| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | August 27, 1991 |
| PATENT TITLE |
Method for hydroaminating olefins |
| PATENT ABSTRACT | The reaction of the organolanthanide complexes ([.eta..sup.5 --(CH.sub.3).sub.5 C.sub.5 ].sub.2 MH).sub.2, (M being a lanthanide element) with amino-olefins provides a straight-forward route to a heterocyclic compound. Alternatively, the reaction of olefins with the organolanthanide complex in the presence of an amine results in an aminoalkane |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | February 20, 1990 |
| PATENT REFERENCES CITED |
Watson, et al., "Homogeneous Lanthanide Complexes as Polymerization and Oligomerization Catalysts: Mechanistic Studies", ACS Symposium SEries, 1983, 212, 459-479. Watson and Parshall, "Organolanthanides in Catalysis", Acc. Chem. Res., 1985, 18, 51-56. Mauermann, Swepston, and Marks, "5f.sup.3 vs. 4f.sup.3. Routes to and Properties of Highly Reactive Neodymium (III) Hydrocarbyl and Hydride Complexes", Organometallics, 4, 200, (1985). Jeske, Schock, Swepston, Schumann, and Marks, "Highly Reactive Organolanthanides. Synthesis, Chemistry, and Structures of 4f Hydrocarbyls and Hydrides with Chelating Bis(polymethylcyclopentadienyl Ligands", J. Am. Chem. Soc., 1985, 107, 8103-8110. Jeske, Lauke, Mauermann, Swepston, Schumann, and Marks, "Highly Reactive Organolanthanides, Systematic Routes to and Olefin Chemistry of Early and Late Bis(pentamethylcyclopentadienyl) 4f Hydrocarbyl and Hydride Complexes", J. Am. Chem. Soc., 1985, 107, 8091-8103. Jeske, Lauke, mauermann, Schumann, and Marks, "Highly Reactive Organolanthanides. A Mechanistic Study of Catalytic Olefin Hydrogenation by Bis (pentamethylcyclopentadienyl) and Related 4F Complexes", J. Am. Chem. Soc., 1985, 107, 8111-8118. Evans, et al., "Organolanthanide Hydride Chemistry. 3. Reactivity of Low-Valent Samarium with Unsaturated Hydrocarbons Leading to a Structurally Characterized Samarium Hydride Comples.sup.1 ", J. Am. Chem. Soc., 1983, 105, 1401-1403. Deeba, et al., "Direct Amination of Ethylene by Zeolite Catalysis", J. Chem. Soc. Chem. Commun., 1987, 562-563. Evans, William J., "Polyhedron Report Number 20: The Organometallic Chemistry of the Lanthanide Elements in Low Oxidation States", Polyhedron, 1987, vol. 6, No. 5, 803-835. Finke, et al., "Organolanthanide and Organoactinide Oxidative Additons Exhibiting Enhanced Reactivity. 4. Products, Stoichiometry, and Preliminary Kinetic Studies of the Reaction of (C.sub.5 Me.sub.5).sub.2 Sm.sup.II OEt.sub.2 and (C.sub.5 Me.sub.5).sub.2 Eu.sup.II OEt.sub.2 with Alkyl and Aryl Halides. Evidence of Importance of Electron Transfer in Atom-Abstraction Oxidative Additions", Organometallics, 1987, 6, 1356-1358. Hegedus et al., "palladium-Assisted Amination of Olefins. A Mechanistic Study", J. Am. Chem. Soc. 1984, 106, 7122-7126. Surzur et al., "Bicyclisations Radicalaires Des N-Chloroamines Ethyleniques", Tetrahedron Letters, 1974, No. 25, 2191-2194. Ambuehl et al., "Paltinum-Promoted Cyclization Reactions of Amino-Olefins. I. The Cyclization of 4-Aminopentene and Related Compounds", Journal of Organometallic Chemistry, 160 (1978), 329-335. Fagan et al., "Insertion of Carbon Monoxide into Metal-Nitrogen Bonds, Synthesis, Chemistry, Structures, and Structural Dynamics of Bis(pentamethylcyclopentadienyl) Organoactinide Dialkylamides and .eta..sup.2 -Carbamoyls", J. Am. Chem. Soc., 1981, 103, 2206-2220. Tamaru et al., "Urea as the Most Reactive and Versatile Nitrogen Nucleophile for the Palladium (2+)-Catalyzed Cyclization of Unsaturated Amines", J. Am. Chem. Soc., 1988, 110, 3994-4002. Pez et al., "Metal Amide Catalyzed Amination of Olefins", Pure & Appl. Chem., 1985, vol. 57, No. 12, 1917-1926. Pugin et al., "Palladium-Promoted Cyclization Reactions of Aminoalkenes", Journal of Organometallic Chemistry, 1981, 214, 125-133. Gasc et al., "Tetrahedron Report No. 144: Amination of Alkenes", Tetrahedron, 1983, vol. 39, No. 5, 703-731. Deeba et al., "Heterogeneous Acid-Catalyzed Amination of Isobutene to tert-Butylamine", J. Org. Chem., 1988, 53, 4594-4596. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
