Alkaline earth metal-complexed metal bisamides
View Patent ↗The present invention relates to alkaline earth metal-complexed metal bisamides of the formula (I), to a process for preparation thereof and to the use thereof for metallation of aromatics, heteroaromatics, alkenes, alkynes and other organic compounds having activated C—H bonds.
1. Process for preparing an alkaline earth metal-complexed metal bisamide of formula (I) and/or a tautomer thereof
where
AE is an alkaline earth metal selected from calcium and magnesium;
M is a metal selected from metals from groups 3, 4, 7, 8, 9, 10, 11, 12, 13 of the Periodic Table of the Elements and the group of the lanthanoids;
X is a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine;
R 1 and R 2 are each independently selected from the group consisting of (C 1 -C 8 )alkyl optionally substituted by 1-2 R 3 radicals;
R 3 is independently selected from halogen, (C 1 -C 3 )alkoxy, (C 1 -C 3 )haloalkoxy and (C 2 -C 4 )dialkylamino;
or
R 1 and R 2 together form a —(CH 2 ) 4 —, —(CH 2 ) 5 — or —(CH 2 ) 2 O(CH 2 ) 2 — group, where each of these groups may optionally be substituted by 1-4 R 4 radicals;
R 4 is selected from halogen, (C 1 -C 3 )alkyl, (C 1 -C 3 )alkoxy, (C 1 -C 3 )haloalkoxy and (C 2 -C 4 )dialkylamino or (C 2 -C 4 )alkoxycarbonyl,
by reacting a chloroamine of formula (II)
in which the R 1 and R 2 radicals are each as defined above with
(i) metallic magnesium and/or calcium and/or
(ii) a magnesium and/or calcium halide and
(iii) an amount of a metal halide (M n+ X − n ) and/or
(iv) an amount of a metal (M),
where M and X are each as defined above.
2. Process according to claim 1 , where
AE is an alkaline earth metal selected from calcium and magnesium;
M is a metal selected from Sc, Ti, Mn, Fe, Co, Ni, Cu, Zn and Al;
X is a halogen atom selected from chlorine and bromine;
R 1 and R 2 together form a —(CH 2 ) 4 —, —(CH 2 ) 5 — or —(CH 2 ) 2 O(CH 2 ) 2 — group, where each of these groups may optionally be substituted by 1-4 R 4 radicals;
R 4 is selected from methyl, ethyl, n-propyl and i-propyl.
3. Process according to claim 1 , where
AE is an alkaline earth metal selected from calcium and magnesium;
M is a metal selected from Ti, Mn, Fe, Zn and Al;
X is chlorine;
R 1 and R 2 together form a —(CH 2 ) 5 — group substituted by 4 methyl groups.
4. Process according to claim 1 , where
AE is calcium or magnesium,
M is zinc or manganese;
X is chlorine; and
R 1 and R 2 together form a —C(CH 3 ) 2 (CH 2 ) 3 —C(CH 3 ) 2 — group.
5. Process according to claim 1 , where
AE is calcium or magnesium;
M is zinc;
X is chlorine; and
R 1 and R 2 together form a —C(CH 3 ) 2 (CH 2 ) 3 —C(CH 3 ) 2 — group.
6. Process according to claim 1 , wherein said process is executed within a temperature range from +20 to −20° C.
7. Process according to claim 1 , wherein the reaction is performed in a coordinating solvent selected from THF, 2-methyltetrahydrofuran, t-butyl methyl ether, 1,2-dimethoxyethane, diethyl ether, di-n-butyl ether and methyl cyclopentyl ether, or mixtures thereof.
8. Process according to claim 1 , wherein the reaction is performed in a mixture of a coordinating solvent selected from THF, 2-methyltetrahydrofuran, t-butyl methyl ether, 1,2-dimethoxyethane, di-n-butyl ether, methyl cyclopentyl ether and/or diethyl ether, and one or more noncoordinating solvents selected from aromatics and alkyl-substituted aromatics, preferably benzene, toluene, xylene and/or ethylbenzene, and alkanes, cycloalkanes and/or alkyl-substituted cycloalkanes, optionally cyclohexane, n-heptane, isooctane and/or methylcyclohexane.
9. Process according to claim 1 for preparation of an AE-complexed metal amide of the formula (I), wherein the process is performed in the presence of one or more lithium salts.
10. Alkaline earth metal-complexed metal bisamide of formula (I) and/or a tautomer, oligomer and/or polymer thereof
where
AE is an alkaline earth metal selected from calcium and magnesium;
M is a metal selected from metals from groups 3, 4, 7, 8, 9, 10, 11, 12, 13 of the Periodic Table of the Elements and the group of the lanthanoids;
X is a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine;
R 1 and R 2 are each independently selected from the group consisting of (C 1 -C 8 )alkyl optionally substituted by 1-2 R 3 radicals;
R 3 is independently selected from halogen, (C 1 -C 3 )alkoxy, (C 1 -C 3 )haloalkoxy and (C 2 -C 4 )dialkylamino;
or
R 1 and R 2 together form a —(CH 2 ) 4 —, —(CH 2 ) 5 — or —(CH 2 ) 2 O(CH 2 ) 2 — group, where each of these groups may optionally be substituted by 1-4 R 4 radicals;
R 4 is selected from halogen, (C 1 -C 3 )alkyl, (C 1 -C 3 )alkoxy, (C 1 -C 3 )haloalkoxy and (C 2 -C 4 )dialkylamino or (C 2 -C 4 )alkoxycarbonyl.
11. Alkaline earth metal-complexed metal bisamide of formula (I-iii) and/or a tautomer, oligomer and/or polymer thereof
where
AE is calcium or magnesium,
M is a metal selected from Sc, Ti, Mn, Fe, Co, Ni, Cu, Zn and Al;
X is a halogen atom selected from chlorine and bromine.
12. Mg-complexed zinc bisamide of the formula (I-iv)
13. Ca-complexed zinc bisamide of the formula (I-v)
14. An alkaline earth metal-complexed metal bisamide of the formula (I), according to claim 10 capable of being used as a base for metallation of one or more aromatics, heteroaromatics, alkenes, alkynes and/or other organic compounds having activated C—H bonds.