Ligand compound, organic chromium compound, and catalyst composition comprising same

Abstract

The present invention relates to a ligand compound having a novel structure, an organic chromium compound, a catalyst composition comprising the organic chromium compound, and a method for oligomerizing ethylene by using the catalyst composition, the ligand compound exhibiting high catalytic activity while exhibiting high selectivity of 1-hexene and 1-octene, and having a high selectivity of 1-hexene and 1-octene. Thus, ethylene oligomerization can be achieved with excellent efficiency.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0043953 filed on April 4, 2023, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.

[0003] The present invention relates to a ligand compound, an organochromium compound, a catalyst composition comprising the organochromium compound, and a method for oligomerizing ethylene by using the catalyst composition. Background Art

[0004] Linear α-olefins such as 1-hexene and 1-octene are used as detergents, lubricants, plasticizers, etc., and, in particular, are mainly used as comonomers for polymer density control in the production process of linear low-density polyethylene (LLDPE).

[0005] In a typical production process of linear low density polyethylene (LLDPE), copolymerization is carried out with a comonomer such as an α-olefin, for example 1-hexene or 1-octene, in order to control the density by forming branches in the polymer backbone with ethylene.

[0006] Therefore, in order to produce LLDPE with a high comonomer content, there is a problem that the price of the comonomer accounts for a large part of the production cost. Various attempts have been made to solve the above problem.

[0007] Such linear α-olefins are mainly produced by the Shell Higher Olefin Process. However, the above process simultaneously synthesizes α-olefins having different lengths according to the Schulze-Flory distribution, and thus a separate separation process is required to obtain a specific α-olefin, which is cumbersome.

[0008] In order to solve the above problems, a method for selectively synthesizing 1-hexene by trimerization of ethylene or selectively synthesizing 1-octene by tetramerization of ethylene has been proposed. In addition, many studies have been conducted on catalyst systems capable of achieving such selective oligomerization of ethylene.

[0009] [Prior art literature]

[0010] [Patent Document]

[0011] (Patent Document 1) US 5064802 B2 Summary of the invention

[0012] Technical issues

[0013] One aspect of the present invention provides a ligand compound having a novel structure, an organic chromium compound, and a catalyst composition comprising the organic chromium compound, wherein the ligand compound exhibits high catalytic activity and high selectivity for 1-hexene and 1-octene, thereby enabling ethylene oligomerization to be achieved with excellent efficiency.

[0014] Technical Solution

[0015] According to one aspect of the present invention, a ligand compound, an organochromium compound, a catalyst composition and an ethylene oligomerization method are provided.

[0016] (1) The present invention provides a ligand compound represented by the following formula 1.

[0017] [Formula 1]

[0018]

[0019] In the above formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 6 bonded to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, wherein if R 6 and R 1 are not bonded to each other to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, then R 6 is hydrogen, R 2 To R 4 are each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein R 2 To R 4 are not hydrogen, and R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

[0020] (2) In the ligand compound of the present invention of (1) above, R 1is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 6 The bonds form a monocyclic or polycyclic heterocyclic ring.

[0021] (3) In the above (1) or (2), the present invention provides a ligand compound wherein R 1 is fluoro, trifluoromethyl, methoxy, methyl, trifluoromethoxy, trifluoromethylthio, methylthio, methylsulfonate or trimethylsilyl, or is 6 Bonding forms furan or dibenzofuran.

[0022] (4) In any one of the above (1) to (3), the present invention provides a ligand compound wherein R 2 To R 4 are each independently hydrogen, an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group, wherein R 2 To R 4 Not hydrogen at the same time.

[0023] (5) In any one of the above (1) to (4), the present invention provides a ligand compound wherein R 2 To R 4 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

[0024] (6) In any one of the above (1) to (4), the present invention provides a ligand compound wherein R 2 is hydrogen, and R 3 and R 4 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

[0025] (7) In any one of the above (1) to (6), the present invention provides a ligand compound wherein R 5 It is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused to an aryl group having 6 to 10 carbon atoms.

[0026] (8) In any one of the above (1) to (7), the present invention provides a ligand compound, wherein the ligand compound represented by the above Formula 1 is represented by any one of the following Formulas 2 to 9.

[0027] [Formula 2]

[0028]

[0029] [Formula 3]

[0030]

[0031] [Formula 4]

[0032]

[0033] [Formula 5]

[0034]

[0035] [Formula 6]

[0036]

[0037] [Formula 7]

[0038]

[0039] [Formula 8]

[0040]

[0041] [Formula 9]

[0042]

[0043] In the above formulas 2 to 9, R 1 To R 6 Each is the same as defined in the above formula (1).

[0044] (9) In any one of the above (1) to (8), the present invention provides a ligand compound, wherein the ligand compound represented by the above Formula 1 is represented by any one of the following Formulas 2-1 to 2-96 and 9-1 to 9-20.

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] (10) The present invention provides an organic chromium compound comprising the ligand compound according to any one of (1) to (9) above and chromium bidentiated with the ligand compound.

[0052] (11) In the above (10), the present invention provides an organic chromium compound, wherein in the ligand compound represented by the above formula 1, at least one non-shared electron pair of N and two Ps is in a bidentiation form with chromium.

[0053] (12) The present invention provides a catalyst composition comprising the ligand compound according to any one of (1) to (9) above, chromium and a co-catalyst.

[0054] (13) In the above (12), the present invention provides a catalyst composition, wherein the chromium is derived from a chromium source, wherein the chromium source includes at least one selected from chromium (III) acetylacetonate, tetrahydrofuran chromium (III) chloride, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)chromium (III) and chromium (III) stearate.

[0055] (14) In the above (12) or (13), the present invention provides a catalyst composition, wherein the co-catalyst is at least one selected from the group consisting of compounds represented by the following Formula 10 to Formula 13.

[0056] [Formula 10]

[0057] -[Al(R 13 )-O] a -

[0058] In the above formula 10,

[0059] R 13 are each independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and a is an integer of 2 or more,

[0060] [Formula 11]

[0061] E(R 14 )3

[0062] In the above formula 11,

[0063] E is aluminum or boron, and R 14 are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and

[0064] [Formula 12]

[0065] [LH] + [G(Y)4] -

[0066] [Formula 13]

[0067] [L] + [G(Y)4] -

[0068] In the above formulas 12 and 13, L is a neutral or cationic Lewis acid, [LH] + is a Bronsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and here, if the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0069] (15) The present invention provides a method for preparing linear α-olefins, which comprises S10 oligomerizing ethylene in the presence of the catalyst composition according to any one of (12) to (14) above.

[0070] (16) In the above (15), the present invention provides a method for producing a linear α-olefin, wherein the linear α-olefin is 1-hexene, 1-octene or a mixture thereof.

[0071] Beneficial Effects

[0072] When ethylene oligomerization is carried out using an organic chromium compound and a catalyst composition comprising the ligand compound of the present invention, linear α-olefins having high selectivity for 1-hexene and 1-octene can be produced while having excellent productivity due to high catalytic activity. DETAILED DESCRIPTION

[0073] Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.

[0074] It should be understood that the words or terms used in the description and claims of the present invention should not be interpreted as limited to the meanings defined in commonly used dictionaries. It should also be understood that based on the principle that the inventor can correctly define the meaning of words or terms to best explain the present invention, these words or terms should be interpreted as having a meaning consistent with their meaning in the context of the relevant field and the technical idea of ​​the present invention.

[0075] Ligand compounds

[0076] The present invention provides a ligand compound suitable for a catalyst used in an ethylene oligomerization reaction. When the ligand compound is applied to an ethylene oligomerization reaction, specifically, a catalyst composition for forming linear α-olefins, the selectivity for linear α-olefins is high, while exhibiting excellent catalytic activity, and in particular, when compared with a catalyst containing a symmetrical ligand compound and a typical PNP-based catalyst even under the same reaction conditions, the yield of solid polyethylene is small, thereby making it possible to more efficiently prepare linear α-olefins.

[0077] According to one embodiment of the present invention, the organochromium compound that is double coordinated with the ligand compound can be used to prepare linear α-olefins using ethylene, and the oligomerization reaction is carried out in a reaction under ethylene conditions, so that liquid α-olefins, specifically, liquid 1-hexene or 1-octene can be formed with high selectivity. This is because the selectivity for α-olefins of a certain length is increased by forming a transition state of a metallacycle in the ethylene oligomerization reaction.

[0078] According to one embodiment of the present invention, the ligand compound includes diphosphinoamine moiety, wherein the aryl with specific substituent is connected to the end of the diphosphinoamine moiety, therefore, it is possible to have a form that can itself be used as a strong electron-donating group. Due to this structural feature, the ligand compound can be applied to ethylene oligomerization catalyst systems and show high activity, particularly for 1-hexene, 1-octene, etc. can show high selectivity. This may be due to the interaction between adjacent chromium active sites, particularly, when the aryl replaced by specific substituent is connected to the phosphorus (P) atom of diphosphinoamine, the electron density of phosphorus (P) atom and nitrogen (N) atom contained in diphosphinoamine increases, and the electrical and spatial properties of the whole ligand compound change. Therefore, due to the change in the bond between the ligand and the chromium atom, the structure of the catalyst can become more stable, and compared with the typical metal cycloheptane or metal cyclononane form, α-olefins with higher activity and selectivity can be formed by changing the energy (activation energy) in the transition state, and the amount of by-products such as high molecular weight solid α-olefins (e.g., polyethylene wax (PE wax)) can be further reduced.

[0079] According to one embodiment of the present invention, the ligand compound is characterized in that the phenyl at the end of the diphosphinoamido moiety has a halogen group, an alkyl group, an alkoxy group or an alkoxy group substituted by at least one fluorine as a substituent in the ortho position, and each has an alkyl group with a specific carbon number as a substituent or a silyl group substituted by an alkyl group with a specific carbon number in the meta position and the para position. The substituent substituted in the ortho position of the phenyl can increase the steric strain around the metal atom, thereby improving the selectivity of 1-hexene, and can also protect the metal atom or directly form a double coordination bond, thereby playing the role of improving the stability of the metal coordination compound. Meanwhile, the substituent substituted in the meta position and the para position of the phenyl can increase the solubility of the ligand compound and the metal coordination compound in the polymerization solvent respectively, thereby improving activity and selectivity. Therefore, if the ligand compound is used, a chromium catalyst with high stability and excellent activity and selectivity can be prepared.

[0080] According to one embodiment of the present invention, in the ligand compound, the nitrogen atom bonded with two phosphorus atoms is bonded to a bulky substituent, such as a cycloalkyl or a phenyl group, wherein the bulky substituent bonded to the nitrogen can prevent the rotation of the bond between nitrogen and phosphorus, thereby further improving the stability and activity of the catalyst. At this time, the activity, stability and selectivity of the catalyst vary according to the spatial properties of the substituent entity bonded to the nitrogen atom. If the spatial strain of the substituent bonded to the nitrogen atom is too high, there is a problem that the formation of the ligand synthesis and the metal coordination compound becomes difficult and the generated coordination compound becomes unstable. In addition, if the spatial strain of the substituent bonded to the nitrogen atom is too high, there is a problem that the raw material such as ethylene is difficult to approach, thereby reducing the activity of the catalyst. In addition, if the spatial strain of the substituent bonded to the nitrogen atom is too low, the rotation of the bond between the nitrogen atom and the phosphorus atom cannot be prevented, and the metal central atom cannot be protected, thereby causing the activity and stability of the catalyst to deteriorate. That is, if the spatial strain of the substituent bonded to the nitrogen atom is too high or too low, the activity of the catalyst is reduced, and its stability deteriorates, thereby there is a problem that the byproducts such as polyethylene wax produced will increase. Therefore, it is very important to select a substituent bonded to the nitrogen atom that has an appropriate level of steric strain relative to the substituent bonded to the phosphorus atom. In the ligand compound according to the present invention, the steric strain around the PNP functional group is increased by introducing a substituent at the meta position of the phenyl group bonded to the phosphorus atom. Therefore, by introducing R represented by Formula 1 5 The steric strain of the substituent bonded to the nitrogen atom is significantly increased by using a catalyst composition containing the ligand compound to improve the yield and selectivity during the ethylene oligomerization reaction. In particular, when a substituent in the form of a secondary alkyl group is introduced as R of Formula 1, 5When the substituents represented are used, the efficiency is further improved, and by introducing aromatic groups (such as phenyl groups) at the carbon positions 1 and 2 to compensate for the low steric strain, the substituents in the form of primary alkyl groups can form appropriate steric strain, thereby improving the yield and selectivity.

