Indian Patents. 250117:"A PROCESS FOR MAKING A LIGAND"

Title of Invention	"A PROCESS FOR MAKING A LIGAND"
Abstract	A process for making a ligand having the formula wherein the process comprises the following reactions:

Full Text	The present invention relates to a process for making a ligand. [0001] This invention was made with United States Government support under ATP Award No. 70NANB4H3014 awarded by the National Institute of Standards and Technology (NIST). The United States Government has certain rights in the invention. [0002] This Application claims the benefit of U.S. Provisional Patent Application No. 60/713,172, filed on August 31, 2005. [0003] The present invention relates to a method of synthesizing ligand structures that may be complexed with a late transition metal to form catalyst complexes useful in facilitating various polymerization reactions and/or Heck coupling reactions. [0004] The identification of new ligands for late transition metals and of commercially viable methods for making such ligands are important. For example, the identification of new ligands that complex with late transition metals to form catalyst complexes that are active for catalyzing polymerization reactions is of particular importance. That is, there remains an industry wide need for new molecular catalyst complexes that are capable of polymerizing polar monomers in a controlled fashion and for copolymerizing polar monomers with olefins (e.g., ethylene, propylene) under mild reaction conditions. Of the many approaches to modifying the properties of a polymer, the incorporation of functional groups into an otherwise non-polar material would be ideal in many situations. The incorporation of polar groups into a non-polar material can result in modification to various physical properties of the resultant copolymer, for example, toughness, adhesion, barrier properties and surface properties. Changes in these physical properties can result in improved solvent resistance, miscibility with other polymers and rheological properties, and product performance such as paintability, dyeability, printability, gloss, hardness and mar resistance. [0005] The identification of new ligands that complex with late transition metals to form catalyst complexes that are active for Heck coupling reactions is also or particular commercial importance. [0006] One approach to the preparation of ligands is disclosed in United States Patent No. 5,760,286 to Brandvold. Brandvold disclose a method for the preparation of ligands according to the according to formula IV (Formula Removed) where A is selected from hydrogen, alkali earth metal, alkaline earth metal, quaternary ammonium, and a phosphonium group; RI is selected from the group consisting of hydrogen, an alkyl group having from 1 up to about 20 carbon atoms, an aromatic group or an aralkyl group; R2 is selected from the group consisting of an alkyl group of from 1 up to about 20 carbon atoms, an aromatic group or fused aromatic group, an aralkyl group, and a cycloalkyl group having from 5 up to about 10 ring carbon atoms; and, R3 is selected from the group consisting of hydrogen, an alkyl group of from 1 up to about 20 carbon atoms, an aromatic group or an aralkyl group, and a cycloalkyl group having from 5 up to about 10 ring carbon atoms, comprising: a first reaction of compounds of formula II, with compounds of formula I (Formula Removed) to afford products of formula III (Formula Removed) where said first reaction proceeds by addition of a heterogeneous mixture of one molar proportion of the compound of formula I dispersed in an organic phase to a solution of the compound of formula II in an organic phase to afford a reaction mixture, said addition carried out at a rate such that the reaction mixture is at all times homogeneous, and; subsequent alkylation of the compound of formula III by an organometallic compound of formula R3M to yield the ligand of formula IV where R3M is a Grignard reagent or an organolithium. [0007] Nevertheless, there remains a need for new ligands and new ligand synthesis methods that provide such ligands in good yield and in relatively high purity. [0008] In one aspect of the present invention, there is provided a process for making a ligand having the formula (Formula Removed) wherein the process comprises the following reactions: (b) v1-Q(v3)v2 X2-E2 + X'(R15)-Q(V3)V2 (Compound I) X3-E3 + X'(R15)-Q(V3)-X2 (Compound II) X'(RI5)-Q(V3)V2 (Compound I) X'(R15)-Q(V3)-X2 (Compound II) X1(R15)-Q(X3)-X2 (Compound III); wherein Q is selected from phosphorus, arsenic and antimony; wherein E1, E2 and E3 are electrophilic metals; wherein V1, V2 and V3 are weakly-basic anions; wherein X1 , X2 and X3 are carbon anions; and, wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group. [0009] In another aspect of the present invention, there is provided a process for making a ligand having the formula (Formula Removed) wherein the process comprises the following reactions: V'-Q(V3)V2 (i) X'(R'5)-B' + X1(R15)-Q(V3)V2 (Compound I) X1(R15)-Q(V3)V2 (Compound I) X1(R15)-Q(X2)-X2 (Compound IV); wherein Q is selected from phosphorus, arsenic and antimony; wherein E1 and E2 are electrophilic metals; wherein V1, V2 and V3 are weakly-basic anions; wherein X1 and X2 are carbon anions; and, wherein R15 is selected from -SO3, -SO2N(R18 ), -CO2, -PO3, - AsO3, -SiO2, -C(CF3)2O; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group. [0010] The term "protecting group" as used herein and in the appended claims refers to a group of atoms that when attached to a reactive group in a molecule masks, reduces or prevents undesired reactions with the reactive group. The use of protecting groups is well known in the art. Examples of protecting groups and of how they may be used can be found, among other places, in Protecting Groups in Organic Chemistry, J.W.F. McOmie, (ed.), 1973, Plenum Press and Protective Groups In Organic Synthesis, (Wiley, John & Sons, Inc. 3rd ed. 1999). [0011] In some embodiments of the present invention, the process for making a ligand having the formula comprises the following reactions: (a) X'(R15)-E1 + V1-Q(V3)V2 > X1(RI5)-Q(V3)V2 (Compound 1) (b) x2-E2 + x1(R15)-Q(V3)v2 > x1(Rl5)-Q(v3)-x2 (Compound I) (Compound 11) (c) X3-E3 + X'(R15)-Q(V3)-X2 > X1(R15)-Q(X3)-X2 (Compound II) (Compound III); wherein Q is selected from phosphorus, arsenic and antimony; alternatively Q is selected from phosphorus and arsenic; alternatively Q is phosphorus; wherein E1, E2 and E3 are independently selected from lithium, magnesium, potassium, beryllium, sodium, scandium, yttrium, titanium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; alternatively E1, E2 and E3 are independently selected from lithium, magnesium, potassium and sodium; alternatively E1, E2 and E3 are lithium; wherein V1, V2 and V3 are independently selected from chloride, bromide, fluoride, iodide, toluenesulfonate, methansulfonate, trifluoromethansulfonate, benzenesulfonate; alternatively V1, V2 and V3 are chloride; wherein X1, X2 and X3 are carbon anions; and, wherein R15 is selected from -SO?, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; alternatively R" is selected from -SO3 and -SO2N(R18); alternatively R15 is -SO3; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl 1 8 group; alternatively R is selected from a hydrogen; a halogen; and, a substituted or unsubstituted substituent selected from C1-C20alkyl, C3-C20 cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20carboxylate, C1-C20alkoxy, C2-C20alkenyloxy, C1-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsulfonyI, C1-C20alkylsulfinyl, and silyl. In some aspects of these embodiments, X1, X2 and X3 are all different. In some aspects of these embodiments, X2 and X3 are the same. [0012] In some embodiments of the present invention, reactions (a), (b) and (c) are performed sequentially in the same vessel. [0013] In some embodiments of the present invention, the reaction temperature during reaction (a) is lower than the reaction temperature during reaction (b) and wherein the reaction temperature during reaction (b) is lower than the reaction temperature during reaction (c). [0014] In some embodiments of the present invention, reaction (b) proceeds in the same vessel as reaction (a) without isolation of Compound I. [0015] In some embodiments of the present invention, reaction (c) proceeds in the same vessel as reaction (b) without isolation of Compound II. [0016] In some embodiments of the present invention, the process for making a ligand having the formula (Formula Removed) comprises the following reactions: (i) X1(R15)-Q(V3)V2 V1-Q(V3)V2 X1(R15)-E' (Compound I) X1(R15)-Q(X2)-X2 (Compound IV); X'(R15)-Q(V3)V2 (ii) 2 X-Ez + (Compound I) wherein 0 is selected from phosphorus, arsenic and antimony; alternatively Q is selected from phosphorus and arsenic; alternatively Q is phosphorus; wherein E and E are independently from lithium, magnesium, potassium, beryllium, sodium, scandium, yttrium, titanium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; alternatively E1 and E2 are independently selected from lithium, magnesium, potassium and sodium; alternatively E1 and E2 are lithium; wherein V1 , V2 and V3 are independently selected from chloride, bromide, fluoride, iodide, toluenesulfonate, methansulfonate, trifluoromethansulfonate, benzenesulfonate; alternatively V1 ,V2 and V3 are chloride; wherein X1 and X2 are carbon anions; wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; alternatively Rl5 may be selected from -SO3 and -SO2N(R18); alternatively R15 is -SO3; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group; alternatively where R18 is selected from a hydrogen; a halogen; and, a substituted or unsubstituted substituent selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, C1-C20alkylsulfinyl, and silyl. [0017] In some embodiments of the present invention, reactions (i) and (ii) are performed sequentially in the same vessel. [0018] In some embodiments of the present invention, the reaction temperature during reaction (i) is lower than the reaction temperature during reaction (ii). [0019] In some embodiments of the present invention, reaction (ii) proceeds in the same vessel as reaction (i) without isolation of Compound I. [0020] In some embodiments of the present invention, X1, X2 and X3 are independently selected from aliphatic hydrocarbyl groups and aromatic hydrocarbyl groups; alternatively X1, X2 and X3 are independently selected from aliphatic hydrocarbyl groups and aromatic hydrocarbyl groups having up to 30 carbon atoms; alternatively X1, X2 and X3 are independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, silyl, and derivatives thereof; alternatively X1, X2 and X3 are independently selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C 2-C20 alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20alkylthio, C1-C20 alkylsulfonyl, C1-C20 alkylsulfmyl, silyl, and derivatives thereof; alternatively X1, X2 and X3 are substituted aryl groups. In some aspects of these embodiments, X2 and X3 are independently selected from ortho substituted aryl groups; alternatively X2 and X3 are independently selected from aryl groups with an ortho substituted phenyl; alternatively X2 and X1 are independently selected from aryl groups with an ortho substituted, substituted phenyl; alternatively X2 and X3 are independently selected from aryl groups with an ortho substituted, substituted phenyl having a formula 2,6-R16R17-phenyl; where R16 and R17 are independently selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, C1-C20 alkylsulfinyl, silyl, and derivatives thereof; alternatively X2 and X3 are aryl groups with an ortho substituted 2,6-dimethoxy phenyl. [0021] In some embodiments of the present invention, X1(R15)-E1, X2-E2 and X3-E3 are according to formulas I, II, and III, respectively, (Formula Removed) wherein E1, E2 and E3 are independently selected from lithium, magnesium, potassium, beryllium, sodium, scandium, yttrium, titanium, lanthanum, cerium, praseodymium, neodyrnium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; alternatively E1, E2 and E3 are independently selected from lithium, magnesium, potassium and sodium; alternatively E1, E2 and E are lithium; wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; alternatively R15 is selected from -SO3 and -SO2N(R18); alternatively R15 is -SO3; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group; alternatively R18 is selected from a hydrogen, a halogen, and a substituted or unsubstituted substituent selected from C1-C20 alkyi, C3-C20 cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsulfonyl, C1-C20alkylsulfinyl, and silyl; and, wherein each R20 is independently selected from a hydrogen, a halogen, and a substituted or unsubstituted substituent selected from C1-C20alkyl, C3-C20 cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20carboxylate, C1-C20alkoxy, C2-C20alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsiilfonyI, C1-C20alkylsulfinyl, and silyl; alternatively wherein each R20 is