WO2007080121A2 - Process for preparing imino compounds - Google Patents
Process for preparing imino compounds Download PDFInfo
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- WO2007080121A2 WO2007080121A2 PCT/EP2007/000255 EP2007000255W WO2007080121A2 WO 2007080121 A2 WO2007080121 A2 WO 2007080121A2 EP 2007000255 W EP2007000255 W EP 2007000255W WO 2007080121 A2 WO2007080121 A2 WO 2007080121A2
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- 0 *c(c(*)c1*)c(*)c(*)c1N Chemical compound *c(c(*)c1*)c(*)c(*)c1N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
Definitions
- the present invention relates to a process for preparing imino compounds.
- metallocene catalysts in the polymerization of unsaturated compounds has a great influence on the preparation of polyolefins since it opens up a route to new types of polyolefinic materials or to materials having improved properties. There is therefore great interest in the development of novel families of catalysts for the polymerization of unsaturated compounds in order to obtain even better control over the properties of polyolefins and further novel products.
- transition metal catalysts comprising late transition metals
- Transition metal catalysts derived from late transition metals which are suitable for the polymerization of unsaturated compounds are known from the prior art.
- 1 ,2-diiminenickel and 2,6- bis(imino)pyridyliron complexes have been found to be particularly useful.
- the preparation of unsymmetrical 2,6-bis(imino)pyridyl compounds which bear two different imino groups is usually carried out via a first condensation of the corresponding diketo compounds with a primary amine.
- the intermediate obtained is then reacted with a second primary amine which is different from the first.
- the first step not only the monoimine but also the symmetrical diimine product are formed, so that the yield of the intermediate is usually very low. Particularly when primary amines having electron-pulling or relatively nonbulky groups are used, the yield of monoimine intermediate drops.
- WO 98/27124 discloses the synthesis of unsymmetrical 2,6-bis(imino)pyridyl compounds from the corresponding diketo compounds and anilines in toluene with addition of catalytic amounts of toluenesulfonic acid via monoimine intermediates.
- Monoimine intermediates having electron-pulling substituents are not disclosed.
- anilines which bear an electron-pulling substituent in the ortho position are used, the yield of monoimine intermediate is very low. It is an object of the present invention to provide an improved process for the synthesis of the monoimine intermediate, by means of which even primary amines having electron-pulling or relatively nonbulky substituents can be converted into the corresponding monoimine compounds in improved yields.
- These monoimine compounds are particularly well-suited as starting materials for the synthesis of unsymmetrical diimine compounds and lead to higher yields of unsymmetrical product.
- a 1 is chlorine, bromine or iodine
- the radicals R 1 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 - alkenyl, C 6 -C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical R 1 may also be substituted by halogens, NR 1 * 2 , OR 11 or SiR 12 3 and/or the radical R 1 may also be joined to R 3 to form a five-, six- or seven- membered ring, R 3 -R 5 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl
- G is C ! -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 40 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR 1 ' 2 , SiR 12 3 or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical G may also be substituted by halogens, NR 1 ' 2 , OR 11 or SiR 12 3 ,
- E '-E 3 are each, independently of one another, carbon, nitrogen or phosphorus, in particular carbon, and u is 0 when E '-E 3 is nitrogen or phosphorus and is 1 when E '-E 3 is carbon, which comprises the following steps:
- a primary amine is any compound which bears an NH 2 group, i.e. including hydrazines.
- G-NH 2 As primary amine, use is made of G-NH 2 , where the meaning of G and its preferred embodiments is the same as for the imine compound of the formula I.
- Examples of primary amines are methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert- butylamine, sec-butylamine, isobutylamine, tert-amylamine, n-pentylamine, n-hexylamine, n- octylamine, cyclohexylamine, aniline, 2-methylaniline, 2-chloroaniline, 2-bromoaniline, 2,6- dichloroaniline, 2,4-dichloro-6-methylaniline and 2,6-dibromoaniline.
- G preferably comprises a halogen-comprising substituent.