We claim: 1. A method for hydroaminating an amino-olefin, comprising contacting said amino-olefin with an organolanthanide catalyst under an inert atmosphere, said catalyst having the formula R.sub.2 MR' where R is an alkyl, aryl, amido, or organometalloid group and R' is an alkyl group or hydrogen, and M is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y. 2. A method for hydroaminating an amino-olefin, comprising contacting said amino-olefin with a catalyst under an inert atmosphere, said catalyst having a formula selected from the group consisting of (Cp'.sub.2 MH).sub.2 and Cp" is (CH.sub.2).sub.4 C.sub.5 (CH.sub.3).sub.2 SiCp".sub.2 MCH[Si(CH.sub.3).sub.3 ].sub.2, wherein Cp' is .eta..sup.5 (CH.sub.3).sub.5 C.sub.5 ; and M is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y, whereby a heterocycle is formed. 3. The method of claim 1 wherein said amino-olefin is selected from the group consisting of: ##STR22## 4. The method of claim 2 wherein said catalyst solution has a solvent selected from the group consisting of tetrahydrofuran, cyclohexane, toluene, benzene, and pentane. 5. The method of claim 2 wherein said catalyst is homogeneous. 6. The method of claim 2 wherein said catalyst is heterogeneous. PG,16 7. The method of claim 5 wherein said catalyst is adsorbed on an inorganic substrate selected from the group consisting of silica, silica gel, alumina, magnesium chloride, and magnesium oxide. 8. A method for hydroaminating an unsaturated monomer selected from the group consisting of amino-olefins and amino cycloalkenes comprising the steps of dissolving said unsaturated monomer in a solvent and contacting said olefin and solvent solution with a lanthanide catalyst of the formula R.sub.2 MR' under an inert atmosphere wherein R is selected from the group consisting of alkyl, aryl, amido, and organometalloid group; R' is selected from the group consisting of an alkyl group, organometalloid group and hydrogen, and M is selected from the group consisting of the Lanthanide Series elements and Yttrium. 9. The method of claim 8 wherein said solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof. 10. The method of claim 8 wherein said solvent is toluene. 11. The method of claim 8 wherein M is selected from the group of lanthanide elements consisting of La, Ce, Nd, and Sm. 12. The method of claim 8 wherein said unsaturated monomer is selected from the group consisting of: ##STR23## 13. A method of hydroaminating an amino-olefin, comprising the steps of: (a) evacuating a reaction vessel; (b) adding a solvent to said reaction vessel; (c) adding a catalyst solution containing an organolanthanide compound of the formula R.sub.2 MR' where R is an alkyl, aryl, amido, or organometalloid group, and R' is an alkyl group, organo-metalloid group or hydrogen, and M is a lanthanide selected from the group consisting of: La, Ce, Pr, Nd, Pm, Sm, Ea, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y to said reaction vessel; (d) maintaining pressure with an atmosphere selected from argon or nitrogen in said reaction vessel at approximately one atmosphere; (e) stirring the solvent and catalyst solution rapidly for several minutes; (f) transferring to said mixture an amino-olefin; and (g) heating the reaction vessel, whereby the amino-olefin forms into a heterocyclic compound which may be isolated. 14. A method of claim 13 where R.sub.2 MR' is selected from the group consisting of (Cp'MH).sub.2 and (CH.sub.3).sub.2 SiCp".sub.2 MCH[Si(CH.sub.3).sub.3 ].sub.2. 15. A method for hydroaminating an olefin, to form an aminoalkane comprising contacting said olefin with a catalyst in the presence of an amine selected from the group consisting of NH.sub.3, R"NH.sub.2, R".sub.2 NH, where R" is an alkyl or aryl group, said catalyst having the formula R.sub.2 MR', where R is an alkyl, aryl, amido, or organometalloid; R' is an alkyl group, organo-metalloid group or hydrogen; and M is selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y. 16. The method of claim 15 wherein said olefin is selected from the group consisting of ethylene, propylene, 1-butene, butadiene, 1-hexene, 1-heptene, and 1,5-hexadiene. 17. The method of claim 15 wherein said catalyst solution has a solvent selected from the group consisting of tetrahydrofuran, cyclohexane, toluene, benzene, and pentane. 18. The method of claim 15 wherein said catalyst is homogeneous. 19. The method of claim 15 wherein said catalyst is heterogeneous. 20. The method of claim 15 wherein said catalyst is selected from the group consisting of (Cp'.sub.2 MH).sub.2 and (CH.sub.3).sub.2 SiCp".sub.2 MCH[Si(CH.sub.3).sub.3 ].sub.2. 21. The method of claim 19 wherein said catalyst is adsorbed on an inorganic substrate selected from the group consisting of silica, silica gel, alumina, magnesium chloride, and magnesium oxide. 