independently selected from a hydrogen, a phenyl and a substituted phenyl; alternatively wherein each R20 is independently selected from a hydrogen and a substituted phenyl; alternatively wherein each R20 is independently selected from a hydrogen and an ortho substituted phenyl. In some aspects of these embodiments, the substituted phenyl is an ortho substituted phenyl. In some aspects of these embodiments, the ortho substituted phenyl is 2,6-R16 Rl7-phenyl; where R16 and R17 are selected from C1-C20alkyl, C3-C20 cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20alkoxy, C2-C20alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsulfonyl, C1-C20alkylsulfinyl, and silyl. In some aspects of these embodiments, the ortho substituted phenyl is 2,6-dimethoxy phenyl. [0022] In some embodiments of the present invention, each R20 on formula II is independently selected from a hydrogen, a phenyl and a substituted phenyl. In some aspects of these embodiments, both R20's on formula II that are ortho to E2 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, one R20 that is ortho to E2 and the R20 that is para to E2 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, both R20's on formula II that are ortho to E2 and the R20 that is para to E2 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, the substituted phenyl is 2,6-dimethoxy phenyl. [0023] In some embodiments of the present invention, each R20 on formula III is independently selected from a hydrogen, a phenyl and a substituted phenyl. In some aspects of these embodiments, both R20's on formula III that are ortho to E3 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, one R20 that is ortho to E3 and the R20 that is para to E3 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, both R20's on formula II that are ortho to E3 and the R20 that is para to E3 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, the substituted phenyl is 2,6-dimethoxy phenyl. [0024] In some embodiments of the present invention, the ligand having formula (Formula Removed) is selected from Structures I-XV presented in Table 1. In some aspects of these embodiments, the ligand is selected from Structures I, XI, and XIV. In some aspects of these embodiments, the ligand is selected from Structures I and XIV. In some aspects of these embodiments, the ligand is Structure I. In some aspects of these embodiments, the ligand is Structure XIV. [0025] In some embodiments of the present invention, the reaction conditions for reaction (a) or reaction (i) are controlled such that the temperature of the reagents are maintained at a temperature which enables the reaction of V1-Q(V3)V2 with X1(R15)-E1 to proceed while inhibiting the reaction of V1-Q(V3)V2 with Compound I. In some aspects of these embodiments, the reaction temperature for reaction (a) or reaction (i) is maintained at [0027] In some embodiments of the present invention, the reaction conditions for reaction (b) are controlled such that the temperature of the reagents are maintained at a temperature which enables the reaction of Compound I with X2-E2 to proceed while inhibiting the reaction of Compound I with Compound II. In some aspects of these embodiments, the reaction temperature during reaction (b) is maintained at -30°C; alternatively [0028] In some embodiments of the present invention, the process for making the ligand is performed in a substantially oxygen-free atmosphere. In some aspects of these embodiments, the process is performed in a nitrogen atmosphere. In some aspects of these embodiments, the process is performed in an argon atmosphere. [0029] In some embodiments of the present invention, no protecting groups are used in the process to prepare the ligands. [0030] The ligands prepared by the synthesis methods of the present invention may be complexed with a late transition metal, such as palladium and nickel, to form late transition metal catalyst complexes that may be used for example as polymerization catalysts and/or as Heck coupling reaction catalysts. [0031] Some embodiments of the present invention will now be described in detail in the following Examples. All fractions and percentages set forth below in the Examples are by weight unless otherwise specified. The chemical structures presented in Table 1 have been drawn according to the general rules for drawing Lewis structures of molecules as described in, for example, Brown, et al., Organic Chemistry, Brooks-Cole, 4th ed 2004. Examples 1-16: (Ligand Synthesis) [0032] Following the general procedure presented below using Component A and Component B identified in Table 1 in the amounts listed in Table 1, the Product Solids listed in Table 1 were prepared with the reported yield for examples 1-15, respectively. [0033] Component A was added to a 100 mL flask ("Flask A") then placed under vacuum and refilled with nitrogen and charged with 60 mL of tetrahydrofuran (THF). Flask A was then placed in an ice bath and allowed to cool to 0°C. 10.1 mL of 2.5 molar n-BuLi was then injected. Flask A was then placed in a dry ice/acetone bath and allowed to cool to about -78°C. [0034] A separate 500 mL Schlenk flask ("Flask B") was placed under vacuum. Flask B was purged with nitrogen and charged with -50 mL of THF. Flask B was then placed in a dry ice/acetone bath and allowed to cool to about -78°C. 1.10 mL of PCU was then added to Flask B with agitation. The contents of Flask A were then slowly transferred to Flask B using a cannula with vigorous agitation. [0035] A separate 100 mL flask ("Flask C") was purged and filled with nitrogen. Flask C was then charged with -60 mL of THF and Component B. Flask C was then placed in a dry ice/acetone bath and allowed to cool with agitation to about -78°C. 10.1 mL of 2.5 molar n-BuLi was added to Flask C and allowed to react for about 15 minutes. The contents of Flask C were then transferred to Flask B, maintained at -78°C, using a cannula with continued vigorous agitation. Following the complete addition of the contents of Flask C into Flask B, Flask B was allowed to warm to room temperature for about 30 minutes. The contents of Flask B were then poured into a 500 mL recovery flask (Flask D) and the THF was removed, leaving a solid. The solid in Flask D was then mixed with distilled water and then transferred to a separation flask (Flask E). 100 mL of CH2C12 was added to the contents of Flask E. Flask E was shaken to mix the two layers. About 5 mL of concentrated HC1 was then added to Flask E. Flask E was shaken again. The mixture in Flask E was then allowed to settle, forming two layers-an organic phase on the bottom and a aqueous phase on the top. The organic layer was collected. The aqueous phase was washed with 50 mL of CH2Cl2. The organic wash material was collected and added to the previously collected organic layer material. The combined organic material was then contacted with MgSO4 and rotovaped to dryness, leaving a solid. The solid was then washed first with diethyl ether and then with THF to remove impurities. The washed Product Solid was collected by filtration with the yield reported in Table 1. Table 1 (Table Removed) Table 1, cont'd (Table Removed) Table 1. cont'd (Table Removed) Table 1, cont'd (Table Removed) Example 16: Synthesis of a potassium salt of the ligand of Structure VI [0036] A 0.45 g (0.81 mmol) sample of Product Solid (i.e., ligand Structure VI) prepared according to Example 6 was added to 50 mL of THF in a reaction flask with vigorous agitation to form a ligand solution. In a separate container, 0.10 g (0.88 mmol) of potassium tert-butoxide was dissolved in 20 mL of THF. The resulting potassium tert-butoxide solution was then added dropwise to the contents of the reaction flask with agitation. Following the addition of the potassium tert-butoxide solution, the contents of the reaction flask were reduced by vacuum extraction of some of the THF solvent leaving approximately 25 mL of product solution in the reaction flask. A potassium salt of the ligand was then precipitated from the remaining product solution through the addition of 20 mL of pentane. The precipitated potassium salt of the ligand was recovered by filtration through a fine porosity frit and washed with pentane 3 x 20 mL. The potassium salt of the ligand was then subjected to vacuum to remove the remaining volatiles, leaving a dark orange Product Powder 0.40 g (0.67 mmol, 83 %). Example 17: Synthesis of a silver salt of the ligand of Structure VII [0037] A 0.75 g (1.43 mmol) sample of the Product Solid (i.e., ligand Structure Vll) prepared according to Example 7 was added to 50 mL of methanol in a reaction flask with vigorous agitation. In a separate container, 0.23 g (1.36 mmol) of silver nitrate was dissolved in 50 mL of deionized water. The resulting silver nitrate solution was then added dropwise to the contents of the reaction flask with vigorous agitation. Agitation of the contents of the reaction flask was continued for 20 minutes following addition of the silver nitrate solution. The contents of the reaction flask were then reduced by vacuum extraction of some of the solvent leaving approximately 50 mL and resulting in the formation of a gray precipitate. The precipitate was recovered by filtration through a fine porosity frit and washed with water 2 x 20 mL. The silver salt of the ligand was then dried under reduced pressure, leaving a dark gray Product Powder (0.35 g, 0.62 mmol, 44%). Examples 18-31: (Preparation Transition Metal Catalyst Complexes) [0038] A sample of Component A identified in Table 2 was added to 30 mL of tetrahydrofuran in a reaction flask with agitation. To the contents of the reaction flask was then added Component B identified in Table 2, with continued agitation. The contents of the reaction flask were then agitated for 30 minutes before adding Component C identified in Table 2. The contents of the reaction flask were then reduced under vacuum and pentane was added to precipitate the product catalyst complex. The product catalyst complex was collected by filtration through a fine porosity frit and washed with pentane 2 x 20 mL. The product catalyst complex was then subjected to vacuum to remove the remaining volatiles, leaving the Product Yield reported in Table 2. Table 2 (Table Removed) Table 2, cont'd (Table Removed) Example 32: (Preparation of Transition Metal Catalyst Complex & Heck Coupling) [0039] A reaction flask was charged with 0.02 g (30 u.mol) of palladium acetate and 0.025 g (70 µmol) of a Product Solid (i.e., ligand Structure XIII) prepared according to Example 13. The contents were dissolved in 1.5 mL of benzene. Bromobenzene (50 µL, 0.21 mmol) and methylacrylale (50 µL, 0.58 mmol) were added to the reaction flask followed by the addition of excess sodium acetate. The reaction was heated for 24 hours. Based on limiting reagent, conversion to 3-Phenyl-acrylic acid methyl ester was determined to be 30%. Example 33: (Catalyst Preparation/Polymerization) [0040] An 8 ml., serum vial equipped with a stirring bar in a glovebox was charged with palladium bis(dibenzylideneacetone) (41.1 mg, 72.0 umol); product solid (i.e., ligand Structure IX) prepared according to Example 9 (45.0 mg, 86.4 umol) and toluene (4.5 mL). The contents of the serum vial were allowed to stir for 10 minutes, producing a red/brown mixture (i.e., catalyst complex). [0041 ] A reactor cell in a glovebox was charged with methyl acrylate (1.0 mL, 11.1 mmol), followed by the addition of toluene (4.0 mL). The reactor was then heated to 100 °C with agitation. The reactor cell was then pressurized with ethylene gas to 400 psig. After equilibration, a sample of catalyst complex as described above (0.5 mL , 8 umol Pd) was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The reactor cell was then removed from the glovebox. The reactor cell was observed to contain a green colored liquid with a black precipitate. The black precipitate dissolved when added to acidified MeOH (10% HC1). No polymer was observed to form. Example 34: (Catalyst Preparation/Polymerization) [0042] A sample of Product Solid (i.e., ligand Structure IX) prepared according to Example 9 (0.640 g, 1.40 mmol) was added to 30 mL of THF in a reaction flask with agitation. Dimethyl tetrainethylethylenediamine palladium (II) (0.350 g, 1.40 mmol) was then added to the reaction flask with agitation. The contents of the reaction flask were agitated for 30 minutes before adding dry pyridine (0.185 mL, 2.1 mmol). The contents of the reaction flask were then reduced under vacuum and pentane was added to precipitate the catalyst complex. The catalyst complex was collected by filtration through a fine porosity frit and washed with pentane 2 x 20 mL. The catalyst complex was then subjected to vacuum to remove the remaining volatiles, leaving a white solid (0.68 g, 1.09 mmol, 78 %). [0043] Methyl aery late (1.0 mL, 11.1 mmol), followed by toluene (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the cell were then heated to 80 °C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of the catalyst complex prepared