[0081] According to one embodiment of the present disclosure, the ligand compound may be represented by the following Formula 1.

[0082] [Formula 1]

[0083]

[0084] In the above formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 6 bonded to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, wherein if R 6 and R 1 are not bonded to each other to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, then R 6 is hydrogen, R 2 To R 4 are each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein R 2 To R 4 are not hydrogen, and R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

[0085] In the present invention, the "halogen group" refers to fluorine (-F), chlorine (-Cl), bromine (-Br) and iodine (-I).

[0086] In the present invention, “substituted with a halogen group” may mean that at least one hydrogen atom bonded to a carbon atom of each substituent is substituted with a halogen atom, or if the carbon atom number of each substituent is mentioned, may mean the carbon atom number of each substituent.

[0087] In the present invention, "alkyl" may refer to a straight chain or branched hydrocarbon moiety, and specific examples thereof may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, etc., depending on the defined number of carbon atoms.

[0088] In the present invention, "alkylthio" may mean that the substituent on either side of the thioether bond is an alkyl group, and if the number of carbon atoms is mentioned, it may mean the number of carbon atoms of the alkyl group.

[0089] In the present invention, the "alkylsulfonate group" may mean that the sulfur atom of the sulfonate is substituted with an alkyl group, and if the number of carbon atoms is mentioned, it may mean the number of carbon atoms of the alkyl group.

[0090] In the present invention, a "trialkylsilyl group" is represented by -SiR3 and refers to a substituent in which each R is independently an alkyl group, and the carbon number of the trialkylsilyl group may refer to the sum of the carbon numbers of all Rs.

[0091] In the present invention, a "monocyclic aromatic hydrocarbon ring" may refer to an aromatic hydrocarbon consisting of one ring, such as a benzene ring, and a "polycyclic aromatic hydrocarbon ring" may refer to an aromatic hydrocarbon consisting of two or more rings, such as a naphthalene ring.

[0092] In the present invention, "monocyclic heterocycle" may refer to a heterocycle consisting of one ring containing heteroatoms, such as furan, thiophene, pyrrole and pyridine, and "polycyclic heterocycle" may refer to a heterocycle consisting of two or more rings containing heteroatoms, such as benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, benzopyrrole and dibenzopyrrole. The heterocycle may form an aliphatic ring or an aromatic ring.

[0093] In the present invention, "cycloalkyl" may refer to a cyclic hydrocarbon moiety, and specific examples thereof may be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like according to the defined carbon atom number.

[0094] In the present invention, “alkoxyalkyl” may refer to an alkyl group substituted with an alkoxy group, and the carbon number of the alkoxyalkyl group may refer to the sum of the carbon number of the alkoxy group and the carbon number of the alkyl group.

[0095] In the present invention, “arylalkoxyalkyl” may refer to an alkyl group substituted with an alkoxy group including an aryl group as a substituent, and the carbon number of the arylalkoxyalkyl group may refer to the sum of the carbon number of the alkoxy group and the carbon number of the alkyl group.

[0096] In the present invention, unless otherwise indicated, "aryl" refers to an arbitrarily substituted benzene ring, or refers to a ring system that can be formed by condensing one or more arbitrary substituents. The example of an arbitrary substituent includes an alkyl group having a substitution of 1 to 2 carbon atoms, an alkenyl group having a substitution of 2 to 3 carbon atoms, an alkynyl group having a substitution of 2 to 3 carbon atoms, a heteroaryl group, a heterocyclic group, an aryl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, aroyl group, a heteroaroyl group, an acyloxy group, aroyloxy group, a heteroaroyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, an aminosulfonyl group, a sulfonyl group, a carboxamide group, an aminocarbonyl group, a carboxyl group, an oxo group, a hydroxyl group, a sulfydryl group, an amino group, a nitro group, a cyano group, a halogen group or a urea group. This ring or ring system can be condensed arbitrarily to any aromatic ring (e.g., a benzene ring), a carbocycle or a heterocycle having one or more substituents. It may include, but is not limited to, phenyl, naphthyl, tetrahydronaphthyl, biphenyl, indanyl, anthracenyl or phenanthrenyl and substituted derivatives thereof.

[0097] According to one embodiment of the present invention, R l It may be a fluorine group, a chlorine group, a bromine group, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or may be in combination with R 6 bonded to form a monocyclic or polycyclic heterocyclic ring. As a specific example, R 1 It may be a fluorine group, a trifluoromethyl group, a methoxy group, a methyl group, a trifluoromethoxy group, a trifluoromethylthio group, a methylthio group, a methylsulfonate group or a trimethylsilyl group, or may be bonded to R6 to form furan or dibenzofuran.

[0098] According to one embodiment of the present invention, R 2 To R 4 may be each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxyalkyl group having 6 to 12 carbon atoms, an arylalkoxyalkyl group having 10 to 20 carbon atoms, or a trialkylsilyl group, wherein R 2 To R 4 may not be hydrogen at the same time, in which case the alkyl groups of the trialkylsilyl group may each independently be an alkyl group having 1 to 5 carbon atoms. 2 To R 4 may be each independently hydrogen, an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group, wherein R 2 To R 4 As a more specific example, R2 To R 4 can each independently be n-decyl, tripropylsilyl or tributylsilyl, and as another example, R 2 can be hydrogen, and R 3 and R 4 can be independently n-decyl, tripropylsilyl or tributylsilyl. That is, in the ligand compound, the phenyl group at the end of the diphosphino group can have R 1 substituent, and at the same time may have an alkyl group having 10 carbon atoms as a substituent, or may have a silyl group substituted with an alkyl group having 3 or 4 carbon atoms at the meta-position or para-position.

[0099] According to one embodiment of the present invention, R 5 It may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused to an aryl group having 6 to 10 carbon atoms. As a specific example, R 5 It may be an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms condensed with an aryl group having 6 to 10 carbon atoms.

[0100] According to one embodiment of the present invention, the ligand compound represented by the above Formula 1 may be represented by any one of Formulas 2 to 9 below.

[0101] [Formula 2]

[0102]

[0103] [Formula 3]

[0104]

[0105] [Formula 4]

[0106]

[0107] [Formula 5]

[0108]

[0109] [Formula 6]

[0110]

[0111] [Formula 7]

[0112]

[0113] [Formula 8]

[0114]

[0115] [Formula 9]

[0116]

[0117] In the above formulas 2 to 9, R 1 To R 5 Each is the same as defined in Formula 1 above.

[0118] According to one embodiment of the present invention, the ligand compound represented by the above Formula 1 may be a ligand compound represented by any one of the following Formulas 2-1 to 2-96 and 9-1 to 9-20.

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125] According to one embodiment of the present invention, in addition to the above-mentioned embodiments, the ligand compound may be implemented in various combinations within the range satisfying the above-mentioned conditions, and any compound represented by Formula 1 may be used as the ligand compound of the present invention.

[0126] Organic chromium compounds and catalyst compositions

[0127] The present invention provides an organic chromium compound, which comprises a ligand compound represented by the above formula 1 and chromium (Cr) bidentate with the ligand compound.

[0128] According to one embodiment of the present invention, the organic chromium compound is a chromium coordination compound of a ligand compound, wherein the chromium of the chromium source may have a form in which at least one non-shared electron pair of N and two P in the ligand compound represented by Formula 1 has a bidentate bond. That is, it is a structure in which the phosphorus atom or nitrogen atom of the diphosphine amine moiety provides a non-shared electron pair to the chromium atom, and it may be particularly preferred that the two pairs of non-shared electron pairs are in a bidentate bidentate state. The organic chromium compound may be applied to a catalyst system for ethylene oligomerization, and exhibits excellent catalytic activity and high selectivity for 1-hexene or 1-octene.

[0129] In the present invention, "catalyst composition" may refer to a catalyst composition in the following state: wherein three components including a chromium source, a ligand compound and a co-catalyst, or two components of a transition metal compound and a co-catalyst are added simultaneously or in any order to be obtained as an active catalyst composition. Here, the catalyst composition may also be referred to as a catalyst system, and in the present invention, the catalyst composition and the catalyst system represent the same meaning. The three or two components of the catalyst composition may be added in the presence or absence of a solvent and a monomer, and may be used in a supported or unsupported state.

[0130] The present invention provides a catalyst composition comprising the above-mentioned ligand compound, chromium and a co-catalyst. As described above, the ligand compound represented by the above formula 1 and the chromium can be double coordinated to form an organic chromium compound. That is, the catalyst system can be a three-component catalyst system comprising chromium, a ligand compound represented by the above formula 1 and a co-catalyst, or a two-component catalyst system comprising an organic chromium compound and a co-catalyst. As a specific example, the catalyst composition can include the ligand compound, an organic chromium compound containing chromium double coordinated with the ligand compound, and a co-catalyst. In addition, the catalyst composition can include a chromium compound, wherein some components of the co-catalyst are bonded to the organic chromium compound.

[0131] According to one embodiment of the present invention, chromium may be derived from a chromium source, and the chromium source may be an organic or inorganic chromium compound in which the oxidation state of chromium is from about 0 to about 6. As a specific example, the chromium source may be chromium metal, or a compound in which any organic or inorganic group is bonded to chromium. Here, the organic group may be an alkyl group, an alkoxy group, an ester group, a ketone group, an acylamino group, a carboxylate group, etc., each group having 1 to 20 carbon atoms, and the inorganic group may be a halide, a sulfate, an oxide, etc.

[0132] According to one embodiment of the present invention, the chromium source is a compound that exhibits high activity in olefin oligomerization and is easy to use and obtain, and may be at least one compound selected from chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuranate, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, tris(2,2,6,6-tetramethyl-3,5-heptanedioate)chromium (III) and chromium (III) stearate.

[0133] According to one embodiment of the present invention, the co-catalyst may be one or more selected from the group consisting of compounds represented by the following Formulae 10 to 13.

[0134] [Formula 10]

[0135] -[Al(R 13 )-O] a -

[0136] In the above formula 10, R 13 Each is independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and a is an integer of 2 or more.

[0137] [Formula 11]

[0138] E(R 14 )3

[0139] In the above formula 11, E is aluminum or boron, and R 14 Each is independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group.

[0140] [Formula 12]

[0141] [LH] + [G(Y)4] -

[0142] [Formula 13]

[0143] [L] + [G(Y)4] -

[0144] In Formulas 12 and 13 above, L is a neutral or cationic Lewis acid, [LH] + is a Bronsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and here, if the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

[0145] According to one embodiment of the present invention, the catalyst composition can be prepared by a variety of methods. As a specific example, first, the catalyst composition can be prepared by contacting an organic chromium compound with a compound represented by the above formula 10 or formula 11. Second, the catalyst composition can be prepared by contacting an organic chromium compound with a compound represented by the above formula 10 or formula 11 to obtain a mixture, and adding a compound represented by the above formula 12 or formula 13 to the mixture. Third, the catalyst composition can be prepared by contacting an organic chromium compound with a compound represented by the above formula 12 or formula 13. Fourth, the catalyst composition can be prepared by contacting an organic chromium compound with a compound represented by the above formula 12 or formula 13 to obtain a mixture, and adding a compound represented by the above formula 10 or formula 11 to the mixture. Fifth, the catalyst composition can be prepared by contacting a chromium source with a compound represented by the above formula 12 or formula 13 to obtain a reactant, and contacting the reactant with a ligand compound.

[0146] According to one embodiment of the present invention, in the case of the first method or the third method among the above methods for preparing the catalyst composition, the molar ratio of the compound represented by the above formula 10 or formula 11 to the organic chromium compound can be 1:2 to 5000, as a specific example, it can be 1:100 to 3000, as a more specific example, it can be 1:300 to 1500. Within the above range, the alkylation of the organic chromium compound can be fully achieved, so that the activity of the catalyst composition can be improved, and the activity of the alkylated organic chromium compound can be prevented from decreasing due to the side reaction with the remaining alkylating agent. At the same time, the economic feasibility and purity of the prepared linear α-olefin can be improved.

[0147] According to one embodiment of the present invention, in the case of the second method among the above methods for preparing the catalyst composition, the molar ratio of the compound represented by the above Formula 12 or Formula 13 relative to the organic chromium compound can be 1:1 to 500, as a specific example, it can be 1:1 to 50, as a more specific example, it can be 1:1 to 25. Within the above range, the amount of the activator is sufficient to fully activate the metal compound, thereby improving the activity of the catalyst composition, and the remaining activator is reduced to a minimum, thereby improving the economic feasibility and purity of the prepared linear α-olefin.