22. A method for hydroaminating an unsaturated monomer selected from the group consisting of .alpha.-olefins and cycloalkenes comprising the steps of dissolving said unsaturated monomer in a solvent and contacting said olefin solution with a lanthanide catalyst of the formula R.sub.2 MR' under an ammonia atmosphere wherein R is an alkyl, aryl, amido, or organometalloid group; R' is an alkyl or hydrogen; and M is selected from the group consisting of the Lanthanide Series elements and Yttrium. 23. The method of claim 22 wherein said solvent is selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof. 24. The method of claim 22 wherein said solvent is toluene. 25. The method of claim 22 wherein M is selected from the group of lanthanide elements consisting of La, Nd, and Sm. 26. The method of claim 22 wherein said unsaturated monomer is selected from the group consisting of ethylene, propylene, 1-butene, butadiene, 1-hexene, 1,5-hexadiene, and 1-heptene. 27. The method of claim 22 wherein said catalyst comprises [(.eta..sup.5 (CH.sub.3).sub.5 C.sub.5).sub.2 MH].sub.2. 28. A method of hydroaminating an olefin, comprising the steps of: (a) evacuating a reaction vessel; (b) adding a solvent to said reaction vessel; (c) adding a catalyst solution containing an organolanthanide compound of the formula selected from the group consisting of (Cp'.sub.2 MH).sub.2 and (CH.sub.3).sub.2 SiCp".sub.2 MCH(CH.sub.3).sub.3 Si).sub.2 where M is a lanthanide selected from the group consisting of: La, Ce, Pr, Nd, Pm, Sm, Ea, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y to said reaction vessel; (d) maintaining pressure with an atmosphere of ammonia in said reaction vessel at approximately one atmosphere; (e) stirring the solvent and catalyst solution rapidly for several minutes; (f) transferring to said mixture an olefin; and (g) heating the reaction vessel, whereby an amido-alkane is formed and may be isolated -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
This application relates to catalysts and more particularly to a method for the hydroamination of olefins through the use of organolanthanide catalysts. BACKGROUND OF THE INVENTION The catalytic addition of N-H bonds to olefins (eq.(I)) to yield amines is a process of potentially great technological importance ##STR1## However, presently known catalyst systems, employing palladium, platinum, or alkali metal catalysts, can be relatively inefficient, having very low rates, poor catalyst lifetimes, poor selectivities, or requiring initial modification of the amine--e.g., tosylation. As a result, many current catalytic processes involve the conversion of alcohols to amines with the alcohol, which in turn, is prepared from the olefin. Such hydroamination reactions are exothermic, yet thus far have proven difficult to perform due to a lack of suitable catalysts and, to a lesser extent, unfavorable entropy effects. As a result, more attention has been paid to aminating olefins intramolecularly, and limited successes have been experienced in both stoichiometric and catalytic type reactions. A rapid efficient, direct process for the hydroamination of olefins would be beneficial. Organolanthanide catalysts have been found useful as noted in U.S. Pat. No. 4,668,773 to Marks and Mauermann; The organolanthanide complexes [.eta..sup.5 --(CH.sub.3).sub.5 C.sub.5 ].sub.2 MCL.sub.2 --Li[(C.sub.2 H.sub.5).sub.2 O]2.sup.+, M=La, Nd, Sm, Lu, with LiCH[Si(CH.sub.3).sub.3 ].sub.2 were shown to provide a straight-forward route to ether-free and halide-free bis(pentamethylcyclopentadienyl) lanthanide alkyls [.eta..sup.5 (CH.sub.3).sub.5 C.sub.5] ].sub.2 MCH [Si(CH.sub.3).sub.3 ].sub.2. Such [.eta..sup.5 (CH.sub.3).sub.5 C.sub.5 ].sub.2 MCH[Si(CH.sub.3).sub.3 ].sub.2 complexes react with H.sub.2 under mild conditions to yield the corresponding hydrides [.eta..sup.5 (CH.sub.3).sub.5 (C.sub.5).sub.2 MH].sub.2. These complexes have been found to be extremely active homogeneous olefin polymerization catalysts, as well as catalysts for olefin and acetylene hydrogenation. SUMMARY OF THE INVENTION Therefore, an object of the subject invention is the use of organolanthanide catalysts for use in hydroamination reactions. Another object of the subject invention is a shelf-stable environmentally acceptable organolanthanide catalyst and its use in a method for the hydroamination of olefins. A further object of the subject application is a method for the synthesis of heterocycle compounds from amino-olefins and aminocycloalkenes through hydroamination. These and other objects are attained in accordance with the subject invention wherein organolanthanide catalysts are used as highly active catalysts for the hydroamination of olefins. In a first embodiment, .alpha.