above (3 mg, 4.8 µmol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60 °C under vacuum. The subject reaction yielded 0.10 g of a random copolymer of ethylene and methyl acrylate. Example 35-42: (Polymerization) [0044] A reactor cell in a glovebox was charged with the Monomer Component identified in Table 3, followed by THF (4.0 mL). The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, 0.5 mL of tetrahydrofuran containing the Catalyst Component identified in Table 3 was injected into the reactor cell, followed by a tetrahydrofuran rinse (0.5 mL). After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and added to rapidly stirred MeOH. After stirring for 60 minutes, the polymer was vacuum filtered and dried under vacuum at 60°C for 18 hours. The Product Yield of random copolymer obtained from the reaction was as reported in Table 3. Table 3 (Table Removed) Example 43: (Polymerization) [0045] To an 8 mL serum vial equipped with a stirring bar in a glovebox was added palladium bis(dibenzylideneacetone) (41.1 mg, 72.0 umol); a sample of the Product Solid (i.e., ligand Structure XII) prepared according to Example 12 (45.0 mg, 86.4 µmol) and toluene (4.5 ml). The contents of the serum vial were allowed to stir for 10 minutes, producing a red/brown mixture (i.e., catalyst complex). [0046] Three separate reactor cells in a glovebox were each charged with butyl aery late (1.0 mL, 11.1 mmol), followed by toluene (4.0 mL). The contents of the separate reactor cells were then pressurized with ethylene gas to 400 psig and heated to the temperature noted in Table 4. After equilibration, a 0.5 mL sample of the catalyst complex prepared above (8.0 ujnol Pd) was injected into each reactor cell, followed by a toluene rinse (0.5 mL). After 60 minutes, the reactor cells were vented and allowed to cool. The contents of the reactor cells were then removed from the glovebox and separately added to rapidly stirred MeOH. After stirring for 60 minutes, the product polymer in each reactor cell was separately vacuum filtered and dried under vacuum at 60°C for 18 hours. The polymer yield, butyl acrylate incorporation, weight average molecular weight, Mw, number average molecular weight, Mn and PD1 (i.e., Mw/Mn) for each reactor cell are reported in Table 4. Table 4 (Table Removed) Example 4.4; (Polymerization) [0047] Styrene (1.0 mL, 8.73 mmol) and norbornene (1.0 mL, 7.98 mmol, 85 mol% norbornene in toluene) were charged to a reactor cell in a glovebox. Toluene (4.0 mL) was then charged to the reactor cell. The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of a catalyst complex prepared according to Example 18 (1.6 mg, 2 µmol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 0.20 g of a random copolymer of ethylene, styrene and norbornene. Example 45: (Polymerization) [0048] Methyl acrylate (1.0 mL, 11.1 mmol) and norbornene (1.0 mL, 7.98 mmol, 85 mol% norbornene in toluene) were charged to a reactor cell in a glovebox. Toluene (4.0 mL) was then charged to the reactor cell. The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of a catalyst complex prepared according to Example 18 (1.6 mg, 2 µmol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 0.59 g of a random copolymer of ethylene, methyl acrylate and norbornene. Example 46: (Polymerization) [0049] Methyl acrylate (1.0 mL, 11.1 mmol) and styrene (1.0 mL, 8.73 mmol) were charged to a reactor cell in a glovebox. Toluene (4.0 mL) was then charged to the reactor cell. The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of a catalyst complex prepared according to Example 18 (1.6 mg, 2 umol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 ml toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 0.81 g of a random copolymer of ethylene, methyl acrylate and styrene. Example 47: (Polymerization) [0050] To a 5 mL serum vial was added 41.4 mg (72 µmol) Palladium bis(dibenzylideneacetone) and 53.1 mg (86.4 (imol) of a Product Solid (i.e., ligand Structure 1) prepared according to Example 1. To this vial was then added 4.5 ml THF. The contents of the serum vial were stirred for several minutes to prepare a catalyst complex. [0051] Methyl acrylate (1.0 mL, 11.1 mmol) and THF (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the reactor cell were then heated to 70°C and pressurized with ethylene gas to 400 psig. After equilibration, 0.1 mL (1.6 p.rnol) of the catalyst complex from the serum vial was injected into the reactor cell, followed by a 0.5 mL THF rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight al 6()°C under vacuum. The subject reaction yielded 1.02 g of a random copolymer of ethylene and methyl acrylate with an acrylate incorporation of 4.8 mol %; a weight average molecular weight, Mw, of 474,000 and a number average molecular weight, Mn, of 178,000. Example 48: (Polymerization) [0052] To a 5 ml, serum vial was added 41.4 mg (72 µmol) Palladium bis(dibenzylideneacetone) and 53.1 mg (86.4 µmol) of a Product Solid (i.e., ligand Structure I) prepared according to Example 1. To this vial was then added 4.5 ml THF. The contents of the serum vial were stirred for several minutes to prepare a catalyst complex. [0053] Methyl acrylate (1.0 mL, 11.1 mmol) and THF (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the reactor cell were then heated to 70°C and pressurized with ethylene gas to 400 psig. After equilibration, 0.1 mL (8.0 µmol) of the catalyst complex from the serum vial was injected into the reactor cell, followed by a 0.5 mL THF rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 1.28 g of a random copolymer of ethylene and methyl acrylate with an acrylate incorporation of 2.7 mol % and a weight average molecular weight, Mw of 172,000 and a number average molecular weight, Mn , of 57,000. Example 49: (Polymerization) \|0054] To a 5 mL serum vial was added 41.4 mg (72 p,mol) Palladium bis(dibenzylideneacetone) and 53.1 mg (86.4 µmol) of a Product Solid (i.e., ligand Structure T) prepared according to Example 1. To this vial was added 4.5 ml toluene. The contents of the serum vial were stirred for several minutes to prepare a catalyst complex. [0055] Methyl acrylate (1.0 mL, 11.1 mmol) and toluene (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the reactor cell were then heated to 50°C and pressurized with ethylene gas to 400 psig. After equilibration, 0.5 mL (8.0 µmol) of the catalyst complex from the serum vial was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 0.81 g of a random copolymer of ethylene and methyl acrylate with an acrylate incorporation of 0.4 mol %; a weight average molecular weight, Mw, of 716,000 and a number average molecular weight, Mn, of 388,000. Example 50: (Ligand Synthesis) (Formula Removed) [0056] A first 100 ml, Schlenk flask was charged with benzenesulfonic acid hydrate (1.7 g, 10.7 mmol, C6H6O3S-H2O, 158.71 g/mol, MP Bio Medicals 98-11-3). The flask was evacuated under vacuum. The bottom of the flask was then heated using a heat gun. The flask contents melted to form a brown liquid, which started bubbling. The heating was continued until the liquid started to reflux and the pressure dropped to approximately 10 mTorr. The flask was filled with nitrogen, cooled and THF (anhydrous, Acros, ~50mL) was added to the flask forming a clear colorless solution. At 0°C, n-BuLi (2.5 M hexane solution, 11.4 mmol, 8.6 ml,, Aldrich) was added to yield a beige suspension, which was stirred for 0.5 hr before being cooled at -78°C. [0057] A second 100 mL Schlenk flask was charged with Mg (0.30 g, 0.0125 mmol, powder, Aldrich). THF (50 mL, anhydrous, Acros) and 2-bromoanisole (2.10 g, 0.0112 mmol, C7H7BrO, 187.04 g/mol, Acros) were added to the second Schlenk flask. The contents of the second Schlenk flask were sonicated (~30 sec.) and the contents were observed to exhibit a temperature rise The mixture was stirred until it cooled back down to room temperature. [0058] A 200 mL Schlenk flask was charged with THF (-50 mL). At -78°C, PCl3 (0.93 mL, 1.47 g, 0.0107 mol, 1 .574 g/mL, 137.33 g/mol, Aldrich) was added to the 200mL Schlenk flask via syringe. The beige suspension in the first 100 mL Schlenk flask was transferred to the 200 mL Schlenk flask at -78°C via cannula. The contents of the 200 mL Schlenk flask were then stirred for 0.5 hours while maintaining the temperature at -78°C. The contents of the second 100 ml. Schlenk flask was cooled to -78°C and transferred to the 200 mL Schlenk flask via cannula. The contents of the 200 mL Schlenk flask were then warmed to ambient temperature and stirred for about an hour to yield a yellow solution. [0059] A 500 mL Schlenk flask was charged with 2'-Br-2,6-(Me)2biphenyl (3.14 g, 10.7 mmol, C14H13BrO2, 293,16 g/mol, Aldrich) ant THF (150 mL). The contents of the 500 mL Schlenk flask were cooled to -78°C. n-BuLi (4.3 mL, 2.5 M hexane solution, 10.7 mmol, Aldrich) at -78°C was added to the 500 mL Schlenk flask, yielding a thick, white slurry. The 500 mL Schlenk flask was shaken by hand to ensure mixing. A 0.5 hour after the addition of the n-BuLi, the contents of the 200 mL Schlenk flask were added to the 500 mL Schlenk tlask via cannula. The contents of the 500 mL Schlenk flask were then allowed to gradually warm to ambient temperature. The contents of the 500 mL Schlenk flask were stirred overnight to yield a clear yellow solution. The volatiles were removed from the 500 mL Schlenk flask under vacuum. The resulting solid was extracted using CH2Cl2 (200 mL), H2O (200 mL), HC1 (concentrated, 20 mL). The organic layer from the extract was dried with MgSO4 and the volatile portion of the extract was removed under vacuum to leave a pale yellow solid. The pale yellow solid was collected and washed with THF (3x15 mL) and Et2O (3x15 mL) to yield a white powder product ligand (2.3 g, 44% yield). 1H NMR (CDC13, °C): δ 8.32 (m. 111), 7.71 (q,.7 = 8.5, 211), 7.56 (m, 1H), 7.47-7.40 (m, 4H), 7.33-7.27 (m, 2H), 6.99(m, 211), 6.91 (m, IH), 6.57 (d, .7=8.5, IH), 6.44 (d, J= 8.5, IH), 3.73 (s, 3H), 3.64 (s, 3H), 3.19 (s, 3H). 31P NMR (CDC13, °C): 8 -7.1 (s). LC-MS: m/z = 509.2. Example 51: Polymerization [0060] The vial was charged with Pd(dba)2 (19.8 mg, 0.0340 mmol, Pd(Ci7H,4Q)2, Alfa Aesar, 575.00 g/mol) and the product ligand of Example 50 (20.0 mg, 0.0390 mmol, C27H25O6PS, 508.53 g/mol). Toluene (10 mL) was then added to the vial. The contents of the vial were vigorously shaken to yield a dark red catalyst solution with a trace amount of particles. [0061] A reactor cell was charged with methyl acrylate (1 mL) and toluene (4 mL). The reactor cell was heated to 90°C. Ethylene was then charged to the reactor cell (400 psi). The catalyst solution (0.5 mL) from the vial was added to the reactor cell vial cannula followed by a toluene rinse (0.5 mL). The reactor cell contents were stirred at 90°C for 1 hour. The unreacted ethylene was vented from the reactor cell and the contents of the reactor cell were cooled to ambient temperature. The contents of the reactor cell were then quenched with methanol (100 mL). The precipitated polymer in the reactor cell was separated by centrifuge and dried under vacuum at 60°C overnight to yield a white solid (720 mg). 1H NMR spectroscopy revealed that the white solid had a composition of ethylene (97 mole%) and methyl acrylate (3 mole%). GPC analysis revealed that the white solid had a weight average molecular weight of 115,000 g-mol"1 with a polydispersity of 1.5. We claim 1. A process for making a ligand having the formula (Formula Removed) wherein the process comprises the following reactions: (Formula Removed) wherein Q is phosphorus; wherein E1, E2 and E3 independently selected from lithium, magnesium, potassium and sodium; wherein V1, V2 and V3 are independently selected from chloride, bromide, fluoride, iodide, toluenesulfonate, methasulfonate, trifluoromethansulfonate and benzenesulfonate; wherein R15 is -SO3; wherein X1(R15)-E1, X2-E2 and X3-E3 are according to formulas I, II, and III, respectively. (Formula Removed) (Formula Removed) and, wherein each R20 is independently selected from a hydrogen; a halogen; and, a substituted or unsubstituted substituent selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C 2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20alkylsulfonyl, C1-C2oalkylsulfinyl, and silyl. 2. The process as claimed in claim 1, wherein reactions (a), (b) and (c) are done sequentially in the same vessel, wherein the reaction temperature during reaction (a) is less than the reaction temperature during reaction (b) and wherein the reaction temperature during reaction (b) is less than the reaction temperature during reaction (c). 3. The process as claimed in claim 1, wherein reaction (b) proceeds in the same vessel as reaction (a) without isolation of Compound I. 4. The process as claimed in claim 4, wherein reaction (c) proceeds in the same vessel as reaction (a) and reaction (b) without isolation of Compound II. 5. The process as claimed in claim 1, wherein X2-E2 and X3-E3 are the same. 6. The process as claimed in claim 1, wherein V1, V2 and V3 are chloride.