[0148] According to one embodiment of the present invention, the compound represented by Formula 10 may be an alkylaluminoxane, and as a specific example, it may be methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and as a more specific example, it may be methylaluminoxane.

[0149] According to one embodiment of the present invention, the compound represented by the above Formula 11 may be trialkylaluminum, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum hydride, alkylaluminum dihydride, trialkylboron, or the like. As a specific example, the compound represented by the above formula 6 may be a trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum and tri-p-tolylaluminum; a dialkylaluminum halide such as diethylaluminum chloride; a dialkylaluminum hydride such as diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenethylaluminum hydride, phenyl-n-propylaluminum hydride,

[0047] The invention also includes phenylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyln-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyln-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyln-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisobutylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride and benzyl-n-octylaluminum hydride; alkylaluminum hydrides such as n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride and n-octylaluminum dihydride; trialkylborons such as trimethylboron, triethylboron, triisobutylboron, tripropylboron and tributylboron, etc.

[0150] According to one embodiment of the present invention, the compound represented by Formula 12 or Formula 13 may be trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dioctadecylanilinium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, triethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, tributylammonium tetra(p-tolyl)borate, methyldioctadecylammonium tetra(p-tolyl)borate, N,N-dimethylanilinium tetra(p-tolyl)borate ) borate, N,N-diethylanilinium tetra(p-tolyl) borate, N,N-dioctadecylanilinium tetra(p-tolyl) borate, trimethylammonium tetra(o-, p-dimethylphenyl) borate, triethylammonium tetra(o-, p-dimethylphenyl) borate, tripropylammonium tetra(o-, p-dimethylphenyl) borate, tributylammonium tetra(o-, p-dimethylphenyl) borate, methyldioctadecylammonium tetra(o-, p-dimethylphenyl) borate, N,N-dimethylanilinium tetra(o-, p-dimethylphenyl) borate, N,N-diethylanilinium tetra(o-, p-dimethylphenyl) borate, N,N-dioctadecylanilinium tetra(o-, p-dimethylphenyl) borate, trimethylammonium tetra(p-trifluoromethylphenyl) ) borate, triethylammonium tetrakis(p-trifluoromethylphenyl)borate, tripropylammonium tetrakis(p-trifluoromethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-diethylanilinium tetrakis(p-trifluoromethylphenyl)borate, N,N-dioctadecylammonium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tributylammonium tetrakis(pentafluorophenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N- Diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dioctadecylammonium tetrakis(pentafluorophenyl)borate, trimethylphosphonium tetraphenylborate, triethylphosphonium tetraphenylborate, tripropylphosphonium tetraphenylborate, tributylphosphonium tetraphenylborate, trimethylcarbonium tetraphenylborate, triethylcarbonium tetraphenylborate, tripropylcarbonium tetraphenylborate, tributylcarbonium tetraphenylborate, trimethylammonium tetraphenylaluminate, triethylammonium tetraphenylaluminate, tripropyltetraphenylaluminate, tributylammonium tetraphenylaluminate, trimethylammonium tetra(p-tolyl)aluminate, triethylammonium tetra(p-tolyl)aluminate, tripropylammonium tetra(p-tolyl)aluminate, tributylammonium tetra(p-tolyl)aluminate, and the like.

[0151] According to one embodiment of the present invention, the content ratio of the components used to form the catalyst composition can be determined in consideration of the catalyst activity and the selectivity to linear α-olefins. As a specific example, when the catalyst composition is a three-component catalyst composition, the molar ratio of the diphosphinoamine moiety of the ligand compound: the chromium source: the co-catalyst can be controlled to be about 1:1:1 to about 10:1:10000, or about 1:1:100 to about 5:1:3000. In addition, when the catalyst composition is a two-component catalyst composition, the molar ratio of the diphosphinoamine moiety of the ligand compound: the co-catalyst can be controlled to be about 1:1 to about 1:10000, about 1:1 to about 1:5000, or about 1:1 to about 1:3000.

[0152] According to one embodiment of the present invention, when preparing the catalyst composition, a hydrocarbon-based solvent such as pentane, hexane, and heptane, or an aromatic solvent such as benzene and toluene may be used as a reaction solvent.

[0153] According to one embodiment of the present invention, the components for forming the catalyst composition can be added simultaneously or in any order in the presence or absence of a suitable solvent and monomer, and serve as an active catalyst composition. At this time, a suitable solvent can be heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, etc.

[0154] According to one embodiment of the present invention, the organic chromium compound and the co-catalyst may be used in the form of being supported on a carrier, and in this case, the carrier may be silicon oxide or aluminum oxide.

[0155] According to one embodiment of the present invention, the catalyst composition may further include a carrier. As a specific example, the ligand compound represented by the above formula 1 may be applied to ethylene oligomerization in the form of being supported on a carrier. The carrier may be a metal, a metal salt or a metal oxide applied to a supported catalyst, and as a specific example, the carrier may be silicon oxide, silicon oxide-aluminum oxide, silicon oxide-magnesium oxide, etc., and may include metal oxides, carbonates, sulfates or nitrate components, such as Na2O, K2CO3, BaSO4 and Mg(NO3)2.

[0156] According to one embodiment of the present invention, the catalyst composition can be used for the trimerization or tetramerization reaction of ethylene, and due to the high selectivity mentioned above, 1-hexene or 1-octene can be produced.

[0157] Ethylene oligomerization process

[0158] The present invention provides a linear α-olefin production method as a method for oligomerizing ethylene, wherein the method comprises S10 oligomerizing ethylene in the presence of a catalytic composition.

[0159] In the present invention, "oligomerization" refers to the polymerization of olefins. Depending on the number of olefins polymerized, "oligomerization" is called trimerization or tetramerization, which are collectively referred to as polymerization. Specifically, in this specification, "oligomerization" may refer to the selective preparation of 1-hexene and 1-octene as the main comonomers of LLDPE from ethylene.

[0160] According to one embodiment of the present invention, the oligomerization reaction of ethylene can be a trimerization or tetramerization reaction of ethylene, and as a result of the reaction, 1-hexene or 1-octene is formed as a reaction product, so that the linear α-olefin can be 1-hexene, 1-octene or a mixture thereof.

[0161] According to one embodiment of the present invention, the oligomerization process of ethylene can be carried out by using ethylene as a feedstock and applying the aforementioned catalyst composition, typical apparatus and contact technology. As a specific example, the oligomerization reaction of ethylene can be carried out as a homogeneous liquid phase reaction in the presence or absence of an inert solvent, a slurry reaction in which some or all of the catalyst composition is in an undissolved form, a bulk phase reaction in which the product alpha-olefin is the main medium, or a gas phase reaction.

[0162] According to one embodiment of the present invention, the oligomerization reaction of ethylene can be carried out in an inert solvent. As a specific example, the inert solvent can be benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, heptane, cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 1-hexene, 1-octene, 2,2,4-trimethylpentane, etc.

[0163] According to one embodiment of the present invention, the oligomerization reaction of ethylene can be carried out at a temperature of about 0° C. to about 200° C., about 0° C. to about 150° C., about 30° C. to about 100° C., or about 50° C. to about 100° C. In addition, the reaction can be carried out at a pressure of about 15 psig to about 3000 psig, about 15 psig to about 1500 psig, or about 15 psig to about 1000 psig.

[0164] The embodiments of the present invention will be described in detail below so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in many different forms and is not limited to the embodiments set forth herein.

[0165] Synthesis Examples and Comparative Examples

[0166] Synthesis Examples 1 to 66: Synthesis of Ligand Compounds Represented by Formula 2-1 to Formula 2-66

[0167] 20mmol (2 equivalents) of p-bromo-(tri-n-butylsilyl)-C6H4 was dissolved in 20ml of tetrahydrofuran and then cooled to -78°C. While maintaining the temperature, 20mmol (2 equivalents) of n-butyllithium were added dropwise thereto and then stirred for 3 hours. Subsequently, 10mmol (1 equivalent) of dichloro(diethylamino)phosphine dissolved in 10mL of tetrahydrofuran was added dropwise thereto, the temperature was then raised to room temperature, and the mixture was stirred overnight. Thereafter, the solvent was removed by vacuum, and the obtained intermediate was dissolved in 30mL of hexane, to which HCl (2 equivalents in ether) was then added, stirred for 15 minutes, and filtered. The filtrate was dried under vacuum to obtain (p-(tri-n-butylsilyl)-C6H4)2PCl. 11mmol (2.2 equivalents) of R 5 -NH2 and 10ml of dichloromethane were introduced into a fully dried flask and stirred. 5mmol (1 equivalent) of (p-(tri-n-butylsilyl)-C6H4)2PCl was diluted in 10ml of dichloromethane and then slowly introduced into the flask. After stirring for 4 hours, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and then (p-(tri-n-butylsilyl)-C6H4)2P-NHR was obtained by column chromatography. 5 .

[0168] 5mmol (1 equivalent) (p-(tri-n-butylsilyl)-C6H4)PCl2 was dissolved in 10ml of ether and then cooled to 0°C. Subsequently, 10mmol (2 equivalents) HNEt2 dissolved in 10ml of ether was slowly added thereto and stirred overnight. The solid was removed by a filter, and 1 equivalent of ArMgBr prepared from Ar and Mg flakes (Mg turnings) was slowly introduced thereto, and then stirred at room temperature overnight. Thereafter, HCl (2 equivalents in ether) was introduced thereto and stirred at room temperature for 30 minutes. The solid was removed by a filter and the pressure was reduced to obtain (p-(tri-n-butylsilyl)-C6H4)ArPCl. 5mmol (1 equivalent) (p-(tri-n-butylsilyl)-C6H4)ArPCl was dissolved in 10ml of dichloromethane and then 15mmol (3 equivalents) of triethylamine was added thereto. Subsequently, 5 mmol (1 equivalent) of (p-(tri-n-butylsilyl)-C6H4)2P-NHR 5 Dissolve in dichloromethane, then slowly introduce therein, and stir the mixture at room temperature overnight. Remove the solvent using vacuum, dissolve in hexane, and obtain ligand compounds represented by Formula 2-1 to Formula 2-66 by column chromatography.

[0169] R as a substituent of the reactants used in Synthesis Examples 1 to 66 5and Ar are each shown in Table 1 below, and the structures and 1 The H NMR data are described below.

[0170] [Table 1]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] Synthesis Example 1 (Formula 2-1)

[0182]

[0183] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0184] 1 H NMR (500MHz, CDCl3): δ7.48(m,6H),7.39(m,1H),7.27(m,1H),7.14(m,7H),7.12(m,1H),2.57(m,3H),1.46(m,36H),1.23(m,18H),0.97(m,27H)

[0185] Synthesis example 2 (Formula 2-2)

[0186]

[0187] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0188] 1H NMR (500MHz, CDCl3): δ7.52(m,1H),7.48(m,1H),7.44(m,6H),7.17(m,1H),7.16(m,6 H),7.12(m,1H),2.54(m,3H),1.49(m,18H),1.39(m,18H),1.31(m,18H),0.95(m,27H)

[0189] Synthesis Example 3 (Formula 2-3)

[0190]

[0191] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-methoxyphenyl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0192] 1 H NMR (500MHz, CDCl3): δ7.45(m,6H),7.39(m,1H),7.15(m,1H),7.14(m,6H),7.12(m,1H),6.9 8(m,1H),3.97(m,3H),2.55(m,3H),1.51(m,18H),1.42(m,18H),1.27(m,18H),0.96(m,27H)

[0193] Synthesis Example 4 (Formula 2-4)

[0194]

[0195] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(o-tolyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0196] 1 H NMR (500MHz, CDCl3): δ7.46(m,6H),7.36(m,1H),7.24(m,1H),7.23(m,1H),7.13(m,6H),7.1 0(m,1H),2.55(m,3H),2.38(m,3H),1.45(m,18H),1.44(m,18H),1.28(m,18H),0.96(m,27H)

[0197] Synthesis Example 5 (Formula 2-5)

[0198]

[0199] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0200] 1 H NMR (500MHz, CDCl3): δ7.47(m,6H),7.38(m,1H),7.14(m,7H),7.13(m,1H),6.9 7(m,1H),2.49(m,3H),1.48(m,18H),1.38(m,18H),1.30(m,18H),1.00(m,27H)

[0201] Synthesis Example 6 (Formula 2-6)

[0202]

[0203] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)-1-(2-((trifluoromethyl)thio)phenyl)phosphinamine