-amino olefins are utilized with an organolanthanide catalyst to form a heterocyclic compound. Amino cycloalkenes may also be utilized, providing steric hindrances are not too great. Organolanthanide catalysts such as those disclosed in U.S. Pat. No. 4,668,773, i.e., R.sub.2 MR' where R=an alkyl, aryl, amido, or organometalloid group; R'=an alkyl group or hydrogen and M=a lanthanide series element, i.e., La, Ce, Pr, Nd, Pm, Sm, Ea, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; M may also be Yttrium, primarily in view of its similar properties. Equation II illustrates one example of a reaction cycle with a pentamethylcyclopentadienyl ((CH.sub.3).sub.5 C.sub.5 =Cp') lanthanum catalyst and an amino .alpha.-olefin. The first step (i) comprises the insertion of the .alpha.-olefin into the metal-nitrogen (M--N) bond. The second step (ii) is the protonolysis of the (metal-carbon (M--C) bond to release the heterocyclic product and regenerate the metal amide. This simple, efficient, and direct process results in the facile synthesis of a variety of heterocyclic compounds. The same general mechanism can be useful in forming alkylamines. ##STR2## In a second embodiment, all other amino olefins may be reacted with an organolanthanide catalyst to result in a heterocycle; here the amino olefin should not be of a structure as would sterically hinder the reaction. In yet another embodiment of the invention, aminoalkanes can be synthesized by stirring solutions of an .alpha.-olefin or other non-sterically hindered olefin under an ammonia or other amine atmosphere or solution with an organolanthanide catalyst (R.sub.2 MR') present. DETAILED DESCRIPTION OF THE INVENTION All operations were performed with rigorous exclusion of oxygen and moisture in flamed Schlenk-type glassware in a dual manifold Schlenk line or interfaced to a high vacuum (10.sup.-5 torr) system, or in a nitrogen or argon filled glovebox with a high capacity atmosphere recirculator. Argon, ethylene, propylene, dihydrogen, and deuterium gas were purified by passage through a supported MnO oxygen removal column and a molecular sieve column. Aliphatic hydrocarbon solvents were pretreated with concentrated H.sub.2 SO.sub.4, KMnO.sub.4 solution, MgSO.sub.4, and Na+4A molecular sieves. All reaction solvents were distilled from Na/K/benzophenone under nitrogen and were condensed and stored in vacuo in bulbs on the vacuum line containing a small amount of [Ti(.eta..sup.5 -C.sub.5 H.sub.5).sub.2 Cl].sub.2 ZnCl.sub.2 as indicator. Cyclohexane and heptane were additionally vacuum transferred onto Na/K and stirred for at least a day before use in catalytic experiments. The olefins, all hexenes, and cyclohexene were purified by stirring over Na/K for at least 6 hours and were freshly vacuum transferred. The amines were purified by stirring over Na/K for 1/2 hour, followed by at least 3 successive vacuum transfers onto freshly activated 4.ANG. molecular sieves (at least 1 day each); and freshly vacuum transferred before use. Deuterated solvents were dried over Na/K and vacuum transferred before use. Anhydrous lanthanide halides were prepared from the corresponding oxide and ammonium chloride. Pentamethylcyclopentadiene was prepared by the procedure set forth in Organometallics, 1984, 3, 819-821. The complexes Cp'.sub.2 NdCl.sub.2 --Li((C.sub.2 H.sub.5).sub.2 O).sub.2.sup.+ and Cp'.sub.2 LuCl.sub.2 --Li((C.sub.2 H.sub.5).sub.2 O).sub.2.sup.+ were prepared as known in the art. Bis(trimethylsilyl)methyllithium (LiCHTMS.sub.2) and 2-lithium-mesitylene were also prepared as known in the art. I. Catalyst Syntheses In general, Cp'.sub.2 MCHTMS.sub.2 and 2-(Cp'.sub.2 M)mesitylene may be prepared by mixing approximately equimolar amounts of Cp'.sub.2 MCl.sub.2 Li(C.sub.2 H.sub.5).sub.2 O).sub.2 ' and LiCHTMS.sub.2 or 2-lithium-mesitylene, as appropriate, in toluene for 8-16 hours (preferably 12 hours) and -10.degree. C. to 25.degree. C. (preferably O.degree. C.). The solvent is then removed and the residue extracted with another solvent, preferably pentane. The extract is cooled to recrystallize the Cp'.sub.2 MCHTMS.sub.2 or 2-(Cp'.sub.2 M)mesitylene. |
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