metalation groups
  • the DMG allow for a fast and ort/io-selective metalation mainly by chelation (entropic effect).
  • Polar DMG may furthermore transfer electron density to the metal base and increase their metalating power.
  • magnesiate bases have proven to be of great structural and synthetic interest for the functional! zation of aromatics.
  • the magnesiation of substrates 61 and 62using TMP 2 Mg'2LiCl (40a) proceeds smoothly within a few hours at 0 0 C for cyano- and ester-substituted phosphorodiamidates 60a and 61a (entries 1-3, 10-13).
  • This electronic effect increases the metalation power of the base and no additional chelation or inductive effects are necessary for achieving the magnesiation.
  • this phosphorodiamidate-triggered magnesiation preferentially occurs at the sterically less hindered position of the aromatic ring promoting formal m ⁇ -metalation.
  • the inventors observed that the regioselectivity of the metalation is affected by the competitive directing effects of these halogens.
  • the ketone 62a was converted to the diketone 66a in 77% yield. Furthermore, the double functionalization of the bromo- and chloro-substituted phosphorodiamidates 60b and 6Od led to the preparation of the highly functionalized phosphorodiamidates 66b and 66c in good overall yields, showing the high directing power of the OP(O)(NMe 2 ) 2 group (Scheme 15).
  • this approach allows to achieve new functionalization pattern of aromatics by performing magnesiations using the powerful TMP 2 Mg*2LiCl base (40a) combined with the phosphorodiamidate (-OP(O)(NMe 2 ) 2 ) as strong directing metalation group.
  • This methodology allows a general preparation of various meta-, para- and meta, meta'- polyfunctionalized aromatics which are not easily accessible by using conventional synthetic strategies. Applications toward the synthesis of biologically active molecules seem to be feasible with this approach.
  • the new mixed Mg/Li-bases are very effective in deprotonating organic compounds.
  • the deprotonation can be achieved in different solvents and can preferably be conducted at temperatures between -9O 0 C and 100 0 C.
  • the amides of the present invention preferably only require the use of 0.9-5 equivalents, more preferably 1-2 equivalents and most preferably 1.1-1.5 equivalents per proton to be deprotonated.
  • the MgCl 2 solution was then transferred via cannula into the TMPLi solution and the reaction mixture was stirred at 0 0 C for 30 min, then warmed to room temperature and stirred for an additional 1 h. The solvents were removed then in vacuo followed by addition of THF while stirring until complete dissolution of the salts.
  • the fresh (TMP) 2 Mg- 2LiCl solution was titrated prior to use at 0 0 C against benzoic acid using 4-(phenylazo)-diphenylamine as indicator.Average concentration in THF was 0,6 mol/1.
  • Benzotriazole (Bt)(1.19 g, 10.0 mmol) was placed in a flame dried, argon flushed 5O mI Schlenk tube equipped with magnetic stirring bar and septum. THF (10 ml) was added. The solution was cooled to -40 0 C. Then n-BuLi (3.62 ml, 2.76 M in hexane, 10.0 mmol) was added drop wise. White precipitate was formed immediately. After the end of the addition the resulting suspension was stirred at -40 0 C for 30 min. Then solvents were removed in vacuo followed by addition of TMPMgCl LiCl (8.93 ml, 1.12 M in THF, 10.0 mmol).
  • THF was removed in vacuo. To the resulting brownish gel, THF was added while stirring until complete dissolution of the salts.
  • the fresh (TMP)Mg(Bt) 2LiCl solution was titrated at room temperature against benzoic acid using 4-(phenylazo)-diphenylamine as an indicator. Average concentration in THF was found to be 0.35 mol/1.
  • TMPH 2,2,6,6-tetramethylpiperidine
  • (2-Ethyl-hexyl) 2 NMgClLiCl is prepared by reacting bis(2-ethylhexyl)amine with J-Pr 2 NMgCl LiCl in THF at room temperature for 48h.
  • J-Pr 2 NMgCl LiCl is prepared by reacting bis(2-ethylhexyl)amine with J-Pr 2 NMgCl LiCl in THF at room temperature for 48h.

Abstract

La présente invention concerne des amides de Mg/Li mélangés de formule générale R1R2N-Mg-NR3R4.zLiY (II) où R1, R2, R3 et R4 sont choisis, indépendamment, parmi H, un groupe aryle ou hétéroaryle substitué ou non substitué contenant un ou plusieurs hétéroatomes, un groupe linéaire, ramifié ou cyclique, substitué ou non substitué alkyle, alcényle, alcynyle ou leurs dérivés silyle ; et R1 et R2 ensemble, ou R3 et R4 ensemble peuvent faire partie d'une structure cyclique ou polymère ; et où au moins l'un de R1 et R2 et au moins l'un de R3 et R4 est différent de H ; Y est choisi dans le groupe constitué de F ; Cl ; Br ; I ; CN ; SCN ; NCO ; HalOn, où n = 3 ou 4 et Hal est choisi parmi Cl, Br et I ; NO3 ; BF4 ; PF6 ; H ; un carboxylate de formule générale RxCO2 ; un alcoolat de formule générale ORx ; un thiolate de formule générale SRx ; RxP(O)O2 ; ou SCORx ; ou SCSRx ; OnSRx, où n = 2 ou 3 ; ou NOn, où n = 2 ou 3 ; et leurs dérivés ; où Rx représente un groupe aryle ou hétéroaryle substitué ou non substitué contenant un ou plusieurs hétéroatomes, un groupe linéaire, ramifié ou cyclique, substitué ou non substitué alkyle, alcényle, alcynyle, ou leurs dérivés, ou H ; m vaut 0 ou 1 ; et z > 1 ; ainsi qu'un procédé de préparation des amides de Mg/Li mélangés et l'utilisation de ces amides, par exemple, en tant que bases.
EP08701246A 2007-01-18 2008-01-04 Préparation et utilisation d'amides de magnésium Withdrawn EP2142556A1 (fr)

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EP08701246A EP2142556A1 (fr) 2007-01-18 2008-01-04 Préparation et utilisation d'amides de magnésium

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/EP2007/050492 WO2007082911A1 (fr) 2006-01-18 2007-01-18 Preparation et utilisation d’amides-magnesium
PCT/EP2008/050066 WO2008087057A1 (fr) 2006-01-18 2008-01-04 Préparation et utilisation d'amides de magnésium
EP08701246A EP2142556A1 (fr) 2007-01-18 2008-01-04 Préparation et utilisation d'amides de magnésium

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EP2142556A1 true EP2142556A1 (fr) 2010-01-13

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Non-Patent Citations (1)

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