[0204] 1 H NMR (500MHz, CDCl3): δ7.41(m,6H),7.26(m,1H),7.23(m,2H),7.16(m,6H),7.0 3(m,1H),2.57(m,3H),1.46(m,18H),1.38(m,18H),1.28(m,18H),0.99(m,27H)

[0205] Synthesis Example 7 (Formula 2-7)

[0206]

[0207] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(2-(methylthio)phenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0208] 1 H NMR (500MHz, CDCl3): δ7.44(m,6H),7.28(m,2H),7.25(m,1H),7.17(m,6H),7.07(m,1 H),2.53(m,3H),2.47(m,3H),1.45(m,18H),1.37(m,18H),1.25(m,18H),0.97(m,27H)

[0209] Synthesis Example 8 (Formula 2-8)

[0210]

[0211] 2-(((Bis(4-(tributylsilyl)phenyl)phosphino)(methyl)amino)(4-tributylsilyl)phenyl)phosphino)phenyl methanesulfonate

[0212] 1 H NMR (500MHz, CDCl3): δ7.54(m,1H),7.44(m,6H),7.43(m,1H),7.36(m,1H),7.25(m,1H),7.1 1(m,6H),3.55(m,3H),2.57(m,3H),1.53(m,18H),1.46(m,18H),1.29(m,18H),0.94(m,27H)

[0213] Synthesis Example 9 (Formula 2-9)

[0214]

[0215] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trimethylsilyl)phenyl)phosphinamine

[0216] 1 H NMR (500MHz, CDCl3): δ7.45(m,8H),7.33(m,1H),7.12(m,7H),2.48(m,3H),1.49(m,18H),1.40(m,18H),1.24(m,18H),0.92(m,27H),0.35(m,9H)

[0217] Synthesis Example 10 (Formula 2-10)

[0218]

[0219] 1-(Benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0220] 1 H NMR (500MHz, CDCl3): δ7.66(m,1H),7.46(m,6H),7.35(m,1H),7.32(m,1H),7.15(m,6 H),6.82(m,1H),2.54(m,3H),1.50(m,18H),1.44(m,18H),1.28(m,18H),1.01(m,27H)

[0221] Synthesis Example 11 (Formula 2-11)

[0222]

[0223] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(dibenzo[b,d]furan-4-yl)-N-methyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0224] 1 H NMR (500MHz, CDCl3): δ7.99(m,2H),7.55(m,1H),7.43(m,6H),7.41(m,1H),7.33(m,2H),7.2 8(m,1H),7.19(m,6H),2.52(m,3H),1.52(m,18H),1.41(m,18H),1.33(m,18H),1.00(m,27H)

[0225] Synthesis Example 12 (Formula 2-12)

[0226]

[0227] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(2-fluorophenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0228] 1 H NMR (500MHz, CDCl3): δ7.50(m,6H),7.35(m,1H),7.25(m,1H),7.17(m,7H),7.11(m,1H),2.71(m,2 H),1.49(m,18H),1.45(m,2H),1.42(m,18H),1.41(m,2H),1.25(m,18H),1.00(m,27H),0.94(m,3H)

[0229] Synthesis Example 13 (Formula 2-13)

[0230]

[0231] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0232] 1H NMR (500MHz, CDCl3): δ7.44(m,8H),7.23(m,1H),7.14(m,6H),7.11(m,1H),2.67(m,2H),1.5 2(m,2H),1.46(m,18H),1.41(m,18H),1.33(m,2H),1.30(m,18H),0.93(m,27H),0.92(m,3H)

[0233] Synthesis Example 14 (Formula 2-14)

[0234]

[0235] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(2-methoxyphenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0236] 1 H NMR (500MHz, CDCl3): δ7.43(m,6H),7.38(m,1H),7.18(m,1H),7.13(m,7H),6.97(m,1H),3.93(m,3H),2.6 5(m,2H),1.50(m,2H),1.49(m,18H),1.42(m,2H),1.41(m,18H),1.27(m,18H),0.98(m,27H),0.95(m,3H)

[0237] Synthesis Example 15 (Formula 2-15)

[0238]

[0239] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(o-tolyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0240] 1 H NMR (500MHz, CDCl3): δ7.45(m,6H),7.36(m,1H),7.22(m,1H),7.19(m,1H),7.17(m,6H),7.16(m,1H),2.67(m,2 H),2.32(m,3H),1.48(m,18H),1.47(m,2H),1.44(m,18H),1.33(m,18H),1.32(m,2H),0.99(m,3H),0.95(m,27H)

[0241] Synthesis Example 16 (Formula 2-16)

[0242]

[0243] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0244] 1 H NMR (500MHz, CDCl3): δ7.46(m,1H),7.42(m,6H),7.19(m,1H),7.15(m,6H),7.14(m,1H),6.98(m,1H),2.6 6(m,2H),1.48(m,2H),1.45(m,18H),1.36(m,18H),1.35(m,2H),1.24(m,18H),0.99(m,3H),0.96(m,27H)

[0245] Synthesis Example 17 (Formula 2-17)

[0246]

[0247] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(4-(tributylsilyl)phenyl)-1-(2-((trifluoromethyl)thio)phenyl)phosphinamide

[0248] 1H NMR (500MHz, CDCl3): δ7.49(m,6H),7.24(m,1H),7.22(m,2H),7.13(m,6H),7.03(m,1H),2.73(m,2 H),1.50(m,2H),1.43(m,18H),1.41(m,18H),1.38(m,2H),1.31(m,18H),0.95(m,27H),0.94(m,3H)

[0249] Synthesis Example 18 (Formula 2-18)

[0250]

[0251] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(2-(methylthio)phenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0252] 1H NMR (500MHz, CDCl3): δ7.45(m,6H),7.21(m,2H),7.17(m,1H),7.14(m,6H),7.04(m,1H),2.69(m,2H),2.4 7(m,3H),1.45(m,2H),1.43(m,18H),1.38(m,18H),1.33(m,2H),1.23(m,18H),1.02(m,27H),0.93(m,3H)

[0253] Synthesis Example 19 (Formula 2-19)

[0254]

[0255] 2-(((Bis(4-(tributylsilyl)phenyl)phosphino)(butyl)amino)(4-tributylsilyl)phenyl)phosphino)phenyl methanesulfonate

[0256] 1 H NMR (500MHz, CDCl3): δ7.51(m,1H),7.47(m,1H),7.43(m,6H),7.35(m,1H),7.23(m,1H),7.17(m,6H),3.62(m,3 H),2.65(m,2H),1.53(m,2H),1.45(m,18H),1.41(m,18H),1.39(m,2H),1.31(m,18H),0.94(m,27H),0.92(m,3H)

[0257] Synthesis Example 20 (Formula 2-20)

[0258]

[0259] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(4-(trimethylsilyl)phenyl)-1-(2-(trimethylsilyl)phenyl)phosphinamine

[0260] 1 H NMR (500MHz, CDCl3): δ7.43(m,8H),7.26(m,1H),7.16(m,7H),2.64(m,2H),1.45(m,3 6H),1.44(m,2H),1.37(m,2H),1.30(m,18H),1.01(m,27H),0.93(m,3H),0.28(m,9H)

[0261] Synthesis Example 21 (Formula 2-21)

[0262]

[0263] 1-(Benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0264] 1 H NMR (500MHz, CDCl3): δ7.68(m,2H),7.41(m,6H),7.36(m,1H),7.28(m,1H),7.19(m,6H),6.84(m,1H),2.6 3(m,2H),1.50(m,2H),1.48(m,18H),1.39(m,2H),1.38(m,18H),1.29(m,18H),1.00(m,27H),0.91(m,3H)

[0265] Synthesis Example 22 (Formula 2-22)

[0266]

[0267] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(dibenzo[b,d]furan-4-yl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0268] 1 H NMR (500MHz, CDCl3): δ8.02(m,2H),7.57(m,1H),7.47(m,1H),7.44(m,6H),7.38(m,1H),7.32(m,1H),7.30(m,1H),7.1 1(m,6H),2.72(m,2H),1.51(m,18H),1.47(m,2H),1.44(m,18H),1.40(m,2H),1.26(m,18H),0.94(m,3H),0.93(m,27H)

[0269] Synthesis Example 23 (Formula 2-23)

[0270]

[0271] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N-isopropyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0272] 1H NMR (500MHz, CDCl3): δ7.47(m,6H),7.33(m,1H),7.23(m,1H),7.15(m,7H),7.10(m,1 H),2.92(m,1H),1.48(m,18H),1.39(m,18H),1.32(m,18H),1.07(m,6H),0.94(m,27H)

[0273] Synthesis Example 24 (Formula 2-24)

[0274]

[0275] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0276] 1 H NMR (500MHz, CDCl3): δ7.54(m,1H),7.52(m,1H),7.45(m,6H),7.26(m,1H),7.13(m,6 H),7.09(m,1H),2.89(m,1H),1.44(m,36H),1.31(m,18H),1.13(m,6H),0.96(m,27H)

[0277] Synthesis Example 25 (Formula 2-25)

[0278]

[0279] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(2-methoxyphenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0280] 1 H NMR (500MHz, CDCl3): δ7.48(m,6H),7.40(m,1H),7.20(m,1H),7.18(m,7H),7.03(m,1H),3.9 9(m,3H),2.91(m,1H),1.49(m,18H),1.44(m,18H),1.28(m,18H),1.16(m,6H),1.00(m,27H)

[0281] Synthesis Example 26 (Formula 2-26)

[0282]

[0283] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(o-tolyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0284] 1 H NMR (500MHz, CDCl3): δ7.40(m,6H),7.37(m,1H),7.20(m,1H),7.19(m,1H),7.14(m,6H),7. 07(m,1H),2.87(m,1H),2.36(m,3H),1.44(m,36H),1.30(m,18H),1.14(m,6H),0.96(m,27H)

[0285] Synthesis Example 27 (Formula 2-27)

[0286]

[0287] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0288] 1 H NMR (500MHz, CDCl3): δ7.45(m,1H),7.43(m,6H),7.20(m,2H),7.14(m,6H),7.02(m,1 H),2.92(m,1H),1.46(m,18H),1.42(m,18H),1.30(m,18H),1.14(m,6H),0.93(m,27H)

[0289] Synthesis Example 28 (Formula 2-28)

[0290]

[0291] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(4-(tributylsilyl)phenyl)-1-(2-((trifluoromethyl)thio)phenyl)phosphine

[0292] 1 H NMR (500MHz, CDCl3): δ7.42(m,6H),7.19(m,2H),7.17(m,1H),7.16(m,6H),7.06(m,1 H),2.84(m,1H),1.49(m,18H),1.40(m,18H),1.25(m,18H),1.11(m,6H),0.99(m,27H)

[0293] Synthesis Example 29 (Formula 2-29)

[0294]

[0295] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(2-(methylthio)phenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0296] 1 H NMR (500MHz, CDCl3): δ7.49(m,6H),7.22(m,2H),7.18(m,1H),7.15(m,6H),7.11(m,1H),2.8 8(m,1H),2.48(m,3H),1.44(m,18H),1.42(m,18H),1.30(m,18H),1.14(m,6H),0.98(m,27H)

[0297] Synthesis Example 30 (Formula 2-30)

[0298]

[0299] 2-(((Bis(4-(tributylsilyl)phenyl)phosphino)(isopropyl)amino)(4-tributylsilyl)phenyl)phosphino)phenyl methanesulfonate

[0300] 1 H NMR (500MHz, CDCl3): δ7.45(m,1H),7.42(m,7H),7.34(m,1H),7.22(m,1H),7.15(m,6H),3.5 4(m,3H),2.92(m,1H),1.51(m,18H),1.39(m,18H),1.27(m,18H),1.15(m,6H),0.97(m,27H)

[0301] Synthesis Example 31 (Formula 2-31)

[0302]

[0303] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)-1-(2-(trimethylsilyl)phenyl)phosphinamine

[0304] 1H NMR (500MHz, CDCl3): δ7.44(m,8H),7.27(m,1H),7.10(m,7H),2.92(m,1H),1.4 9(m,18H),1.43(m,18H),1.26(m,18H),1.12(m,6H),0.96(m,27H),0.29(m,9H)

[0305] Synthesis Example 32 (Formula 2-32)

[0306]

[0307] 1-(Benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0308] 1 H NMR (500MHz, CDCl3): δ7.67(m,1H),7.62(m,1H),7.44(m,6H),7.35(m,1H),7.23(m,1H),7.17(m,6 H),6.82(m,1H),2.84(m,1H),1.45(m,18H),1.44(m,18H),1.28(m,18H),1.15(m,6H),1.00(m,27H)