Full Text

The present invention relates to a process for making a ligand. [0001] This invention was made with United States Government support under ATP Award
No. 70NANB4H3014 awarded by the National Institute of Standards and Technology (NIST). The United States Government has certain rights in the invention. [0002] This Application claims the benefit of U.S. Provisional Patent Application No. 60/713,172, filed on August 31, 2005. [0003] The present invention relates to a method of synthesizing ligand structures that may be complexed with a late transition metal to form catalyst complexes useful in facilitating various polymerization reactions and/or Heck coupling reactions. [0004] The identification of new ligands for late transition metals and of commercially viable methods for making such ligands are important. For example, the identification of new ligands that complex with late transition metals to form catalyst complexes that are active for catalyzing polymerization reactions is of particular importance. That is, there remains an industry wide need for new molecular catalyst complexes that are capable of polymerizing
polar monomers in a controlled fashion and for copolymerizing polar monomers with olefins (e.g., ethylene, propylene) under mild reaction conditions. Of the many approaches to modifying the properties of a polymer, the incorporation of functional groups into an otherwise non-polar material would be ideal in many situations. The incorporation of polar groups into a non-polar material can result in modification to various physical properties of the resultant copolymer, for example, toughness, adhesion, barrier properties and surface properties. Changes in these physical properties can result in improved solvent resistance, miscibility with other polymers and rheological properties, and product performance such as paintability, dyeability, printability, gloss, hardness and mar resistance. [0005] The identification of new ligands that complex with late transition metals to form catalyst complexes that are active for Heck coupling reactions is also or particular commercial importance. [0006] One approach to the preparation of ligands is disclosed in United States Patent No. 5,760,286 to Brandvold. Brandvold disclose a method for the preparation of ligands according to the according to formula IV
(Formula Removed)
where A is selected from hydrogen, alkali earth metal, alkaline earth metal, quaternary ammonium, and a phosphonium group; RI is selected from the group consisting of hydrogen, an alkyl group having from 1 up to about 20 carbon atoms, an aromatic group or an aralkyl group; R2 is selected from the group consisting of an alkyl group of from 1 up to about 20 carbon atoms, an aromatic group or fused aromatic group, an aralkyl group, and a cycloalkyl group having from 5 up to about 10 ring carbon atoms; and, R3 is selected from the group consisting of hydrogen, an alkyl group of from 1 up to about 20 carbon atoms, an aromatic group or an aralkyl group, and a cycloalkyl group having from 5 up to about 10 ring carbon atoms, comprising: a first reaction of compounds of formula II,
with compounds of formula I
(Formula Removed)
to afford products of formula III
(Formula Removed)
where said first reaction proceeds by addition of a heterogeneous mixture of one molar proportion of the compound of formula I dispersed in an organic phase to a solution of the compound of formula II in an organic phase to afford a reaction mixture, said addition carried out at a rate such that the reaction mixture is at all times homogeneous, and; subsequent alkylation of the compound of formula III by an organometallic compound of formula R3M to yield the ligand of formula IV where R3M is a Grignard reagent or an organolithium.
[0007] Nevertheless, there remains a need for new ligands and new ligand synthesis methods
that provide such ligands in good yield and in relatively high purity.
[0008] In one aspect of the present invention, there is provided a process for making a ligand
having the formula (Formula Removed)

wherein the process comprises the following reactions:

