Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
  • C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
  • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
  • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
  • C07C2603/20—Acenaphthenes; Hydrogenated acenaphthenes

Definitions

• these diimines are symmetrical, that is the organic group attached to the two imino nitrogen atoms in the diimine by a single bond are identical. Since imine groups are most commonly made by reacting a carbonyl group (ketone or aldehyde) with a primary amine, in such a synthesis a symmetrical diimine is made by reacting two carbonyl groups in the same compound with the same diimine. For various reasons it is sometimes preferred that a diimine be unsymmetrical, that is each of the groups attached to an imino nitrogen atom through a single bond are different.
• one of the organic groups attached to an imino ni- trogen atom by a single bond may desirably contain a polar group, see for instance World Patent Application 02/79276, which is hereby included by reference.
• This invention concerns a process for the preparation of an unsymmetrical diimine, comprising, forming a mixture of an unsymmetrical diimine and two symmetrical diimines, and then subjecting said mixture to liquid chromatography and isolating said unsymmetrical diimine, provided that said unsymmetrical diimine has a polar group attached to the group bonded to one of the imino carbon atoms by a single bond. Also disclosed herein is an unsymmetrical diimine of the formula
• each R 1 is independently hydrogen, a heteroatom connected monovalent radical, hydrocarbyl, or substituted hydrocarbyl, Y is a covalent bond or a divalent bridging group; R 2 is hydrocarbyl or substituted hydrocarbyl; and R 3 is substituted hydrocarbyl containing a polar group; and provided that both of R 1 taken together may form a ring; and R 2 and R 3 are different.
• R 1 is independently hydrogen, a heteroatom connected monovalent radical, hydrocarbyl, or substituted hydrocarbyl
• Y is a covalent bond or a divalent bridging group
• R 2 is hydrocarbyl or substituted hydrocarbyl
• R 3 is substituted hydrocarbyl containing a polar group
• each R 1 is independently hydrogen, a heteroatom connected monovalent radical, hydrocarbyl, or substituted hydrocarbyl
• Y is a cova- lent bond or a divalent bridging group
• R 2 and R 3 are each independently hydrocarbyl or substituted hydrocarbyl, provided that both of R 1 taken together may form a ring.
• ⁇ -diimine is meant a compound of formula (I) in which Y is a covalent bond.
• an "unsymmetrical diimine” is meant a diimine of formula (I) in which R 2 and R 3 are different.
• an unsymmetrical diimine containing a polar group is meant a diimine in which R 2 contains at least one polar group, and R 3 contains no polar groups or one or more less polar groups.
• liquid chromatography is meant any method by which a solute containing two or more different compounds is dissolved in a liquid, and the resulting solution is passed over an adsorbent that separates two or more of the solute compounds. The solute compounds are typically re- moved from the adsorbent by eluting with liquid (solvent). Such methods are well know, see for instance P. Lembke, et al in Ullmann's Encyclopedia of Chemical Technology, 6 th Ed., Vol. 19, Wiley-VCH, Weinheim, p.
• hydrocarbyl group is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein preferably contain 1 to about 30 carbon atoms.
• substituted hydrocarbyl herein is meant a hydrocarbyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected (e.g., an inert functional group, see below).
• substituted hydrocarbyl groups also do not substantially detrimentally interfere with the polymerization process or operation of the polymerization catalyst system. If not other- wise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are chains or rings containing one or more heteroatoms, such as nitrogen, oxygen and/or sulfur, and the free valence of the substituted hydrocarbyl may be to the heteroatom. In a substituted hydrocarbyl, all of the hydro- gens may be substituted, as in trifluoromethyl.
• (inert) functional group herein is meant a group other than hydrocarbyl or substituted hydrocarbyl that is inert under the process conditions to which the compound containing the group is subjected.
• the functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in.
• Examples of functional groups include halo (fluoro, chloro, bromo and iodo), ether such as -OR 25 , -CO 2 R 22 , -NO 2 , and -NR 22 2 , wherein each R 22 is independently hydrocarbyl or substituted hydrocarbyl.
• aryl is meant a monovalent aromatic group in which the free valence is to the carbon atom of an aromatic ring.
• An aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups, such as 9-anthracenyl or 1-naphthyl. Unless otherwise stated aryl groups preferably contain 5 to 30 carbon atoms.
• substituted aryl is meant a monovalent aromatic group substituted as set forth in the above definition of “substituted hydrocarbyl”. Suitable substituents include alkyl, aryl such as phenyl, halo, alkoxy, ester, dialkylamino and nitro. Similar to an aryl, a substituted aryl may have one or more aromatic rings that may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. Unless otherwise stated, substituted aryl groups contain 5 to about 30 carbon atoms.
• alkyl groups and substituted alkyl groups preferably have 1 to about 30 carbon atoms.
• a heteroatom connected monovalent radical is meant a substi- tuted hydrocarbyl which is a monovalent radical or group which is connected to the rest of the compound through a valence of a heteroatom (an atom other than C and H). The group may be more than monovalent if it is part of a ring connected by a bridging group.