- a 1 is chlorine, bromine or iodine
- the radicals R 1 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 - alkenyl, C 6 -C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical R 1 may also be substituted by halogens, NR 1 ' 2 , OR 11 or SiR 12 3 and/or the radical R 1 may also be joined to R 3 to form a five-, six- or seven- membered ring, R 3 -R 10 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalky
- E'-E 3 are each, independently of one another, carbon, nitrogen or phosphorus, in particular carbon, and is 0 when E '-E 3 is nitrogen or phosphorus and is 1 when E '-E 3 is carbon.
- primary amines G-NH 2 used are anilines of the formula III
- G is preferably
- R 6 -R 10 are each, independently of one another, hydrogen, Cj-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR 1 ' 2 , OR 11 , halogen, SiR 12 3 or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R 6 -R 10 may also be substituted by halogens, NR 1 ' 2 , OR 11 or SiR 12 3 and/or two radicals R 6 -R 10 may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R 6 -R 10 are joined to one another to form a five-, six- or seven-membered heterocycle comprising at least
- E 1 to E 3 of the imine compound of the formula I or Ia and of the carbonyl compound II can be identical or different.
- E 1 to E 3 are each nitrogen, phosphorus or carbon, in particular nitrogen or carbon and particularly preferably carbon.
- the substituents R 1 of the imine compound of the formula I or Ia and of the carbonyl compound of the formula II can be varied within a wide range.
- Possible carboorganic substituents R 1 are, for example, the following: Ci-C 22 -alkyl which may be linear or branched, e.g.
- cyclopropane cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C 2 -C 22 -alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g.
- the organic radicals R 1 may also be substituted by halogens such as fluorine, chlorine or bromine, by amino NR 2 , for example dimethylamino, n-pyrrolidinyl or picolinyl, by alkoxy or aryloxy OR 11 , e.g.
- organosilicon substituents SiR 12 3 e.g. trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylphenylsilyl.
- Possible substituents R 11 are the same carboorganic radicals as described above for R 1 , where, if appropriate, two radicals R 11 may also be joined to form a 5- or 6-membered ring and/or may be substituted by halogen.
- organosilicon substituents SiR 12 3 possible radicals R 12 are the same carboorganic radicals described above for R 1 , where, if appropriate, two radicals R 12 may also be joined to form a 5- or 6-membered ring.
- Preferred radicals R 1 are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl or phenyl, in particular methyl.
- the substituents R 3 -R 10 of the imine compound of the formula I or Ia, of the carbonyl compound of the formula II and of the aniline of the formula III can also be varied within a wide range.
- Possible carboorganic substituents R 3 -R 10 are, for example, the following: Ci- C 22 -alkyl which may be linear or branched, e.g.
- cyclopropane cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane or cyclododecane, C 2 -C 22 -alkenyl which may be linear, cyclic or branched and in which the double bond may be internal or terminal, e.g.
- R 3 -R 10 may be amino NR 1 ' 2 , for example dimethylamino, N-pyrrolidinyl or picolinyl, alkoxy or aryloxy OR , e.g. methoxy, ethoxy or isopropoxy, or halogens, such as fluorine, chlorine or bromine.
- Possible substituents R 11 are the same carboorganic radicals described above for R'-R 2 , where, if appropriate, two radicals R 11 may also be joined to form a 5- or 6-membered ring and/or be substituted by halogen.
- radicals R 12 are the same carboorganic radicals described above for R 1 -R 2 , where, if appropriate, two radicals R 12 may also be joined to form a 5- or 6-membered ring, e.g. trimethylsilyl, triethylsilyl, butyldimethylsilyl, tributylsilyl, tri-tert-butylsilyl, triallylsilyl, triphenylsilyl or dimethylpheny lsi IyI .
- Preferred radicals R 3 -R 5 are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen.
- R 6 -R 7 are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, fluorine, chlorine and bromine.
- R 6 is particularly preferably fluorine, chlorine and bromine and R 7 is particularly preferably a Ci-C 20 -alkyl group, with R 7 preferably being bound to the aryl ring via a primary or secondary, preferably primary, carbon atom.
- R 8 and R 10 are hydrogen, methyl, ethyl, n-propyl, fluorine, chlorine and bromine, in particular hydrogen. R and R are preferably identical.