(b)

v1-Q(v3)v2
X2-E2 + X'(R15)-Q(V3)V2 (Compound I)
X3-E3 + X'(R15)-Q(V3)-X2 (Compound II)

X'(RI5)-Q(V3)V2 (Compound I) X'(R15)-Q(V3)-X2 (Compound II) X1(R15)-Q(X3)-X2 (Compound III);

wherein Q is selected from phosphorus, arsenic and antimony; wherein E1, E2 and E3 are electrophilic metals; wherein V1, V2 and V3 are weakly-basic anions; wherein X1 , X2 and X3 are carbon anions; and, wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group.
[0009] In another aspect of the present invention, there is provided a process for making a ligand having the formula (Formula Removed)

wherein the process comprises the following reactions:
V'-Q(V3)V2
(i) X'(R'5)-B' +
X1(R15)-Q(V3)V2 (Compound I)
X1(R15)-Q(V3)V2 (Compound I) X1(R15)-Q(X2)-X2 (Compound IV);
wherein Q is selected from phosphorus, arsenic and antimony; wherein E1 and E2 are electrophilic metals; wherein V1, V2 and V3 are weakly-basic anions; wherein X1 and X2 are

carbon anions; and, wherein R15 is selected from -SO3, -SO2N(R18 ), -CO2, -PO3, - AsO3,
-SiO2, -C(CF3)2O; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and
a substituted hydrocarbyl group.
[0010] The term "protecting group" as used herein and in the appended claims refers to a
group of atoms that when attached to a reactive group in a molecule masks, reduces or
prevents undesired reactions with the reactive group. The use of protecting groups is well
known in the art. Examples of protecting groups and of how they may be used can be found,
among other places, in Protecting Groups in Organic Chemistry, J.W.F. McOmie, (ed.),
1973, Plenum Press and Protective Groups In Organic Synthesis, (Wiley, John & Sons, Inc.
3rd ed. 1999).
[0011] In some embodiments of the present invention, the process for making a ligand having
the formula
comprises the following reactions:
(a) X'(R15)-E1 + V1-Q(V3)V2 > X1(RI5)-Q(V3)V2
(Compound 1)
(b) x2-E2 + x1(R15)-Q(V3)v2 > x1(Rl5)-Q(v3)-x2
(Compound I) (Compound 11)
(c) X3-E3 + X'(R15)-Q(V3)-X2 > X1(R15)-Q(X3)-X2
(Compound II) (Compound III);
wherein Q is selected from phosphorus, arsenic and antimony; alternatively Q is selected from phosphorus and arsenic; alternatively Q is phosphorus;
wherein E1, E2 and E3 are independently selected from lithium, magnesium, potassium, beryllium, sodium, scandium, yttrium, titanium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; alternatively E1, E2 and E3 are independently selected from lithium, magnesium, potassium and sodium; alternatively E1, E2 and E3 are lithium; wherein V1, V2 and V3 are independently selected from chloride, bromide, fluoride, iodide, toluenesulfonate, methansulfonate, trifluoromethansulfonate, benzenesulfonate; alternatively V1, V2 and V3 are chloride; wherein X1, X2 and X3 are carbon anions; and,
wherein R15 is selected from -SO?, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; alternatively R" is selected from -SO3 and -SO2N(R18); alternatively R15 is -SO3; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl
1 8
group; alternatively R is selected from a hydrogen; a halogen; and, a substituted or
unsubstituted substituent selected from C1-C20alkyl, C3-C20 cycloalkyl, C2-C20alkenyl,
C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20carboxylate, C1-C20alkoxy,
C2-C20alkenyloxy, C1-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20alkylthio,
C1-C20alkylsulfonyI, C1-C20alkylsulfinyl, and silyl. In some aspects of these embodiments,
X1, X2 and X3 are all different. In some aspects of these embodiments, X2 and X3 are the
same.
[0012] In some embodiments of the present invention, reactions (a), (b) and (c) are
performed sequentially in the same vessel.
[0013] In some embodiments of the present invention, the reaction temperature during
reaction (a) is lower than the reaction temperature during reaction (b) and wherein the
reaction temperature during reaction (b) is lower than the reaction temperature during
reaction (c).
[0014] In some embodiments of the present invention, reaction (b) proceeds in the same
vessel as reaction (a) without isolation of Compound I.
[0015] In some embodiments of the present invention, reaction (c) proceeds in the same
vessel as reaction (b) without isolation of Compound II.
[0016] In some embodiments of the present invention, the process for making a ligand having
the formula
(Formula Removed)
comprises the following reactions: (i)
X1(R15)-Q(V3)V2
V1-Q(V3)V2
X1(R15)-E'
(Compound I) X1(R15)-Q(X2)-X2 (Compound IV);