[0309] Synthesis Example 33 (Formula 2-33)

[0310]

[0311] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(dibenzo[b,d]furan-4-yl)-N-isopropyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0312] 1 H NMR (500MHz, CDCl3): δ8.03(m,2H),7.64(m,H),7.46(m,1H),7.44(m,6H),7.38(m,1H),7.37(m,4H),7.2 3(m,1H),7.12(m,6H),2.88(m,1H),1.48(m,18H),1.40(m,18H),1.28(m,18H),1.14(m,6H),0.95(m,27H)

[0313] Synthesis Example 34 (Formula 2-34)

[0314]

[0315] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(2-fluorophenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0316] 1 H NMR (500MHz, CDCl3): δ7.50(m,6H),7.35(m,1H),7.27(m,1H),7.17(m,7H),7.05(m,1H),2.60(m,4H),1.80(m,2H),1.5 4(m,2H),1.49(m,1H),1.48(m,18H),1.47(m,1H),1.40(m,18H),1.32(m,18H),1.28(m,2H),1.18(m,2H),0.99(m,27H)

[0317] Synthesis Example 35 (Formula 2-35)

[0318]

[0319] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0320] 1 H NMR (500MHz, CDCl3): δ7.47(m,6H),7.45(m,1H),7.44(m,1H),7.25(m,1H),7.14(m,6H),7.11(m,1H),2.62(m,1 H),1.79(m,2H),1.50(m,2H),1.47(m,19H),1.45(m,19H),1.28(m,2H),1.26(m,18H),1.21(m,2H),0.99(m,27H)

[0321] Synthesis Example 36 (Formula 2-36)

[0322]

[0323] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(2-methoxyphenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0324] 1H NMR (500MHz, CDCl3): δ7.42(m,6H),7.37(m,1H),7.12(m,7H),7.10(m,1H),7.03(m,1H),3.98(m,3H),2.62(m,1H),1.7 6(m,2H),1.56(m,2H),1.49(m,1H),1.48(m,19H),1.46(m,18H),1.32(m,18H),1.28(m,2H),1.17(m,2H),0.98(m,27H)

[0325] Synthesis Example 37 (Formula 2-37)

[0326]

[0327] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(o-tolyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0328] 1 H NMR (500MHz, CDCl3): δ7.40(m,6H),7.38(m,1H),7.22(m,1H),7.14(m,1H),7.13(m,1H),7.11(m,6H),2.66(m,1H),2.38(m,3 H),1.83(m,2H),1.52(m,2H),1.51(m,19H),1.49(m,1H),1.38(m,18H),1.30(m,18H),1.28(m,2H),1.21(m,2H),0.96(m,27H)

[0329] Synthesis Example 38 (Formula 2-38)

[0330]

[0331] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0332] 1H NMR (500MHz, CDCl3): δ7.50(m,6H),7.45(m,1H),7.14(m,1H),7.13(m,6H),7.12(m,1H),7.01(m,1H),2.66(m,1H),1.8 0(m,2H),1.53(m,2H),1.52(m,19H),1.44(m,1H),1.42(m,18H),1.25(m,18H),1.24(m,2H),1.15(m,2H),0.94(m,27H)

[0333] Synthesis Example 39 (Formula 2-39)

[0334]

[0335] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(4-(tributylsilyl)phenyl)-1-(2-((trifluoromethyl)thio)phenyl)phosphinamine

[0336] 1 H NMR (500MHz, CDCl3): δ7.49(m,6H),7.20(m,2H),7.17(m,1H),7.12(m,6H),7.02(m,1H),2.62(m,1H),1.75(m,2H),1.5 7(m,2H),1.54(m,1H),1.47(m,18H),1.45(m,1H),1.43(m,18H),1.28(m,2H),1.25(m,18H),1.12(m,2H),0.99(m,27H)

[0337] Synthesis Example 40 (Formula 2-40)

[0338]

[0339] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(2-(methylthio)phenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0340] 1H NMR (500MHz, CDCl3): δ7.45(m,6H),7.26(m,2H),7.17(m,1H),7.15(m,6H),7.02(m,1H),2.59(m,1H),2.53(m,3H),1.7 5(m,2H),1.50(m,1H),1.49(m,3H),1.45(m,18H),1.36(m,18H),1.26(m,2H),1.24(m,18H),1.19(m,2H),0.96(m,27H)

[0341] Synthesis Example 41 (Formula 2-41)

[0342]

[0343] 2-(((Bis(4-(tributylsilyl)phenyl)phosphino)(cyclohexyl)amino)(4-tributylsilyl)phenyl)phosphino)phenyl methanesulfonate

[0344] 1 H NMR (500MHz, CDCl3): δ7.54(m,1H),7.48(m,6H),7.46(m,1H),7.38(m,1H),7.26(m,1H),7.12(m,6H),3.63(m,3H),2.63(m,1 H),1.76(m,2H),1.53(m,1H),1.50(m,18H),1.49(m,2H),1.48(m,1H),1.44(m,18H),1.23(m,20H),1.19(m,2H),0.94(m,27H)

[0345] Synthesis Example 42 (Formula 2-42)

[0346]

[0347] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trimethylsilyl)phenyl)phosphinamine

[0348] 1H NMR (500MHz, CDCl3): δ7.48(m,8H),7.32(m,1H),7.17(m,7H),2.57(m,1H),1.79(m,2H),1.55(m,1H),1.51(m,2 H),1.49(m,1H),1.46(m,18H),1.44(m,18H),1.32(m,18H),1.30(m,2H),1.12(m,2H),0.99(m,27H),0.30(m,9H)

[0349] Synthesis Example 43 (Formula 2-43)

[0350]

[0351] 1-(Benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0352] 1 H NMR (500MHz, CDCl3): δ7.70(m,1H),7.68(m,1H),7.47(m,6H),7.38(m,1H),7.28(m,1H),7.17(m,6H),6.82(m,1H),2.60(m,1 H),1.79(m,2H),1.56(m,2H),1.51(m,18H),1.47(m,2H),1.38(m,18H),1.29(m,18H),1.23(m,2H),1.20(m,2H),0.94(m,27H)

[0353] Synthesis Example 44 (Formula 2-44)

[0354]

[0355] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(dibenzo[b,d]furan-4-yl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0356] 1H NMR (500MHz, CDCl3): δ8.05(m,2H),7.59(m,1H),7.47(m,1H),7.41(m,6H),7.37(m,1H),7.31(m,1H),7.28(m,1H),7.14(m,6H),2.64(m,1 H),1.81(m,2H),1.54(m,1H),1.52(m,2H),1.50(m,18H),1.48(m,1H),1.46(m,18H),1.30(m,18H),1.25(m,2H),1.21(m,2H),0.99(m,27H)

[0357] Synthesis Example 45 (Formula 2-45)

[0358]

[0359] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0360] 1 H NMR (500MHz, CDCl3): δ7.48(m,6H),7.39(m,1H),7.38(m,1H),7.34(m,4H),7.25(m,1H),7.1 6(m,7H),7.04(m,1H),4.01(m,2H),1.47(m,18H),1.41(m,18H),1.30(m,18H),0.97(m,27H)

[0361] Synthesis Example 46 (Formula 2-46)

[0362]

[0363] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0364] 1 H NMR (500MHz, CDCl3): δ7.48(m,1H),7.47(m,6H),7.46(m,1H),7.40(m,4H),7.32(m,1H),7.22(m,1 H),7.13(m,6H),7.12(m,1H),3.95(m,2H),1.50(m,18H),1.45(m,18H),1.24(m,18H),1.00(m,27H)

[0365] Synthesis Example 47 (Formula 2-47)

[0366]

[0367] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-methoxyphenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0368] 1 H NMR (500MHz, CDCl3): δ7.49(m,6H),7.38(m,5H),7.37(m,1H),7.19(m,1H),7.13(m,1H),7.1 1(m,6H),6.99(m,1H),4.01(m,5H),1.45(m,18H),1.44(m,18H),1.31(m,18H),0.93(m,27H)

[0369] Synthesis Example 48 (Formula 2-48)

[0370]

[0371] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(o-tolyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0372] 1 H NMR (500MHz, CDCl3): δ7.40(m,6H),7.37(m,1H),7.36(m,5H),7.21(m,2H),7.14(m,6H),7.1 1(m,1H),3.94(m,2H),2.32(m,3H),1.51(m,18H),1.42(m,18H),1.24(m,18H),0.95(m,27H)

[0373] Synthesis Example 49 (Formula 2-49)

[0374]

[0375] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0376] 1H NMR (500MHz, CDCl3): δ7.46(m,7H),7.34(m,1H),7.31(m,4H),7.20(m,1H),7.17(m,1H),7.1 3(m,6H),7.00(m,1H),3.99(m,2H),1.46(m,18H),1.39(m,18H),1.28(m,18H),0.99(m,27H)

[0377] Synthesis Example 50 (Formula 2-50)

[0378]

[0379] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)-1-(2-((trifluoromethyl)thio)phenyl)phosphinamine

[0380] 1 H NMR (500MHz, CDCl3): δ7.44(m,6H),7.40(m,4H),7.37(m,1H),7.24(m,2H),7.19(m,1H),7.1 2(m,6H),7.10(m,1H),3.94(m,2H),1.53(m,18H),1.42(m,18H),1.30(m,18H),0.96(m,27H)

[0381] Synthesis Example 51 (Formula 2-51)

[0382]

[0383] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-(methylthio)phenyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0384] 1 H NMR (500MHz, CDCl3): δ7.43(m,6H),7.39(m,4H),7.31(m,1H),7.27(m,2H),7.23(m,1H),7. 12(m,6H),7.06(m,1H),3.99(m,2H),2.54(m,3H),1.45(m,36H),1.24(m,18H),0.98(m,27H)

[0385] Synthesis Example 52 (Formula 2-52)

[0386]

[0387] 2-((Benzyl(bis(4-(tributylsilyl)phenyl)phosphino)amino)(4-tributylsilyl)phenyl)phosphino)phenyl methanesulfonate

[0388] 1 H NMR (500MHz, CDCl3): δ7.46(m,1H),7.44(m,6H),7.41(m,1H),7.40(m,4H),7.36(m,2H),7.24(m,1 H),7.17(m,6H),3.92(m,2H),3.62(m,3H),1.46(m,18H),1.41(m,18H),1.32(m,18H),0.95(m,27H)

[0389] Synthesis Example 53 (Formula 2-53)

[0390]

[0391] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)-1-(2-(trimethylsilyl)phenyl)phosphinamine

[0392] 1 H NMR (500MHz, CDCl3): δ7.48(m,8H),7.35(m,4H),7.33(m,2H),7.19(m,7H),3.9 7(m,2H),1.45(m,18H),1.43(m,18H),1.25(m,18H),1.00(m,27H),0.32(m,9H)

[0393] Synthesis Example 54 (Formula 2-54)

[0394]

[0395] 1-(Benzofuran-7-yl)-N-benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0396] 1 H NMR (500MHz, CDCl3): δ7.70(m,1H),7.67(m,1H),7.43(m,6H),7.33(m,2H),7.32(m,1H),7.31(m,4 H),7.16(m,6H),6.80(m,1H),3.97(m,2H),1.45(m,18H),1.42(m,18H),1.26(m,18H),0.97(m,27H)

[0397] Synthesis Example 55 (Formula 2-55)

[0398]

[0399] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(dibenzo[b,d]furan-4-yl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0400] 1 H NMR (500MHz, CDCl3): δ8.06(m,2H),7.59(m,1H),7.49(m,6H),7.44(m,1H),7.40(m,5H),7.31(m,1H),7.3 0(m,1H),7.23(m,1H),7.19(m,6H),4.01(m,2H),1.46(m,18H),1.38(m,18H),1.33(m,18H),0.95(m,27H)

[0401] Synthesis Example 56 (Formula 2-56)

[0402]

[0403] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0404] 1 H NMR (500MHz, CDCl3): δ7.47(m,6H),7.39(m,1H),7.25(m,1H),7.18(m,7H),7.13(m,2H),7.0 7(m,1H),6.84(m,1H),6.64(m,2H),1.49(m,18H),1.37(m,18H),1.31(m,18H),0.93(m,27H)

[0405] Synthesis Example 57 (Formula 2-57)

[0406]