- Preferred radicals R 9 are hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, benzyl, phenyl, fluorine, chlorine and bromine, in particular hydrogen, methyl, fluorine, chlorine or bromine, very particularly preferably chlorine.
- a primary carbon atom is a carbon atom having the following substitution pattern -CH 2 -R, where R is a linear, branched or cyclic hydrocarbon radical having 1-30 carbon atoms, preferably C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or hydrogen, particularly preferably Ci-Ci 9 -alkyl or hydrogen.
- a secondary carbon atom is a carbon atom having the following substitution pattern -CH-R 2 , where R is a linear, branched or cyclic hydrocarbon radical having 1-30 carbon atoms, preferably Ci-Ci 9 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or hydrogen, particularly preferably Ci-C ⁇ -alkyl or hydrogen.
- Preferred anilines of the formula III are 2-chloroaniline, 2-bromoaniline, 2,6- dichloroaniline, 2,4-dichloro-6-methylaniline or 2,6-dibromoaniline.
- the molar ratio of the carbonyl compound II to the amine G-NH 2 used or the aniline of the formula III is generally from 1 :5 to 1 :0.8, preferably from 1 :2 to 1 :0.9 and particularly preferably from 1 : 1 to 1 : 1.2.
- the order of addition of the individual components is not critical.
- the carbonyl compound can be initially charged and the amine G- NH 2 or the aniline of the formula III can be added thereto.
- an acid catalyst for example Ci-Cio-carboxylic acids such as formic acid or acetic acid, sulfonic acids such as para-toluenesulfonic acid, also HCl, HBr, HI or H 2 SO 4 .
- the molar ratio of carbonyl compound II to acid catalyst is preferably in the range from 1 :0.00001 to 1 :0.01, preferably from 1 :0.0001 to 1 :0.001.
- reagents for absorbing the water formed in the reaction for example molecular sieves, phosphorus pentoxide or Si(OR) 4 , where R is a Ci-Cio-alkyl group.
- the phosphorus pentoxide can be used as the pure substance or as a mixture with an inert solid such as aluminum oxide, silica gel or aluminosilicate. Such mixtures are commercially available under the trade name Sicapent.
- the molar ratio of carbonyl compound II to phosphorus pentoxide is preferably in the range from 1 :0.1 to 1 : 100, preferably from 1 :1 to 1 :10 and particularly preferably from 1 : 1.5 to 1 :3.
- the ratio of Sicapent (about 50% by weight water uptake capacity) to carbonyl compound II is preferably in the range from 1 g of Sicapent per 0.1 mmol of carbonyl compound II to 1 g of Sicapent per 100 mmol of carbonyl compound II, preferably from 1 g of Sicapent per 1 mmol of carbonyl compound II to 1 g of Sicapent per 10 mmol of carbonyl compound II and particularly preferably from 1 g of Sicapent per 1.8 mmol of carbonyl compound II to 1 g of Sicapent per 6 mmol of carbonyl compound II.
- the order of addition of the phosphorus pentoxide is not critical; it is preferably added to the mixture of carbonyl compound II and primary amine G-NH 2 .
- the total amount of phosphorus pentoxide to be used can be added at the beginning of the reaction, or it can be added at intervals in a plurality of portions during the ongoing reaction. It has been found that the process proceeds particularly quickly when the total amount of phosphorus pentoxide is added at the beginning of the reaction.
- the order of addition of the acid catalyst and/or the reagent for the absorption of water is not critical; it is preferably added to the mixture of carbonyl compound II and amine G- NH 2 .
- aliphatic hydrocarbons such as pentane such as n- pentane, hexane such as n-hexane and isohexane, heptane such as n-heptane, octane such as n- octane, benzene, toluene, ethylbenzene, halogenated hydrocarbons such as dichloromethane or oxygen-comprising hydrocarbons such as diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol ethers, methanol, ethanol or isopropanol or mixtures thereof.
- pentane such as n- pentane
- hexane such as n-hexane and isohexane
- heptane such as n-heptane
- octane such as n- octane
- benzene tol
- the reaction is generally carried out at from 18 to 150°C, preferably from 30 to HO 0 C and particularly preferably from 50 to 9O 0 C.