X'(R15)-Q(V3)V2
(ii) 2 X-Ez +
(Compound I)
wherein 0 is selected from phosphorus, arsenic and antimony; alternatively Q is selected from phosphorus and arsenic; alternatively Q is phosphorus;
wherein E and E are independently from lithium, magnesium, potassium, beryllium,
sodium, scandium, yttrium, titanium, lanthanum, cerium, praseodymium, neodymium,
samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium
and lutetium; alternatively E1 and E2 are independently selected from lithium, magnesium,
potassium and sodium; alternatively E1 and E2 are lithium;
wherein V1 , V2 and V3 are independently selected from chloride, bromide, fluoride, iodide,
toluenesulfonate, methansulfonate, trifluoromethansulfonate, benzenesulfonate; alternatively
V1 ,V2 and V3 are chloride;
wherein X1 and X2 are carbon anions;
wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O;
alternatively Rl5 may be selected from -SO3 and -SO2N(R18); alternatively R15 is -SO3; where
R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted
hydrocarbyl group; alternatively where R18 is selected from a hydrogen; a halogen; and, a
substituted or unsubstituted substituent selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20
alkenyl, C2-C20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate,
C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20
alkylthio, C1-C20 alkylsulfonyl, C1-C20alkylsulfinyl, and silyl.
[0017] In some embodiments of the present invention, reactions (i) and (ii) are performed
sequentially in the same vessel.
[0018] In some embodiments of the present invention, the reaction temperature during
reaction (i) is lower than the reaction temperature during reaction (ii).
[0019] In some embodiments of the present invention, reaction (ii) proceeds in the same
vessel as reaction (i) without isolation of Compound I.
[0020] In some embodiments of the present invention, X1, X2 and X3 are independently
selected from aliphatic hydrocarbyl groups and aromatic hydrocarbyl groups; alternatively
X1, X2 and X3 are independently selected from aliphatic hydrocarbyl groups and aromatic
hydrocarbyl groups having up to 30 carbon atoms; alternatively X1, X2 and X3 are
independently selected from alkyl, cycloalkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl,
phenyl, biphenyl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl,
alkylthio, alkylsulfonyl, alkylsulfinyl, silyl, and derivatives thereof; alternatively X1, X2 and
X3 are independently selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20
alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C
2-C20 alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20alkylthio, C1-C20
alkylsulfonyl, C1-C20 alkylsulfmyl, silyl, and derivatives thereof; alternatively X1, X2 and X3
are substituted aryl groups. In some aspects of these embodiments, X2 and X3 are independently selected from ortho substituted aryl groups; alternatively X2 and X3 are independently selected from aryl groups with an ortho substituted phenyl; alternatively X2 and X1 are independently selected from aryl groups with an ortho substituted, substituted phenyl; alternatively X2 and X3 are independently selected from aryl groups with an ortho substituted, substituted phenyl having a formula 2,6-R16R17-phenyl; where R16 and R17 are independently selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, C1-C20 alkylsulfinyl, silyl, and derivatives thereof; alternatively X2 and X3 are aryl groups with an ortho substituted 2,6-dimethoxy phenyl.
[0021] In some embodiments of the present invention, X1(R15)-E1, X2-E2 and X3-E3 are according to formulas I, II, and III, respectively,
(Formula Removed)
wherein E1, E2 and E3 are independently selected from lithium, magnesium, potassium, beryllium, sodium, scandium, yttrium, titanium, lanthanum, cerium, praseodymium, neodyrnium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium; alternatively E1, E2 and E3 are independently selected from lithium, magnesium, potassium and sodium; alternatively E1, E2 and E are lithium;
wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; alternatively R15 is selected from -SO3 and -SO2N(R18); alternatively R15 is -SO3; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group; alternatively R18 is selected from a hydrogen, a halogen, and a substituted or unsubstituted substituent selected from C1-C20 alkyi, C3-C20 cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsulfonyl, C1-C20alkylsulfinyl, and silyl; and,
wherein each R20 is independently selected from a hydrogen, a halogen, and a substituted or unsubstituted substituent selected from C1-C20alkyl, C3-C20 cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20carboxylate, C1-C20alkoxy, C2-C20alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsiilfonyI, C1-C20alkylsulfinyl, and silyl; alternatively wherein each R20 is independently selected from a hydrogen, a phenyl and a substituted phenyl; alternatively wherein each R20 is independently selected from a hydrogen and a substituted phenyl; alternatively wherein each R20 is independently selected from a hydrogen and an ortho substituted phenyl. In some aspects of these embodiments, the substituted phenyl is an ortho substituted phenyl. In some aspects of these embodiments, the ortho substituted phenyl is 2,6-R16 Rl7-phenyl; where R16 and R17 are selected from C1-C20alkyl, C3-C20 cycloalkyl, C2-C20alkenyl, C2-C20alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20alkoxy, C2-C20alkenyloxy, C2-C20alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20alkylthio, C1-C20alkylsulfonyl, C1-C20alkylsulfinyl, and silyl. In some aspects of these embodiments, the ortho substituted phenyl is 2,6-dimethoxy phenyl. [0022] In some embodiments of the present invention, each R20 on formula II is independently selected from a hydrogen, a phenyl and a substituted phenyl. In some aspects of these embodiments, both R20's on formula II that are ortho to E2 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, one R20 that is ortho to E2 and the R20 that is para to E2 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, both R20's on formula II that are ortho to E2 and the R20 that is para to E2 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, the substituted phenyl is 2,6-dimethoxy phenyl. [0023] In some embodiments of the present invention, each R20 on formula III is independently selected from a hydrogen, a phenyl and a substituted phenyl. In some aspects
of these embodiments, both R20's on formula III that are ortho to E3 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, one R20 that is ortho to E3 and the R20 that is para to E3 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, both R20's on formula II that are ortho to E3 and the R20 that is para to E3 are selected from a phenyl and a substituted phenyl; alternatively a substituted phenyl. In some aspects of these embodiments, the substituted phenyl is 2,6-dimethoxy phenyl. [0024] In some embodiments of the present invention, the ligand having formula
(Formula Removed)
is selected from Structures I-XV presented in Table 1. In some aspects of these embodiments, the ligand is selected from Structures I, XI, and XIV. In some aspects of these embodiments, the ligand is selected from Structures I and XIV. In some aspects of these embodiments, the ligand is Structure I. In some aspects of these embodiments, the ligand is Structure XIV.
[0025] In some embodiments of the present invention, the reaction conditions for reaction (a) or reaction (i) are controlled such that the temperature of the reagents are maintained at a temperature which enables the reaction of V1-Q(V3)V2 with X1(R15)-E1 to proceed while inhibiting the reaction of V1-Q(V3)V2 with Compound I. In some aspects of these embodiments, the reaction temperature for reaction (a) or reaction (i) is maintained at [0027] In some embodiments of the present invention, the reaction conditions for reaction (b) are controlled such that the temperature of the reagents are maintained at a temperature which enables the reaction of Compound I with X2-E2 to proceed while inhibiting the reaction of Compound I with Compound II. In some aspects of these embodiments, the reaction
temperature during reaction (b) is maintained at -30°C; alternatively [0028] In some embodiments of the present invention, the process for making the ligand is
performed in a substantially oxygen-free atmosphere. In some aspects of these embodiments,
the process is performed in a nitrogen atmosphere. In some aspects of these embodiments,
the process is performed in an argon atmosphere.
[0029] In some embodiments of the present invention, no protecting groups are used in the
process to prepare the ligands.
[0030] The ligands prepared by the synthesis methods of the present invention may be
complexed with a late transition metal, such as palladium and nickel, to form late transition
metal catalyst complexes that may be used for example as polymerization catalysts and/or as
Heck coupling reaction catalysts.
[0031] Some embodiments of the present invention will now be described in detail in the
following Examples. All fractions and percentages set forth below in the Examples are by
weight unless otherwise specified. The chemical structures presented in Table 1 have been
drawn according to the general rules for drawing Lewis structures of molecules as described
in, for example, Brown, et al., Organic Chemistry, Brooks-Cole, 4th ed 2004.
Examples 1-16: (Ligand Synthesis)
[0032] Following the general procedure presented below using Component A and Component B identified in Table 1 in the amounts listed in Table 1, the Product Solids listed in Table 1 were prepared with the reported yield for examples 1-15, respectively. [0033] Component A was added to a 100 mL flask ("Flask A") then placed under vacuum and refilled with nitrogen and charged with 60 mL of tetrahydrofuran (THF). Flask A was then placed in an ice bath and allowed to cool to 0°C. 10.1 mL of 2.5 molar n-BuLi was then injected. Flask A was then placed in a dry ice/acetone bath and allowed to cool to about -78°C.
[0034] A separate 500 mL Schlenk flask ("Flask B") was placed under vacuum. Flask B was purged with nitrogen and charged with -50 mL of THF. Flask B was then placed in a dry ice/acetone bath and allowed to cool to about -78°C. 1.10 mL of PCU was then added to Flask B with agitation. The contents of Flask A were then slowly transferred to Flask B using a cannula with vigorous agitation.
[0035] A separate 100 mL flask ("Flask C") was purged and filled with nitrogen. Flask C was then charged with -60 mL of THF and Component B. Flask C was then placed in a dry ice/acetone bath and allowed to cool with agitation to about -78°C. 10.1 mL of 2.5 molar
n-BuLi was added to Flask C and allowed to react for about 15 minutes. The contents of Flask C were then transferred to Flask B, maintained at -78°C, using a cannula with continued vigorous agitation. Following the complete addition of the contents of Flask C into Flask B, Flask B was allowed to warm to room temperature for about 30 minutes. The contents of Flask B were then poured into a 500 mL recovery flask (Flask D) and the THF was removed, leaving a solid. The solid in Flask D was then mixed with distilled water and then transferred to a separation flask (Flask E). 100 mL of CH2C12 was added to the contents of Flask E. Flask E was shaken to mix the two layers. About 5 mL of concentrated HC1 was then added to Flask E. Flask E was shaken again. The mixture in Flask E was then allowed to settle, forming two layers-an organic phase on the bottom and a aqueous phase on the top. The organic layer was collected. The aqueous phase was washed with 50 mL of CH2Cl2. The organic wash material was collected and added to the previously collected organic layer material. The combined organic material was then contacted with MgSO4 and rotovaped to dryness, leaving a solid. The solid was then washed first with diethyl ether and then with THF to remove impurities. The washed Product Solid was collected by filtration with the yield reported in Table 1.
Table 1 (Table Removed)
Table 1, cont'd
(Table Removed)

Table 1. cont'd
(Table Removed)

Table 1, cont'd

(Table Removed)
Example 16: Synthesis of a potassium salt of the ligand of Structure VI [0036] A 0.45 g (0.81 mmol) sample of Product Solid (i.e., ligand Structure VI) prepared according to Example 6 was added to 50 mL of THF in a reaction flask with vigorous agitation to form a ligand solution. In a separate container, 0.10 g (0.88 mmol) of potassium tert-butoxide was dissolved in 20 mL of THF. The resulting potassium tert-butoxide solution was then added dropwise to the contents of the reaction flask with agitation. Following the addition of the potassium tert-butoxide solution, the contents of the reaction flask were reduced by vacuum extraction of some of the THF solvent leaving approximately 25 mL of product solution in the reaction flask. A potassium salt of the ligand was then precipitated from the remaining product solution through the addition of 20 mL of pentane. The precipitated potassium salt of the ligand was recovered by filtration through a fine porosity frit and washed with pentane 3 x 20 mL. The potassium salt of the ligand was then subjected to vacuum to remove the remaining volatiles, leaving a dark orange Product Powder 0.40 g (0.67 mmol, 83 %).
Example 17: Synthesis of a silver salt of the ligand of Structure VII [0037] A 0.75 g (1.43 mmol) sample of the Product Solid (i.e., ligand Structure Vll) prepared according to Example 7 was added to 50 mL of methanol in a reaction flask with vigorous agitation. In a separate container, 0.23 g (1.36 mmol) of silver nitrate was dissolved in 50 mL of deionized water. The resulting silver nitrate solution was then added dropwise to the contents of the reaction flask with vigorous agitation. Agitation of the contents of the reaction flask was continued for 20 minutes following addition of the silver nitrate solution. The contents of the reaction flask were then reduced by vacuum extraction of some of the solvent leaving approximately 50 mL and resulting in the formation of a gray precipitate. The precipitate was recovered by filtration through a fine porosity frit and washed with water 2 x 20 mL. The silver salt of the ligand was then dried under reduced pressure, leaving a dark gray Product Powder (0.35 g, 0.62 mmol, 44%).
Examples 18-31: (Preparation Transition Metal Catalyst Complexes) [0038] A sample of Component A identified in Table 2 was added to 30 mL of tetrahydrofuran in a reaction flask with agitation. To the contents of the reaction flask was then added Component B identified in Table 2, with continued agitation. The contents of the reaction flask were then agitated for 30 minutes before adding Component C identified in Table 2. The contents of the reaction flask were then reduced under vacuum and pentane was added to precipitate the product catalyst complex. The product catalyst complex was collected by filtration through a fine porosity frit and washed with pentane 2 x 20 mL. The product catalyst complex was then subjected to vacuum to remove the remaining volatiles, leaving the Product Yield reported in Table 2. Table 2
(Table Removed)