[0407] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0408] 1H NMR (500MHz, CDCl3): δ7.49(m,1H),7.48(m,1H),7.40(m,6H),7.24(m,1H),7.13(m,2H),7.12(m,6 H),7.11(m,1H),6.86(m,1H),6.62(m,2H),1.49(m,18H),1.43(m,18H),1.24(m,18H),0.92(m,27H)

[0409] Synthesis Example 58 (Formula 2-58)

[0410]

[0411] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-methoxyphenyl)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0412] 1 H NMR (500MHz, CDCl3): δ7.49(m,6H),7.42(m,1H),7.18(m,3H),7.12(m,7H),6.96(m,1 H),6.85(m,1H),6.62(m,2H),3.99(m,3H),1.44(m,36H),1.32(m,18H),1.01(m,27H)

[0413] Synthesis Example 59 (Formula 2-59)

[0414]

[0415] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(o-tolyl)-1-(4-(tributylsilyl)phenyl)phosphinamine

[0416] 1 H NMR (500MHz, CDCl3): δ7.47(m,2H),7.35(m,1H),7.24(m,6H),7.18(m,1H),7.17(m,1H),7.16(m,1H),7.1 1(m,1H),6.80(m,1H),6.65(m,6H),2.32(m,2H),1.43(m,18H),1.41(m,18H),1.29(m,18H),0.98(m,27H)

[0417] Synthesis Example 60 (Formula 2-60)

[0418]

[0419] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0420] 1 H NMR (500MHz, CDCl3): δ7.45(m,1H),7.44(m,6H),7.17(m,1H),7.16(m,2H),7.15(m,6H),7.11(m,1 H),7.06(m,1H),6.80(m,1H),6.67(m,2H),1.50(m,18H),1.44(m,18H),1.31(m,18H),0.94(m,27H)

[0421] Synthesis Example 61 (Formula 2-61)

[0422]

[0423] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)-1-(2-((trifluoromethyl)thio)phenyl)phosphinamine

[0424] 1 H NMR (500MHz, CDCl3): δ7.44(m,6H),7.26(m,2H),7.18(m,1H),7.17(m,2H),7.14(m,6 H),7.11(m,1H),6.81(m,1H),6.66(m,2H),1.45(m,36H),1.27(m,18H),1.00(m,27H)

[0425] Synthesis Example 62 (Formula 2-62)

[0426]

[0427] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-(methylthio)phenyl)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0428] 1 H NMR (500MHz, CDCl3): δ7.48(m,6H),7.23(m,1H),7.22(m,2H),7.16(m,6H),7.11(m,2H),7.02(m,1 H),6.79(m,1H),6.68(m,2H),2.52(m,3H),1.49(m,18H),1.46(m,18H),1.32(m,18H),0.93(m,27H)

[0429] Synthesis Example 63 (Formula 2-63)

[0430]

[0431] 2-(((Bis(4-(tributylsilyl)phenyl)phosphino)(phenyl)amino)(4-tributylsilyl)phenyl)phosphino)phenyl methanesulfonate

[0432] 1 H NMR (500MHz, CDCl3): δ7.54(m,1H),7.47(m,7H),7.34(m,1H),7.28(m,1H),7.10(m,8H),6.8 0(m,1H),6.64(m,2H),3.54(m,3H),1.45(m,18H),1.44(m,18H),1.29(m,18H),1.01(m,27H)

[0433] Synthesis Example 64 (Formula 2-64)

[0434]

[0435] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)-1-(2-(trimethylsilyl)phenyl)phosphinamine

[0436] 1 H NMR (500MHz, CDCl3): δ7.50(m,8H),7.31(m,1H),7.17(m,9H),6.87(m,1H),6.6 2(m,2H),1.50(m,18H),1.39(m,18H),1.29(m,18H),0.93(m,27H),0.27(m,9H)

[0437] Synthesis Example 65 (Formula 2-65)

[0438]

[0439] 1-(Benzofuran-7-yl)-N-(bis(4-(tributylsilyl)phenyl)phosphino)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0440] 1H NMR (500MHz, CDCl3): δ7.69(m,1H),7.65(m,1H),7.48(m,6H),7.30(m,1H),7.29(m,1H),7.19(m,6H),7.1 5(m,2H),6.81(m,1H),6.80(m,1H),6.70(m,2H),1.47(m,18H),1.42(m,18H),1.29(m,18H),0.99(m,27H)

[0441] Synthesis Example 66 (Formula 2-66)

[0442]

[0443] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(dibenzo[b,d]furan-4-yl)-N-phenyl-1-(4-(tributylsilyl)phenyl)phosphinamine

[0444] 1 H NMR (500MHz, CDCl3): δ8.01(m,2H),7.64(m,1H),7.46(m,6H),7.43(m,1H),7.41(m,1H),7.33(m,1H),7.30(m,1 H),7.13(m,2H),7.09(m,6H),6.84(m,1H),6.63(m,2H),1.52(m,18H),1.43(m,18H),1.24(m,18H),0.97(m,27H)

[0445] Synthesis Examples 67 to 86: Synthesis of Ligand Compounds Represented by Formulas 9-1 to 9-20

[0446] 20mmol (2 equivalents) of m-bromo-(tri-n-butylsilyl)-C6H4 was dissolved in 20ml of tetrahydrofuran and then cooled to -78°C. While maintaining the temperature, 20mmol (2 equivalents) of n-butyllithium were added dropwise thereto and then stirred for 3 hours. Subsequently, 10mmol (1 equivalent) of dichloro(diethylamino)phosphine dissolved in 10mL of tetrahydrofuran was added dropwise thereto, the temperature was then raised to room temperature, and the mixture was stirred overnight. Thereafter, a vacuum was used to remove the solvent, and the obtained intermediate was dissolved in 30mL of hexane, HCl (2 equivalents in ether) was then added thereto, stirred for 15 minutes, and filtered. The filtrate was dried under vacuum to obtain (m-(tri-n-butylsilyl)-C6H4)2PCl. 11mmol (2.2 equivalents) of R 5-NH2 and 10ml of dichloromethane were introduced into a fully dried flask and stirred. 5mmol (1 equivalent) of (m-(tri-n-butylsilyl)-C6H4)2PCl was diluted in 10ml of dichloromethane and then slowly introduced into the flask. After stirring for 4 hours, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and then (m-(tri-n-butylsilyl)-C6H4)2P-NHR was obtained by column chromatography. 5 .

[0447] 5mmol (1 equivalent) of (meta-(tri-n-butylsilyl)-C6H4)PCl2 was dissolved in 10ml of ether and then cooled to 0°C. Subsequently, 10mmol (2 equivalents) of HNEt2 dissolved in 10ml of ether was slowly added thereto, and stirred overnight. The solid was removed by a filter, and 1 equivalent of ArMgBr prepared from Ar and Mg flakes (magnesium turnings) was slowly introduced thereto, and then stirred at room temperature overnight. Thereafter, HCl (2 equivalents in ether) was introduced thereto and stirred at room temperature for 30 minutes. The solid was removed by a filter and the pressure was reduced to obtain (meta-(tri-n-butylsilyl)-C6H4)ArPCl. 5mmol (1 equivalent) of (meta-(tri-n-butylsilyl)-C6H4)ArPCl was dissolved in 10ml of dichloromethane, and then 15mmol (3 equivalents) of triethylamine was added thereto. Subsequently, 5 mmol (1 equivalent) of (m-(tri-n-butylsilyl)-C6H4)2P-NHR 5 It was dissolved in dichloromethane and then slowly introduced thereinto, and the mixture was stirred at room temperature overnight. The solvent was removed using vacuum, dissolved in hexane, and ligand compounds represented by Formula 9-1 to Formula 9-20 were obtained by column chromatography.

[0448] R as a substituent of the reactants used in Synthesis Examples 67 to 86 5 and Ar are each shown in Table 2 below, and the structures and 1 The H NMR data are described below.

[0449] [Table 2]

[0450]

[0451]

[0452]

[0453] Synthesis Example 67 (Formula 9-1)

[0454]

[0455] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N-methyl-1-(3-(tributylsilyl)phenyl)phosphinamine

[0456] 1 H NMR (500MHz, CDCl3): δ7.63(m,3H),7.44(m,3H),7.40(m,3H),7.31(m,1H),7.23(m,1H),7.1 6(m,4H),7.08(m,1H),2.51(m,3H),1.51(m,18H),1.42(m,18H),1.33(m,18H),0.94(m,27H)

[0457] Synthesis Example 68 (Formula 9-2)

[0458]

[0459] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0460] 1 H NMR (500MHz, CDCl3): δ7.62(m,3H),7.52(m,1H),7.45(m,1H),7.44(m,3H),7.37(m,3H),7.24(m,1 H),7.18(m,3H),7.04(m,1H),2.49(m,3H),1.44(m,18H),1.41(m,18H),1.33(m,18H),0.99(m,27H)

[0461] Synthesis Example 69 (Formula 9-3)

[0462]

[0463] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-1-(2-methoxyphenyl)-N-methyl-1-(3-(tributylsilyl)phenyl)phosphinamine

[0464] 1 H NMR (500MHz, CDCl3): δ7.60(m,3H),7.47(m,3H),7.38(m,1H),7.32(m,3H),7.16(m,1H),7.15(m,1H),7.1 1(m,3H),7.00(m,1H),3.97(m,3H),2.51(m,3H),1.48(m,18H),1.43(m,18H),1.31(m,18H),0.94(m,27H)

[0465] Synthesis Example 70 (Formula 9-4)

[0466]

[0467] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(o-tolyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0468] 1 H NMR (500MHz, CDCl3): δ7.61(m,3H),7.44(m,3H),7.37(m,1H),7.33(m,3H),7.28(m,1H),7.17(m,1H),7.1 6(m,1H),7.14(m,3H),2.57(m,3H),2.31(m,3H),1.44(m,18H),1.42(m,18H),1.28(m,18H),0.94(m,27H)

[0469] Synthesis Example 71 (Formula 9-5)

[0470]

[0471] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-methyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0472] 1 H NMR (500MHz, CDCl3): δ7.59(m,3H),7.42(m,3H),7.39(m,1H),7.37(m,3H),7.20(m,1H),7.13(m,1 H),7.10(m,3H),7.02(m,1H),2.48(m,3H),1.48(m,18H),1.43(m,18H),1.28(m,18H),0.92(m,27H)

[0473] Synthesis Example 72 (Formula 9-6)

[0474]

[0475] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(2-fluorophenyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0476] 1H NMR (500MHz, CDCl3): δ7.56(m,3H),7.47(m,3H),7.40(m,3H),7.31(m,1H),7.28(m,1H),7.12(m,4H),7.09(m,1 H),2.67(m,2H),1.49(m,2H),1.47(m,18H),1.41(m,18H),1.40(m,2H),1.29(m,18H),1.00(m,3H),0.95(m,27H)

[0477] Synthesis Example 73 (Formula 9-7)

[0478]

[0479] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0480] 1 H NMR (500MHz, CDCl3): δ7.64(m,3H),7.46(m,1H),7.45(m,3H),7.42(m,1H),7.34(m,3H),7.20(m,1H),7.19(m,3H),7.0 5(m,1H),2.67(m,2H),1.52(m,2H),1.44(m,18H),1.40(m,18H),1.37(m,2H),1.33(m,18H),1.01(m,3H),0.98(m,27H)

[0481] Synthesis Example 74 (Formula 9-8)

[0482]

[0483] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(2-methoxyphenyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0484] 1H NMR (500MHz, CDCl3): δ7.62(m,3H),7.46(m,3H),7.39(m,1H),7.32(m,3H),7.15(m,1H),7.12(m,3H),7.10(m,1H),7.05(m,1 H),3.99(m,3H),2.63(m,2H),1.51(m,18H),1.46(m,2H),1.37(m,2H),1.36(m,18H),1.28(m,18H),1.00(m,27H),0.97(m,3H)

[0485] Synthesis Example 75 (Formula 9-9)

[0486]

[0487] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(o-tolyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0488] 1 H NMR (500MHz, CDCl3): δ7.65(m,3H),7.46(m,3H),7.35(m,3H),7.34(m,1H),7.22(m,1H),7.16(m,1H),7.14(m,1H),7.1 2(m,3H),2.64(m,2H),2.31(m,3H),1.52(m,18H),1.46(m,2H),1.39(m,18H),1.38(m,2H),1.27(m,18H),1.00(m,30H)

[0489] Synthesis Example 76 (Formula 9-10)

[0490]