• a dicarbonyl compound (II) may be reacted with two primary amines R 2 NH 2 (III) and R 3 NH 2 (IV), per the reaction: (1) R 1 - II II 4. II II N N N + II II / ⁇ N N + H 2 0 / R 2 (V) R 3 R 2 ⁇ 2 / ⁇ , (VI) R R 3 (VII) R
• Typical techniques for forming imines from carbonyl compounds may be used, such as heating, the use of catalysts, and removal of the byproduct water to drive the reaction to completion.
• Typical catalysts include Bron- sted acids such as p-toluenesulfonic and sulfuric acids.
• Water may be removed by azeotropic distillation or by chemical removal by forming a hydrate by reacting the water, for instance with CaO.
• the three diimines obtained in equation (1) will be present in relative quantities that reflect a random statistical formation of the diimines.
• the reaction with (II) and (IV) may be carried out simultaneously or sequentially in any order.
• the second step should be run under conditions that at least partially randomizes the R 2 and R 3 groups in the diimines formed. Since all of the imine group forming reactions are in fact equilibria, this is usually readily accomplished. Oftentimes the reaction(s) involved in equation 1 are run in a solvent or a liquid medium. At the end of the reaction the solvent may be removed, for example by vaporization, or the solution (assuming the prod- ucts are soluble) may be used directly for the liquid chromatography, assuming the solvent is suitable for use in chromatography. The diimines may be concentrated by removal of some of solvent before the chromatography is started.
• the diimines may be redissolved in another solvent and that solution used for the liquid chroma- tography.
• forms of liquid chromatography useful in the present process include column chromatography, flash chromatography, and high-pressure liquid chromatography, and flash chromatography is preferred.
• the solute is adsorbed on an adsorbent, often called the stationary phase, and that components of the solute are separated because they are more or less strongly adsorbed on the solid phase.
• Solvents are used to separate and "move" the various solute compounds on the stationary phase, and eventually to elute these separated solute compounds from the stationary phase.
• Both of R 1 are alkyl, more preferably methyl, or a heteroatom connected monovalent radical which taken together may form a ring, or both of R 1 taken together are
• Y is a covalent bond or -(CH 2 )n- wherein n is 1 , 2 or 3, more preferably a covalent bond, or
• R 2 is substituted aryl; and/or R 3 is aryl or substituted aryl, preferably containing no polar groups except it may optionally contain halogen.
• Polar groups are groups which react with a support (or compounds attached to a support), or which may be reacted with a second compound to form a third compound which reacts with a support.
• a preferred type of polar group is a group that may hydrogen bond, such as hydroxyl, amino (especially primary and secondary amino), thiol, and car- boxyl.
• polar group is an acid that has a pK a (in water) of about 0 to about 15, more preferably about 3 to about 13.
• One type of preferred polar group, which is part of R2 is a group that may be used to bond, preferably c ⁇ valently bond, a transition metal complex in which the unsymmetrical diimine is a ligand to a support.
• the unsymmetrical diimine containing transition metal complex becomes a component of a catalyst system, preferably a polymerization catalyst sys- tem that is supported on a support.
• a catalyst system preferably a polymerization catalyst sys- tem that is supported on a support.
• Such preferred polar groups include hydroxyl, amino (especially primary and secondary amino), thiol, and carboxyl, and hydroxyl is especially preferred. Formation of such transition metal complexes is also well known; see for instance U.S. Patents 5,955,555, 6,103,658,
• This reequilibration can also be carried out in a reaction in which the symmetrical diimines are added to the mixtures of 2 different primary amines the dicarbonyl compound. If only one of the symmetrical diimines is placed in this reaction, then the stoichiometry should be adjusted so that the amounts of the two "primary amines" added (as primary amines or part of a diimine) should be about equimolar. The following illustrates a somewhat different overall synthesis of the unsymmetrical diimine.
• Two appropriate symmetrical diimines [made by a process similar to the reaction in equation (1 )], one having the appropriate polar group and the other not, may be prepared separately and then equilibrated to form a mixture of the two symmetrical diimines and the unsymmetrical diimine.
• the unsymmetrical diimine may then be purified us- ing liquid chromatography.
• one or both of the symmetrical diimines may be recycled in the process to form unsymmetrical diimine. This is particularly valuable if the dicarbonyl compound and/or one or both of the primary amines is particularly expensive.
• a 36 cm long x 4.5 cm diameter column was used and it was about 2/3 filled with silica gel (Scientific Adsorbents #02826-25, particle size 22-63 ⁇ m, pore size 60 Angstroms, Scientific Adsorbents, Inc., Atlanta, GA 30340, USA).

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• 2005
  • 2005-04-27 CN CNA2005800118727A patent/CN1942433A/zh active Pending
  • 2005-04-27 EP EP05744356A patent/EP1758848A1/de not_active Withdrawn
  • 2005-04-27 WO PCT/US2005/014597 patent/WO2005105734A1/en not_active Application Discontinuation

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