- the reaction time is usually in the range from 30 minutes to 15 days, preferably from 5 hours to 5 days, particularly preferably from 8 hours to 3 days.
- the work-up is carried out in a customary manner, e.g. by the filtering of the product before or after removing the solvent under reduced pressure. Purification of the product obtained can subsequently be carried out in the usual ways, for example by means of chromatography or recrystallization.
- An advantage of the reaction in aliphatic, nonaromatic solvents is the purity of the product obtained directly after filtration, which makes a further work-up unnecessary.
- Carbonyl compounds of the formula II are prepared, for example, from 2,6- dibromopyridine as described in J. Organomet. Chem. 1973, 56, pp. 53-66.
- the imine compound of the formula I can be reacted with carbonyl compounds of the formula V to form imine compounds of the formula IV.
- R 1 -R 2 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R'-R 2 may also be substituted by halogens, NR 1 S, OR 11 or SiR 12 3 and/or the two radicals R -R may also be joined to R -R 5 to form a five-, six- or seven-membered ring, R 3 -R 5 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 2 2-aryl, arylalkyl having from 1 to 10 carbon
- radicals R 11 may also be substituted by halogens and two radicals R 11 may also be joined to form a five- or six-membered ring and the radicals R 12 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 - alkenyl, C 6 -C 22 -aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical and two radicals R 12 may also be joined to form a five- or six-membered ring,
- G is C ! -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 40 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR 1 ' 2 , SiR 12 3 or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radical G may also be substituted by halogens, NR 1 ' 2 , OR 11 or SiR 12 3 ,
- E 1 -E 3 are each, independently of one another, carbon, nitrogen or phosphorus, in particular carbon, and u is 0 when E '-E 3 is nitrogen or phosphorus and is 1 when E '-E 3 is carbon, which comprises the following steps: a) reaction of an imine compound of the formula I,
- M 1A is Li, Na, K, Mg, Ca, Sr or Ba, in particular Li,
- X 1A is Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, fluorine, chlorine, bromine, iodine, hydrogen, NR 2A 2 , OR 2A , SR 2A , SO 3 R 2A , OC(O)R 2A , CN, SCN, where the organic radical X 1A may also be substituted by halogens,
- R 2A are each Cj-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, where the organic radicals R 1A - R 2A may also be substituted by halogens, and n is 0 when M 1A is Li, Na or K and is 1 when M IA is Mg, Ca, Sr or Ba and b) subsequent reaction of the product obtained from step a) with a carbonyl compound of the formula V
- R 3A -C(O)X 2A where X 2A is fluorine, chlorine, bromine, iodine, OM 3A , NR 4A 2 , OR 4A , SR 4A or
- R 3A is hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or SiR 4A 3 , where the organic radical R 3A may also be substituted by halogens, and the radicals R 4A are each, independently of one another, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl or arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and
- R'-R 2 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R'-R 2 may also be substituted by halogens, NR 1 ' 2 , OR 11 or SiR 12 3 and/or the two radicals R'-R 2 may also be joined to R 3 -R 5 to form a five-, six- or seven-membered ring,
- R 3 -R 10 are each, independently of one another, hydrogen, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 - C 22 -aryl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and 6-20 carbon atoms in the aryl radical, NR 1 ' 2 , OR 1 1 , halogen, SiR 12 3 or a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, where the organic radicals R 3 -R 10 may also be substituted by halogens, NR 1 ' 2 , OR 11 or SiR 12 3 and/or two radicals R 3 -R 5 or two radicals R 6 -R 10 may also be joined to one another to form a five-, six- or seven-membered ring and/or two radicals R 3 -R 5 or two radicals R 6 -R 10 may be joined to one another
- E '-E 3 are each, independently of one another, carbon, nitrogen or phosphorus, in particular carbon, and u is 0 when E '-E 3 is nitrogen or phosphorus and is 1 when E '-E 3 is carbon.
- the metal alkyls M'R 1A X 1A n are commercially available from FlukaAldrich or can be obtained, for example, by reaction of the corresponding R 1A halide with the metal M 1 ⁇ .