[0491] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0492] 1H NMR (500MHz, CDCl3): δ7.64(m,3H),7.47(m,1H),7.40(m,3H),7.33(m,3H),7.18(m,1H),7.15(m,1H),7.10(m,3 H),7.02(m,1H),2.70(m,2H),1.48(m,18H),1.44(m,20H),1.40(m,2H),1.24(m,18H),1.01(m,27H),0.98(m,3H)

[0493] Synthesis Example 77 (Formula 9-11)

[0494]

[0495] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N-isopropyl-1-(3-(tributylsilyl)phenyl)phosphinamine

[0496] 1 H NMR (500MHz, CDCl3): δ7.60(m,3H),7.43(m,3H),7.32(m,4H),7.20(m,1H),7.17(m,4H),7.0 8(m,1H),2.87(m,1H),1.51(m,18H),1.44(m,18H),1.31(m,18H),1.07(m,6H),0.95(m,27H)

[0497] Synthesis Example 78 (Formula 9-12)

[0498]

[0499] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0500] 1 H NMR (500MHz, CDCl3): δ7.61(m,3H),7.52(m,1H),7.50(m,1H),7.42(m,3H),7.39(m,3H),7.23(m,1H),7.1 0(m,3H),7.08(m,1H),2.83(m,1H),1.51(m,18H),1.40(m,18H),1.27(m,18H),1.14(m,6H),1.00(m,27H)

[0501] Synthesis Example 79 (Formula 9-13)

[0502]

[0503] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(2-methoxyphenyl)-1-(3-(tributylsilyl)phenyl)phosphine

[0504] 1 H NMR (500MHz, CDCl3): δ7.58(m,3H),7.43(m,1H),7.40(m,6H),7.20(m,1H),7.19(m,1H),7.13(m,3H),6.9 7(m,1H),3.96(m,3H),2.89(m,1H),1.46(m,18H),1.36(m,18H),1.24(m,18H),1.16(m,6H),0.94(m,27H)

[0505] Synthesis Example 80 (Formula 9-14)

[0506]

[0507] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(o-tolyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0508] 1 H NMR (500MHz, CDCl3): δ7.56(m,3H),7.48(m,3H),7.40(m,1H),7.32(m,3H),7.27(m,1H),7.21(m,1H),7.15(m,3 H),7.09(m,1H),2.91(m,1H),2.35(m,3H),1.47(m,18H),1.39(m,18H),1.25(m,18H),1.13(m,6H),0.92(m,27H)

[0509] Synthesis Example 81 (Formula 9-15)

[0510]

[0511] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0512] 1H NMR (500MHz, CDCl3): δ7.60(m,3H),7.49(m,3H),7.41(m,1H),7.36(m,3H),7.17(m,3H),7.15(m,2 H),6.96(m,1H),2.87(m,1H),1.51(m,18H),1.45(m,18H),1.27(m,18H),1.06(m,6H),0.99(m,27H)

[0513] Synthesis Example 82 (Formula 9-16)

[0514]

[0515] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(2-fluorophenyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0516] 1 H NMR (500MHz, CDCl3): δ7.62(m,3H),7.42(m,3H),7.40(m,3H),7.38(m,1H),7.23(m,1H),7.17(m,4H),7.13(m,1H),2.64(m,1H),1.7 5(m,2H),1.54(m,18H),1.50(m,2H),1.49(m,1H),1.45(m,1H),1.44(m,18H),1.30(m,18H),1.22(m,2H),1.15(m,2H),1.00(m,27H)

[0517] Synthesis Example 83 (Formula 9-17)

[0518]

[0519] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0520] 1 H NMR (500MHz, CDCl3): δ7.56(m,3H),7.51(m,1H),7.44(m,4H),7.36(m,3H),7.26(m,1H),7.13(m,3H),7.05(m,1H),2.6 2(m,1H),1.80(m,2H),1.51(m,2H),1.47(m,1H),1.44(m,19H),1.40(m,18H),1.29(m,20H),1.12(m,2H),0.99(m,27H)

[0521] Synthesis Example 84 (Formula 9-18)

[0522]

[0523] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(2-methoxyphenyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0524] 1 H NMR (500MHz, CDCl3): δ7.65(m,3H),7.48(m,3H),7.45(m,1H),7.32(m,3H),7.19(m,1H),7.16(m,3H),7.14(m,1H),7.01(m,1H),3.98(m,3H),2.6 6(m,1H),1.77(m,2H),1.55(m,2H),1.52(m,1H),1.48(m,1H),1.45(m,1 8H),1.44(m,18H),1.25(m,18H),1.21(m,2H),1.17(m,2H),0.96(m,27H)

[0525] Synthesis Example 85 (Formula 9-19)

[0526]

[0527] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(o-tolyl)-1-(3-(tributylsilyl)phenyl)phosphinamine

[0528] 1 H NMR (500MHz, CDCl3): δ7.60(m,3H),7.43(m,3H),7.40(m,3H),7.36(m,1H),7.26(m,1H),7.17(m,1H),7.16(m,3H),7.15(m,1H),2.60(m,1 H),2.39(m,3H),1.80(m,2H),1.53(m,3H),1.48(m,18H),1.47(m,1H),1.42(m,18H),1.30(m,2H),1.24(m,18H),1.24(m,2H),0.99(m,27H)

[0529] Synthesis Example 86 (Formula 9-20)

[0530]

[0531] N-(Bis(3-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(3-(tributylsilyl)phenyl)-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0532] 1 H NMR (500MHz, CDCl3): δ7.62(m,3H),7.45(m,1H),7.42(m,3H),7.37(m,3H),7.19(m,1H),7.13(m,4H),7.11(m,3H),7.05(m,1H),2.6 7(m,1H),1.79(m,2H),1.57(m,2H),1.48(m,2H),1.46(m,18H),1.40(m,18H),1.31(m,18H),1.28(m,2H),1.18(m,2H),0.96(m,27H)

[0533] Synthesis Examples 87 to 116: Synthesis of Ligand Compounds Represented by Formula 2-67 to Formula 2-96

[0534] 20mmol (2 equivalents) of p-bromo-(tri-n-butylsilyl)-C6H4 was dissolved in 20ml of tetrahydrofuran and then cooled to -78°C. While maintaining the temperature, 20mmol (2 equivalents) of n-butyllithium were added dropwise thereto and then stirred for 3 hours. Subsequently, 10mmol (1 equivalent) of dichloro(diethylamino)phosphine dissolved in 10mL of tetrahydrofuran was added dropwise thereto, the temperature was then raised to room temperature, and the mixture was stirred overnight. Thereafter, a vacuum was used to remove the solvent, and the obtained intermediate was dissolved in 30mL of hexane, HCl (2 equivalents in ether) was then added thereto, stirred for 15 minutes, and filtered. The filtrate was dried under vacuum to obtain (p-(tri-n-butylsilyl)-C6H4)2PCl. 11mmol (2.2 equivalents) of R 5 -NH 2 and 10 ml of dichloromethane were introduced into a fully dried flask and stirred. 5 mmol (1 equivalent) of (p-(tri-n-butylsilyl)-C6H4)2PCl was diluted in 10 ml of dichloromethane and then slowly introduced into the flask. After stirring for 4 hours, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and then (p-(tri-n-butylsilyl)-C6H4)2P-NHR was obtained by column chromatography. 5 .

[0535] 5mmol (1 equivalent) of PhPCl2 was dissolved in 10ml of ether. Then cooled to 0°C. Subsequently, 10mmol (2 equivalents) of HNEt2 dissolved in 10ml of ether was slowly introduced thereto and stirred overnight. The solid was removed by a filter, and 1 equivalent of ArMgBr prepared from Ar and Mg flakes (magnesium chips) was slowly introduced thereto, and then stirred at room temperature overnight. Thereafter, HCl (2 equivalents in ether) was introduced thereto and stirred at room temperature for 30 minutes. The solid was removed by a filter and the pressure was reduced to obtain PhArPCl. 5mmol (1 equivalent) of PhArPCl was dissolved in 10ml of dichloromethane, and then 15mmol (3eq) of triethylamine was added thereto. Subsequently, 5mmol (1 equivalent) of (p-(tri-n-butylsilyl)-C6H4)2P-NHR 5 Dissolve in dichloromethane, then slowly introduce thereinto, and stir the mixture at room temperature overnight. Remove the solvent using vacuum, dissolve in hexane, and obtain ligand compounds represented by Formula 2-67 to Formula 2-96 by column chromatography.

[0536] R as a substituent of the reactants used in Synthesis Examples 97 to 116 5 and Ar are shown in Table 3 below, Ph is phenyl, and the structures and 1 The H NMR data are described below.

[0537] [Table 3]

[0538]

[0539]

[0540]

[0541]

[0542] Synthesis Example 87 (Formula 2-67)

[0543]

[0544] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N-methyl-1-phenylphosphinamine

[0545] 1H NMR (500MHz, CDCl3): δ7.49(m,3H),7.45(m,4H),7.36(m,1H),7.28(m,1H),7.16(m,2H),7.1 3(m,5H),7.07(m,1H),2.56(m,3H),1.47(m,12H),1.40(m,12H),1.23(m,12H),0.94(m,18H)

[0546] Synthesis Example 88 (Formula 2-68)

[0547]

[0548] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-phenyl-1-(2-(trifluoromethyl)phenyl)phosphinamine 1 H NMR (500MHz, CDCl3): δ7.47(m,1H),7.45(m,4H),7.42(m,4H),7.22(m,1H),7.12(m,6 H),7.07(m,1H),2.55(m,3H),1.45(m,12H),1.40(m,12H),1.30(m,12H),0.96(m,18H)

[0549] Synthesis Example 89 (Formula 2-69)

[0550]

[0551] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-methoxyphenyl)-N-methyl-1-phenylphosphinamine

[0552] 1 H NMR (500MHz, CDCl3): δ7.48(m,3H),7.44(m,1H),7.41(m,4H),7.18(m,3H),7.15(m,4H),7.14(m,1 H),7.02(m,1H),3.95(m,3H),2.55(m,3H),1.45(m,12H),1.39(m,12H),1.27(m,12H),0.98(m,18H)

[0553] Synthesis Example 90 (Formula 2-70)

[0554]

[0555] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-phenyl-1-(o-tolyl)phosphinamine

[0556] 1 H NMR (500MHz, CDCl3): δ7.47(m,4H),7.42(m,3H),7.37(m,1H),7.26(m,1H),7.21(m,2H),7.13(m,1 H),7.12(m,5H),2.56(m,3H),2.37(m,3H),1.45(m,12H),1.43(m,12H),1.30(m,12H),0.98(m,18H)

[0557] Synthesis Example 91 (Formula 2-71)

[0558]

[0559] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-methyl-1-phenyl-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0560] 1 H NMR (500MHz, CDCl3): δ7.46(m,3H),7.42(m,4H),7.41(m,1H),7.19(m,3H),7.11(m,1H),7.1 0(m,4H),7.01(m,1H),2.54(m,3H),1.51(m,12H),1.41(m,12H),1.31(m,12H),0.97(m,18H)

[0561] Synthesis Example 92 (Formula 2-72)

[0562]

[0563] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(2-fluorophenyl)-1-phenylphosphinamine

[0564] 1 H NMR (500MHz, CDCl3): δ7.49(m,3H),7.46(m,4H),7.37(m,1H),7.24(m,1H),7.17(m,2H),7.15(m,5H),7.14(m,1 H),2.63(m,2H),1.49(m,12H),1.45(m,2H),1.37(m,12H),1.35(m,2H),1.30(m,12H),0.97(m,18H),0.91(m,3H)

[0565] Synthesis Example 93 (Formula 2-73)

[0566]

[0567] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-phenyl-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0568] 1 H NMR (500MHz, CDCl3): δ7.51(m,1H),7.42(m,4H),7.40(m,4H),7.24(m,1H),7.19(m,4H),7.15(m,2H),7.0 7(m,1H),2.68(m,2H),1.44(m,14H),1.40(m,12H),1.32(m,2H),1.29(m,12H),0.98(m,3H),0.95(m,18H)

[0569] Synthesis Example 94 (Formula 2-74)

[0570]

[0571] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-(2-methoxyphenyl)-1-phenylphosphinamine

[0572] 1 H NMR (500MHz, CDCl3): δ7.44(m,3H),7.43(m,4H),7.41(m,1H),7.18(m,4H),7.15(m,1H),7.11(m,3H),7.02(m,1H),3.9 5(m,3H),2.71(m,2H),1.51(m,12H),1.45(m,2H),1.41(m,2H),1.39(m,12H),1.26(m,12H),1.02(m,18H),0.92(m,3H)