Table 2, cont'd

(Table Removed)
Example 32: (Preparation of Transition Metal Catalyst Complex & Heck Coupling) [0039] A reaction flask was charged with 0.02 g (30 u.mol) of palladium acetate and 0.025 g (70 µmol) of a Product Solid (i.e., ligand Structure XIII) prepared according to Example 13. The contents were dissolved in 1.5 mL of benzene. Bromobenzene (50 µL, 0.21 mmol) and methylacrylale (50 µL, 0.58 mmol) were added to the reaction flask followed by the addition of excess sodium acetate. The reaction was heated for 24 hours. Based on limiting reagent, conversion to 3-Phenyl-acrylic acid methyl ester was determined to be 30%.
Example 33: (Catalyst Preparation/Polymerization)
[0040] An 8 ml., serum vial equipped with a stirring bar in a glovebox was charged with palladium bis(dibenzylideneacetone) (41.1 mg, 72.0 umol); product solid (i.e., ligand Structure IX) prepared according to Example 9 (45.0 mg, 86.4 umol) and toluene (4.5 mL). The contents of the serum vial were allowed to stir for 10 minutes, producing a red/brown mixture (i.e., catalyst complex).
[0041 ] A reactor cell in a glovebox was charged with methyl acrylate (1.0 mL, 11.1 mmol), followed by the addition of toluene (4.0 mL). The reactor was then heated to 100 °C with agitation. The reactor cell was then pressurized with ethylene gas to 400 psig. After equilibration, a sample of catalyst complex as described above (0.5 mL , 8 umol Pd) was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The reactor cell was then removed from the glovebox. The reactor cell was observed to contain a green colored liquid with a black precipitate. The black precipitate dissolved when added to acidified MeOH (10% HC1). No polymer was observed to form.
Example 34: (Catalyst Preparation/Polymerization)
[0042] A sample of Product Solid (i.e., ligand Structure IX) prepared according to Example 9 (0.640 g, 1.40 mmol) was added to 30 mL of THF in a reaction flask with agitation. Dimethyl tetrainethylethylenediamine palladium (II) (0.350 g, 1.40 mmol) was then added to the reaction flask with agitation. The contents of the reaction flask were agitated for 30 minutes before adding dry pyridine (0.185 mL, 2.1 mmol). The contents of the reaction flask were then reduced under vacuum and pentane was added to precipitate the catalyst complex. The catalyst complex was collected by filtration through a fine porosity frit and washed with pentane 2 x 20 mL. The catalyst complex was then subjected to vacuum to remove the remaining volatiles, leaving a white solid (0.68 g, 1.09 mmol, 78 %).

[0043] Methyl aery late (1.0 mL, 11.1 mmol), followed by toluene (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the cell were then heated to 80 °C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of the catalyst complex prepared above (3 mg, 4.8 µmol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60 °C under vacuum. The subject reaction yielded 0.10 g of a random copolymer of ethylene and methyl acrylate.
Example 35-42: (Polymerization)
[0044] A reactor cell in a glovebox was charged with the Monomer Component identified in Table 3, followed by THF (4.0 mL). The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, 0.5 mL of tetrahydrofuran containing the Catalyst Component identified in Table 3 was injected into the reactor cell, followed by a tetrahydrofuran rinse (0.5 mL). After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and added to rapidly stirred MeOH. After stirring for 60 minutes, the polymer was vacuum filtered and dried under vacuum at 60°C for 18 hours. The Product Yield of random copolymer obtained from the reaction was as reported in Table 3. Table 3
(Table Removed)

Example 43: (Polymerization)
[0045] To an 8 mL serum vial equipped with a stirring bar in a glovebox was added palladium bis(dibenzylideneacetone) (41.1 mg, 72.0 umol); a sample of the Product Solid (i.e., ligand Structure XII) prepared according to Example 12 (45.0 mg, 86.4 µmol) and toluene (4.5 ml). The contents of the serum vial were allowed to stir for 10 minutes, producing a red/brown mixture (i.e., catalyst complex).
[0046] Three separate reactor cells in a glovebox were each charged with butyl aery late (1.0 mL, 11.1 mmol), followed by toluene (4.0 mL). The contents of the separate reactor cells were then pressurized with ethylene gas to 400 psig and heated to the temperature noted in Table 4. After equilibration, a 0.5 mL sample of the catalyst complex prepared above (8.0 ujnol Pd) was injected into each reactor cell, followed by a toluene rinse (0.5 mL). After 60 minutes, the reactor cells were vented and allowed to cool. The contents of the reactor cells were then removed from the glovebox and separately added to rapidly stirred MeOH. After stirring for 60 minutes, the product polymer in each reactor cell was separately vacuum filtered and dried under vacuum at 60°C for 18 hours. The polymer yield, butyl acrylate incorporation, weight average molecular weight, Mw, number average molecular weight, Mn and PD1 (i.e., Mw/Mn) for each reactor cell are reported in Table 4. Table 4 (Table Removed)
Example 4.4; (Polymerization)
[0047] Styrene (1.0 mL, 8.73 mmol) and norbornene (1.0 mL, 7.98 mmol, 85 mol% norbornene in toluene) were charged to a reactor cell in a glovebox. Toluene (4.0 mL) was then charged to the reactor cell. The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of a catalyst complex prepared according to Example 18 (1.6 mg, 2 µmol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight

at 60°C under vacuum. The subject reaction yielded 0.20 g of a random copolymer of ethylene, styrene and norbornene.
Example 45: (Polymerization)
[0048] Methyl acrylate (1.0 mL, 11.1 mmol) and norbornene (1.0 mL, 7.98 mmol, 85 mol% norbornene in toluene) were charged to a reactor cell in a glovebox. Toluene (4.0 mL) was then charged to the reactor cell. The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of a catalyst complex prepared according to Example 18 (1.6 mg, 2 µmol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 0.59 g of a random copolymer of ethylene, methyl acrylate and norbornene.
Example 46: (Polymerization)
[0049] Methyl acrylate (1.0 mL, 11.1 mmol) and styrene (1.0 mL, 8.73 mmol) were charged to a reactor cell in a glovebox. Toluene (4.0 mL) was then charged to the reactor cell. The contents of the reactor cell were then heated to 80°C and pressurized with ethylene gas to 400 psig. After equilibration, a sample of a catalyst complex prepared according to Example 18 (1.6 mg, 2 umol) was dissolved in 0.5 mL toluene and was injected into the reactor cell, followed by a 0.5 ml toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 0.81 g of a random copolymer of ethylene, methyl acrylate and styrene.
Example 47: (Polymerization)
[0050] To a 5 mL serum vial was added 41.4 mg (72 µmol) Palladium bis(dibenzylideneacetone) and 53.1 mg (86.4 (imol) of a Product Solid (i.e., ligand Structure 1) prepared according to Example 1. To this vial was then added 4.5 ml THF. The contents of the serum vial were stirred for several minutes to prepare a catalyst complex. [0051] Methyl acrylate (1.0 mL, 11.1 mmol) and THF (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the reactor cell were then heated to 70°C and pressurized
with ethylene gas to 400 psig. After equilibration, 0.1 mL (1.6 p.rnol) of the catalyst complex from the serum vial was injected into the reactor cell, followed by a 0.5 mL THF rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight al 6()°C under vacuum. The subject reaction yielded 1.02 g of a random copolymer of ethylene and methyl acrylate with an acrylate incorporation of 4.8 mol %; a weight average molecular weight, Mw, of 474,000 and a number average molecular weight, Mn, of 178,000.
Example 48: (Polymerization)
[0052] To a 5 ml, serum vial was added 41.4 mg (72 µmol) Palladium bis(dibenzylideneacetone) and 53.1 mg (86.4 µmol) of a Product Solid (i.e., ligand Structure I) prepared according to Example 1. To this vial was then added 4.5 ml THF. The contents of the serum vial were stirred for several minutes to prepare a catalyst complex. [0053] Methyl acrylate (1.0 mL, 11.1 mmol) and THF (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the reactor cell were then heated to 70°C and pressurized with ethylene gas to 400 psig. After equilibration, 0.1 mL (8.0 µmol) of the catalyst complex from the serum vial was injected into the reactor cell, followed by a 0.5 mL THF rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 1.28 g of a random copolymer of ethylene and methyl acrylate with an acrylate incorporation of 2.7 mol % and a weight average molecular weight, Mw of 172,000 and a number average molecular weight, Mn , of 57,000.
Example 49: (Polymerization)
|0054] To a 5 mL serum vial was added 41.4 mg (72 p,mol) Palladium bis(dibenzylideneacetone) and 53.1 mg (86.4 µmol) of a Product Solid (i.e., ligand Structure T) prepared according to Example 1. To this vial was added 4.5 ml toluene. The contents of the serum vial were stirred for several minutes to prepare a catalyst complex. [0055] Methyl acrylate (1.0 mL, 11.1 mmol) and toluene (4.0 mL), were charged to a reactor cell in a glovebox. The contents of the reactor cell were then heated to 50°C and pressurized with ethylene gas to 400 psig. After equilibration, 0.5 mL (8.0 µmol) of the catalyst complex
from the serum vial was injected into the reactor cell, followed by a 0.5 mL toluene rinse. After 60 minutes, the reactor cell was vented and allowed to cool. The contents of the reactor cell were then removed from the glovebox and were added to rapidly stirred MeOH. After 60 minutes, the resulting mixture was filtered on a glass frit, washed with excess MeOH and dried overnight at 60°C under vacuum. The subject reaction yielded 0.81 g of a random copolymer of ethylene and methyl acrylate with an acrylate incorporation of 0.4 mol %; a weight average molecular weight, Mw, of 716,000 and a number average molecular weight, Mn, of 388,000.
Example 50: (Ligand Synthesis)
(Formula Removed)
[0056] A first 100 ml, Schlenk flask was charged with benzenesulfonic acid hydrate (1.7 g, 10.7 mmol, C6H6O3S-H2O, 158.71 g/mol, MP Bio Medicals 98-11-3). The flask was evacuated under vacuum. The bottom of the flask was then heated using a heat gun. The flask contents melted to form a brown liquid, which started bubbling. The heating was continued until the liquid started to reflux and the pressure dropped to approximately 10 mTorr. The flask was filled with nitrogen, cooled and THF (anhydrous, Acros, ~50mL) was added to the flask forming a clear colorless solution. At 0°C, n-BuLi (2.5 M hexane solution, 11.4 mmol, 8.6 ml,, Aldrich) was added to yield a beige suspension, which was stirred for 0.5 hr before being cooled at -78°C.
[0057] A second 100 mL Schlenk flask was charged with Mg (0.30 g, 0.0125 mmol, powder, Aldrich). THF (50 mL, anhydrous, Acros) and 2-bromoanisole (2.10 g, 0.0112 mmol, C7H7BrO, 187.04 g/mol, Acros) were added to the second Schlenk flask. The contents of the second Schlenk flask were sonicated (~30 sec.) and the contents were observed to exhibit a temperature rise The mixture was stirred until it cooled back down to room temperature. [0058] A 200 mL Schlenk flask was charged with THF (-50 mL). At -78°C, PCl3 (0.93 mL, 1.47 g, 0.0107 mol, 1 .574 g/mL, 137.33 g/mol, Aldrich) was added to the 200mL Schlenk flask via syringe. The beige suspension in the first 100 mL Schlenk flask was transferred to the 200 mL Schlenk flask at -78°C via cannula. The contents of the 200 mL Schlenk flask were then stirred for 0.5 hours while maintaining the temperature at -78°C. The contents of the second 100 ml. Schlenk flask was cooled to -78°C and transferred to the 200 mL Schlenk
flask via cannula. The contents of the 200 mL Schlenk flask were then warmed to ambient temperature and stirred for about an hour to yield a yellow solution. [0059] A 500 mL Schlenk flask was charged with 2'-Br-2,6-(Me)2biphenyl (3.14 g, 10.7 mmol, C14H13BrO2, 293,16 g/mol, Aldrich) ant THF (150 mL). The contents of the 500 mL Schlenk flask were cooled to -78°C. n-BuLi (4.3 mL, 2.5 M hexane solution, 10.7 mmol, Aldrich) at -78°C was added to the 500 mL Schlenk flask, yielding a thick, white slurry. The 500 mL Schlenk flask was shaken by hand to ensure mixing. A 0.5 hour after the addition of the n-BuLi, the contents of the 200 mL Schlenk flask were added to the 500 mL Schlenk tlask via cannula. The contents of the 500 mL Schlenk flask were then allowed to gradually warm to ambient temperature. The contents of the 500 mL Schlenk flask were stirred overnight to yield a clear yellow solution. The volatiles were removed from the 500 mL Schlenk flask under vacuum. The resulting solid was extracted using CH2Cl2 (200 mL), H2O (200 mL), HC1 (concentrated, 20 mL). The organic layer from the extract was dried with MgSO4 and the volatile portion of the extract was removed under vacuum to leave a pale yellow solid. The pale yellow solid was collected and washed with THF (3x15 mL) and Et2O (3x15 mL) to yield a white powder product ligand (2.3 g, 44% yield). 1H NMR (CDC13, °C): δ 8.32 (m. 111), 7.71 (q,.7 = 8.5, 211), 7.56 (m, 1H), 7.47-7.40 (m, 4H), 7.33-7.27 (m, 2H), 6.99(m, 211), 6.91 (m, IH), 6.57 (d, .7=8.5, IH), 6.44 (d, J= 8.5, IH), 3.73 (s, 3H), 3.64 (s, 3H), 3.19 (s, 3H). 31P NMR (CDC13, °C): 8 -7.1 (s). LC-MS: m/z = 509.2.
Example 51: Polymerization
[0060] The vial was charged with Pd(dba)2 (19.8 mg, 0.0340 mmol, Pd(Ci7H,4Q)2, Alfa Aesar, 575.00 g/mol) and the product ligand of Example 50 (20.0 mg, 0.0390 mmol, C27H25O6PS, 508.53 g/mol). Toluene (10 mL) was then added to the vial. The contents of the vial were vigorously shaken to yield a dark red catalyst solution with a trace amount of particles.
[0061] A reactor cell was charged with methyl acrylate (1 mL) and toluene (4 mL). The reactor cell was heated to 90°C. Ethylene was then charged to the reactor cell (400 psi). The catalyst solution (0.5 mL) from the vial was added to the reactor cell vial cannula followed by a toluene rinse (0.5 mL). The reactor cell contents were stirred at 90°C for 1 hour. The unreacted ethylene was vented from the reactor cell and the contents of the reactor cell were cooled to ambient temperature. The contents of the reactor cell were then quenched with methanol (100 mL). The precipitated polymer in the reactor cell was separated by centrifuge and dried under vacuum at 60°C overnight to yield a white solid (720 mg). 1H NMR
spectroscopy revealed that the white solid had a composition of ethylene (97 mole%) and methyl acrylate (3 mole%). GPC analysis revealed that the white solid had a weight average molecular weight of 115,000 g-mol"1 with a polydispersity of 1.5.

We claim
1. A process for making a ligand having the formula
(Formula Removed)
wherein the process comprises the following reactions:
(Formula Removed)
wherein Q is phosphorus;
wherein E1, E2 and E3 independently selected from lithium, magnesium, potassium and
sodium;
wherein V1, V2 and V3 are independently selected from chloride, bromide, fluoride,
iodide, toluenesulfonate, methasulfonate, trifluoromethansulfonate and benzenesulfonate;
wherein R15 is -SO3;
wherein X1(R15)-E1, X2-E2 and X3-E3 are according to formulas I, II, and III, respectively.
(Formula Removed)

(Formula Removed)
and, wherein each R20 is independently selected from a hydrogen; a halogen; and, a substituted or unsubstituted substituent selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C 2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20alkylsulfonyl, C1-C2oalkylsulfinyl, and silyl.
2. The process as claimed in claim 1, wherein reactions (a), (b) and (c) are done sequentially in the same vessel, wherein the reaction temperature during reaction (a) is less than the reaction temperature during reaction (b) and wherein the reaction temperature during reaction (b) is less than the reaction temperature during reaction (c).
3. The process as claimed in claim 1, wherein reaction (b) proceeds in the same vessel as reaction (a) without isolation of Compound I.
4. The process as claimed in claim 4, wherein reaction (c) proceeds in the same vessel as reaction (a) and reaction (b) without isolation of Compound II.
5. The process as claimed in claim 1, wherein X2-E2 and X3-E3 are the same.
6. The process as claimed in claim 1, wherein V1, V2 and V3 are chloride.

Documents:

1854-del-2006-Abstract-(15-02-2011).pdf

1854-del-2006-abstract.pdf

1854-del-2006-Claims-(12-07-2011).pdf

1854-del-2006-Claims-(15-02-2011).pdf

1854-del-2006-claims.pdf

1854-del-2006-Correspodence Others-(12-07-2011).pdf

1854-del-2006-correspondence-others 1.pdf

1854-DEL-2006-Correspondence-Others-(12-10-2010).pdf

1854-del-2006-Correspondence-Others-(15-02-2011).pdf

1854-del-2006-correspondence-others.pdf

1854-del-2006-Description (Complete)-(15-02-2011).pdf

1854-del-2006-description (complete).pdf

1854-del-2006-Form-1-(15-02-2011).pdf

1854-del-2006-form-1.pdf

1854-del-2006-form-18.pdf

1854-del-2006-Form-2-(15-02-2011).pdf

1854-del-2006-form-2.pdf

1854-del-2006-Form-3-(12-07-2011).pdf

1854-DEL-2006-Form-3-(12-10-2010).pdf

1854-del-2006-form-3.pdf

1854-del-2006-form-5.pdf

1854-del-2006-GPA-(15-02-2011).pdf

1854-del-2006-gpa.pdf

1854-del-2006-Petition 137-(15-02-2011).pdf

1854-DEL-2006-Petition-137-(12-10-2010).pdf

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Patent Number

250117

Indian Patent Application Number

1854/DEL/2006

PG Journal Number

49/2011

Publication Date

09-Dec-2011

Grant Date

08-Dec-2011

Date of Filing

18-Aug-2006

Name of Patentee

ROHM AND HAAS COMPANY

Applicant Address

100 INDEPENDENCE MALL WEST, PHILADELPHIA, PENNSYLVANIA, 19106-2399, U.S.A.

Inventors:

#	Inventor's Name	Inventor's Address
1	NATHAN TAIT ALLEN	298 EGYPT ROAD, NORRISTOWN, PENNSYLVANIA 19403, USA.
2	BRIAN LESLIE GOODALL	1259 APPALACHIAN ROAD, AMBLER, PENNSYLVANIA 19002, USA.
3	THOMAS CLEVELAND KIRK	861 SACKETTSFORD RD. IVYLAND, PENNSYLVANIA 18974, USA.
4	LESTER HOWARD MCINTOSH III	1171 PAYNE ROAD, GREEN LANE, PENNSYLVANIA 18054, USA

PCT International Classification Number

C07F9/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/713,172	2005-08-31	U.S.A.
2	11/457,996	2006-07-17	U.S.A.