- lithium alkyls having a Ci-C 22 -alkyl group in particular a Ci- C ⁇ -alkyl group, e.g. n-butyllithium or tert-butyllithium.
- the halogen atom A of the imine compound I or Ia is usually replaced by M'X 1A n by metal-halogen exchange with the metal alkyl M'R 1A X 1A n .
- Particularly suitable metal alkyls are lithium alkyls, magnesium alkyls, magnesium (alkyl) halides or mixtures thereof.
- the molar ratio of metal alkyl to imine compound I or Ia is usually in the range from 0.4:1 to 100:1, preferably in the range from 0.9:1 to 10:1 and particularly preferably from 0.95:1 to 1.1 :1. Examples of such reactions are described, inter alia, by Furukawa et al. in Tet. Lett. 28 (1987), 5845.
- aprotic solvents in particular aliphatic and aromatic hydrocarbons such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene or ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane or diethylene glycol dimethyl ether and mixtures thereof.
- the reaction can be carried out at temperatures of from -100 to +160°C, in particular from -80 to 100°C. At temperatures above 40°C, preference is given to using aromatic or aliphatic solvents which contain no ethers or have only small proportions of ethers as solvents.
- step a) The product obtained from step a) can be isolated and purified or be used directly without further work-up in step b).
- the product obtained from step a) is preferably used in step b) without further work-up and without isolation.
- carbonyl compounds of the formula V preference is given to using carboxamides in which X 2A is NR 4A 2 .
- the carbonyl compounds V are, for example, commercially available from FlukaAldrich.
- the molar ratio of carbonyl compound V to imine compound I or Ia is usually in the range from 0.4:1 to 100:1, preferably in the range from 0.9:1 to 10:1 and particularly preferably from 0.95:1 to 1.1 :1. Examples of such reactions are described, inter alia, by Brandsma, Preparative Polar Organic Chemistry, pp. 30-31 and pp. 142-143, Springer Verlag 1987.
- aprotic solvents in particular aliphatic and aromatic hydrocarbons such as n-pentane, n-hexane, isohexane, n-heptane, isoheptane, decalin, benzene, toluene, ethylbenzene or xylene or ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dimethoxyethane or diethylene glycol dimethyl ether and mixtures thereof.
- the reaction can be carried out at temperatures of from -100 to +160 0 C, in particular from -80 to 100°C. At temperatures above 40 0 C, preference is given to using aromatic or aliphatic solvents which contain no ethers or have only small proportions of ethers as solvents.
- the process of the invention is particularly useful for anilines of the formula III having at least one halogen atom in the ortho position. Such anilines give only low yields of imine compound IV in toluene or alcohol.
- the imine compounds of the formula IV or IVa obtained in this way can be reacted with further amine G-NH 2 or with further aniline of the formula III to give bis(imino) compounds.
- This synthetic route is particularly useful for preparing unsymmetrical bis(imino) compounds.
- unsymmetrical bis(imino) compounds are compounds which comprise at least two imino groups whose aryl radicals are not identically substituted. This is based on the substituents or the substitution pattern of the substituents under the theoretical assumption that the aryl radicals can rotate freely.
- the preparation of the unsymmetrical bis(imino) compounds from imine compounds of the formula IV or IVa and further amine G-NH 2 or aniline of the formula III can be carried out under the same conditions as have been described for the process of the invention for preparing the imine compounds of the formula I or Ia.
- Particularly preferred unsymmetrical bisimine compounds of the formula IV are 2-[l- (2,6-dimethylphenylimino)ethyl]-6-[l-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine, 2- [ 1 -(2,4,6-trimethylphenylimino)ethyl] -6- [ 1 -(2,4-dichloro-6- methylphenylimino)ethyl]pyridine, 2-[l-(2,6-dimethylphenylimino)ethyl]-6-[l-(2-chloro-6- methylphenylimino)ethyl]pyridine, 2-[ 1 -(2,4,6-trimethylphenylimino)ethyl]-6-[ 1 -(2-chloro-6- methylphenylimino)ethyl]pyridine, 2- [ 1 -(2,6-diisopropylphenylimino)ethyl] -6
- 6-methylphenylimino)ethyl]pyridine 2-[l-(2,4,6-trimethylphenylimino)ethyl]-6-[l-(2,4- dichloro-6-methylphenylimino)ethyl]pyridine, 2- [ 1 -(2,6-dimethylphenylimino)ethyl] -6- [ 1 -(2- bromo-6-methylphenylimino)ethyl]pyridine, 2-[l-(2,4,6-trimethylphenylimino)ethyl]-6-[l-(2- bromo-6-methylphenylimino)ethyl]pyridine and 2-[l-(2,6-diisopropylphenylimino)ethyl]-6-
- the unsymmetrical bis(imino) compounds can be reacted further to form the corresponding titanium, zirconium, vanadium, chromium, iron or cobalt complexes. These are suitable as catalysts for the polymerization of olefins.
- the process of the invention enables, in particular, even anilines having electron- pulling substituents to be converted into the corresponding monoimine compounds in good yields.
- the imine compounds IVa are thermodynamically very stable and can be reacted with further aniline to form the unsymmetrical bisimine compounds. If imine compounds which are not substituted by electron-pulling radicals in the ortho position are used as starting materials, a further reaction with further aniline usually leads to mixtures of various symmetrical and unsymmetrical bisimine compounds.
- a further advantage is that the process is also very well suited to the preparation of commercial quantities. Furthermore, 2,6-dibromopyridine is a cheaper starting material than, for example, 2,6-diacetylpyridine.
Abstract
Description
Claims
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EP07702728A EP1973879A2 (en) | 2006-01-13 | 2007-01-12 | Process for preparing imino compounds |
US12/087,533 US7795441B2 (en) | 2006-01-13 | 2007-01-12 | Process for preparing imino compounds |
JP2008549836A JP2009523148A (en) | 2006-01-13 | 2007-01-12 | Method for producing imino compound |
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DE102006001960A DE102006001960A1 (en) | 2006-01-13 | 2006-01-13 | Preparation of an imine compound, useful as a raw material in the preparation of asymmetrical diimine compound, comprises reacting a carbonyl compound with a primary amine compound |
DE102006001960.1 | 2006-01-13 | ||
US79886606P | 2006-05-09 | 2006-05-09 | |
US60/798,866 | 2006-05-09 |
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US (1) | US7795441B2 (en) |
EP (2) | EP1973879A2 (en) |
JP (1) | JP2009523148A (en) |
CN (1) | CN101370777A (en) |
DE (1) | DE102006001960A1 (en) |
RU (1) | RU2008133218A (en) |
WO (1) | WO2007080121A2 (en) |
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IL106786A (en) * | 1992-09-10 | 1997-02-18 | Basf Ag | Substituted pyridine derivatives and fungicidal compositions containing them |
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IT1320771B1 (en) * | 2000-10-26 | 2003-12-10 | Enichem Spa | TRIDENTATED BINDERS AND RELATED COMPLEXES WITH TRANSITION METALS. |
-
2006
- 2006-01-13 DE DE102006001960A patent/DE102006001960A1/en not_active Withdrawn
-
2007
- 2007-01-12 EP EP07702728A patent/EP1973879A2/en not_active Withdrawn
- 2007-01-12 WO PCT/EP2007/000255 patent/WO2007080121A2/en active Application Filing
- 2007-01-12 US US12/087,533 patent/US7795441B2/en active Active
- 2007-01-12 RU RU2008133218/04A patent/RU2008133218A/en not_active Application Discontinuation
- 2007-01-12 CN CNA2007800030077A patent/CN101370777A/en active Pending
- 2007-01-12 EP EP11178387A patent/EP2423193A1/en not_active Withdrawn
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RU2008133218A (en) | 2010-02-20 |
EP1973879A2 (en) | 2008-10-01 |
DE102006001960A1 (en) | 2007-07-19 |
WO2007080121A3 (en) | 2007-11-01 |
EP2423193A1 (en) | 2012-02-29 |
JP2009523148A (en) | 2009-06-18 |
US20090005571A1 (en) | 2009-01-01 |
US7795441B2 (en) | 2010-09-14 |
CN101370777A (en) | 2009-02-18 |
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