[0573] Synthesis Example 95 (Formula 2-75)

[0574]

[0575] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-phenyl-1-(o-tolyl)phosphinamine

[0576] 1H NMR (500MHz, CDCl3): δ7.48(m,4H),7.45(m,3H),7.33(m,1H),7.21(m,1H),7.20(m,3H),7.17(m,4H),7.14(m,1H),2.6 4(m,2H),2.38(m,3H),1.51(m,12H),1.46(m,2H),1.39(m,12H),1.33(m,2H),1.30(m,12H),0.97(m,3H),0.92(m,18H)

[0577] Synthesis Example 96 (Formula 2-76)

[0578]

[0579] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-butyl-1-phenyl-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0580] 1 H NMR (500MHz, CDCl3): δ7.46(m,3H),7.45(m,4H),7.39(m,1H),7.18(m,3H),7.13(m,1H),7.12(m,4H),7.02(m,1 H),2.66(m,2H),1.50(m,12H),1.47(m,2H),1.41(m,12H),1.39(m,2H),1.26(m,12H),1.02(m,18H),0.91(m,3H)

[0581] Synthesis Example 97 (Formula 2-77)

[0582]

[0583] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N-isopropyl-1-phenylphosphinamine

[0584] 1 H NMR (500MHz, CDCl3): δ7.47(m,4H),7.46(m,3H),7.34(m,1H),7.20(m,1H),7.17(m,5H),7.12(m,2 H),7.10(m,1H),2.86(m,1H),1.45(m,12H),1.37(m,12H),1.28(m,12H),1.08(m,6H),1.02(m,18H)

[0585] Synthesis Example 98 (Formula 2-78)

[0586]

[0587] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-phenyl-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0588] 1 H NMR (500MHz, CDCl3): δ7.46(m,1H),7.43(m,8H),7.19(m,1H),7.14(m,2H),7.11(m,4H),7.0 7(m,1H),2.85(m,1H),1.50(m,12H),1.44(m,12H),1.28(m,12H),1.08(m,6H),1.00(m,18H)

[0589] Synthesis Example 99 (Formula 2-79)

[0590]

[0591] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-(2-methoxyphenyl)-1-phenylphosphinamine

[0592] 1 H NMR (500MHz, CDCl3): δ7.51(m,3H),7.49(m,4H),7.45(m,1H),7.18(m,4H),7.15(m,3H),7.13(m,1H),6.9 9(m,1H),4.00(m,3H),2.88(m,1H),1.52(m,12H),1.43(m,12H),1.31(m,12H),1.08(m,6H),0.94(m,18H)

[0593] Synthesis example 100 (Formula 2-80)

[0594]

[0595] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-phenyl-1-(o-tolyl)phosphinamine

[0596] 1H NMR (500MHz, CDCl3): δ7.45(m,4H),7.44(m,3H),7.40(m,1H),7.22(m,1H),7.17(m,1H),7.16(m,2H),7.13(m,1 H),7.11(m,4H),2.87(m,1H),2.33(m,3H),1.44(m,12H),1.41(m,12H),1.28(m,12H),1.12(m,6H),0.93(m,18H)

[0597] Synthesis Example 101 (Formula 2-81)

[0598]

[0599] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-isopropyl-1-phenyl-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0600] 1 H NMR (500MHz, CDCl3): δ7.44(m,3H),7.43(m,4H),7.37(m,1H),7.16(m,1H),7.14(m,3H),7.12(m,4 H),7.01(m,1H),2.89(m,4H),1.52(m,12H),1.37(m,12H),1.32(m,12H),1.07(m,6H),0.92(m,18H)

[0601] Synthesis Example 102 (Formula 2-82)

[0602]

[0603] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(2-fluorophenyl)-1-phenylphosphinamine

[0604] 1 H NMR (500MHz, CDCl3): δ7.49(m,4H),7.45(m,3H),7.40(m,1H),7.22(m,1H),7.21(m,2H),7.13(m,1H),7.10(m,5H),2.61(m,1H),1.8 0(m,2H),1.56(m,2H),1.53(m,12H),1.49(m,1H),1.46(m,1H),1.41(m,12H),1.27(m,12H),1.21(m,2H),1.14(m,2H),0.92(m,18H)

[0605] Synthesis Example 103 (Formula 2-83)

[0606]

[0607] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-phenyl-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0608] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.47(m,4H),7.46(m,1H),7.22(m,1H),7.16(m,2H),7.12(m,4H),7.06(m,1H),2.61(m,1 H),1.76(m,2H),1.52(m,2H),1.51(m,1H),1.50(m,13H),1.39(m,12H),1.25(m,12H),1.24(m,2H),1.14(m,2H),0.92(m,18H)

[0609] Synthesis Example 104 (Formula 2-84)

[0610]

[0611] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-(2-methoxyphenyl)-1-phenylphosphinamine

[0612] 1 H NMR (500MHz, CDCl3): δ7.48(m,3H),7.44(m,1H),7.43(m,4H),7.18(m,3H),7.12(m,4H),7.11(m,1H),6.96(m,1H),4.00(m,3H),2.61(m,1 H),1.78(m,2H),1.52(m,2H),1.49(m,1H),1.48(m,1H),1.45(m,12H),1.41(m,12H),1.32(m,12H),1.27(m,2H),1.13(m,2H),0.99(m,18H)

[0613] Synthesis Example 105 (Formula 2-85)

[0614]

[0615] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-phenyl-1-(o-tolyl)phosphinamine

[0616] 1H NMR (500MHz, CDCl3): δ7.49(m,7H),7.37(m,1H),7.22(m,1H),7.21(m,1H),7.16(m,4H),7.15(m,1H),7.11(m,2H),2.64(m,1H),2.41(m,3 H),1.83(m,2H),1.51(m,12H),1.50(m,2H),1.49(m,1H),1.48(m,1H),1.39(m,12H),1.28(m,12H),1.27(m,2H),1.18(m,2H),0.94(m,18H)

[0617] Synthesis Example 106 (Formula 2-86)

[0618]

[0619] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-cyclohexyl-1-phenyl-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0620] 1 H NMR (500MHz, CDCl3): δ7.50(m,3H),7.46(m,4H),7.40(m,1H),7.18(m,4H),7.17(m,3H),7.12(m,1H),7.03(m,1H),2.64(m,1 H),1.81(m,2H),1.58(m,2H),1.52(m,1H),1.47(m,13H),1.41(m,12H),1.29(m,2H),1.24(m,12H),1.16(m,2H),1.01(m,18H)

[0621] Synthesis Example 107 (Formula 2-87)

[0622]

[0623] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-1-phenylphosphinamine

[0624] 1 H NMR (500MHz, CDCl3): δ7.50(m,3H),7.41(m,4H),7.35(m,4H),7.33(m,2H),7.26(m,1H),7.17(m,2 H),7.14(m,1H),7.13(m,5H),3.94(m,2H),1.51(m,12H),1.44(m,12H),1.24(m,12H),0.96(m,18H)

[0625] Synthesis Example 108 (Formula 2-88)

[0626]

[0627] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-phenyl-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0628] 1 H NMR (500MHz, CDCl3): δ7.50(m,4H),7.47(m,1H),7.45(m,4H),7.35(m,4H),7.33(m,1H),7.20(m,2H),7.1 9(m,1H),7.10(m,4H),7.04(m,1H),3.94(m,2H),1.51(m,12H),1.43(m,12H),1.31(m,12H),0.95(m,18H)

[0629] Synthesis Example 109 (Formula 2-89)

[0630]

[0631] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-methoxyphenyl)-1-phenylphosphinamine

[0632] 1 H NMR (500MHz, CDCl3): δ7.48(m,4H),7.45(m,3H),7.41(m,1H),7.33(m,5H),7.15(m,3H),7.14(m,4 H),7.11(m,1H),7.05(m,1H),3.95(m,5H),1.50(m,12H),1.46(m,12H),1.27(m,12H),0.92(m,18H)

[0633] Synthesis Example 110 (Formula 2-90)

[0634]

[0635] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-phenyl-1-(o-tolyl)phosphinamine

[0636] 1H NMR (500MHz, CDCl3): δ7.43(m,3H),7.42(m,4H),7.37(m,1H),7.35(m,5H),7.20(m,1H),7.16(m,1H),7.14(m,2 H),7.12(m,4H),7.09(m,1H),3.99(m,2H),2.34(m,3H),1.46(m,12H),1.42(m,12H),1.32(m,12H),0.92(m,18H)

[0637] Synthesis Example 111 (Formula 2-91)

[0638]

[0639] N-Benzyl-N-(bis(4-(tributylsilyl)phenyl)phosphino)-1-phenyl-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0640] 1 H NMR (500MHz, CDCl3): δ7.51(m,3H),7.47(m,4H),7.43(m,1H),7.32(m,1H),7.31(m,4H),7.20(m,1H),7.1 7(m,3H),7.13(m,4H),6.97(m,1H),3.98(m,2H),1.52(m,12H),1.39(m,12H),1.30(m,12H),0.96(m,18H)

[0641] Synthesis Example 112 (Formula 2-92)

[0642]

[0643] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-fluorophenyl)-N,1-diphenyl-phosphine

[0644] 1 H NMR (500MHz, CDCl3): δ7.44(m,3H),7.42(m,4H),7.31(m,1H),7.23(m,1H),7.19(m,2H),7.16(m,5H),7.1 2(m,2H),7.09(m,1H),6.83(m,1H),6.68(m,2H),1.50(m,12H),1.45(m,12H),1.23(m,12H),0.94(m,18H)

[0645] Synthesis Example 113 (Formula 2-93)

[0646]

[0647] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N,1-diphenyl-1-(2-(trifluoromethyl)phenyl)phosphinamine

[0648] 1 H NMR (500MHz, CDCl3): δ7.49(m,1H),7.46(m,4H),7.44(m,4H),7.20(m,1H),7.17(m,4H),7.14(m,1 H),7.13(m,4H),6.83(m,1H),6.62(m,2H),1.48(m,12H),1.36(m,12H),1.31(m,12H),1.00(m,18H)

[0649] Synthesis Example 114 (Formula 2-94)

[0650]

[0651] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-1-(2-methoxyphenyl)-N,1-diphenylphosphinamine

[0652] 1 H NMR (500MHz, CDCl3): δ7.50(m,3H),7.44(m,1H),7.43(m,4H),7.15(m,1H),7.12(m,6H),7.11(m,3H),7.0 3(m,1H),6.87(m,1H),6.68(m,2H),3.93(m,3H),1.51(m,12H),1.37(m,12H),1.23(m,12H),0.99(m,18H)

[0653] Synthesis Example 115 (Formula 2-95)

[0654]

[0655] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N,1-diphenyl-1-(o-tolyl)phosphinamine

[0656] 1H NMR (500MHz, CDCl3): δ7.45(m,3H),7.41(m,4H),7.37(m,1H),7.20(m,1H),7.18(m,1H),7.17(m,4H),7.14(m,3 H),7.11(m,2H),6.86(m,1H),6.68(m,2H),2.32(m,3H),1.48(m,12H),1.42(m,12H),1.25(m,12H),0.93(m,18H)

[0657] Synthesis Example 116 (Formula 2-96)

[0658]

[0659] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N,1-diphenyl-1-(2-(trifluoromethoxy)phenyl)phosphinamine

[0660] 1 H NMR (500MHz, CDCl3): δ7.46(m,4H),7.45(m,3H),7.43(m,1H),7.16(m,4H),7.14(m,3H),7.13(m,1H),7.1 0(m,2H),6.99(m,1H),6.77(m,1H),6.63(m,2H),1.46(m,12H),1.44(m,12H),1.30(m,12H),0.94(m,18H)

[0661] Comparative Synthesis Example 1: Synthesis of the Ligand Compound Represented by Formula 14

[0662] 5.5mmol (0.5 equivalent) of 3-methyl-2-butylamine, 22mmol (2 equivalents) of triethylamine and 10ml of dichloromethane were introduced into a dry flask under a nitrogen atmosphere and stirred. Subsequently, the mixture was cooled to 0°C, and then 11mmol (1 equivalent) of chlorobis(4-(tributylsilyl)phenyl)phosphine was slowly introduced therein. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and then a compound represented by Formula 14 was obtained by column chromatography.

[0663] [Formula 14]

[0664]

[0665] N-(Bis(4-(tributylsilyl)phenyl)phosphino)-N-(3-methylbutan-2-yl)-1,1-bis(4-(tributylsilyl)phenyl)phosphinamine

[0666] 1H NMR (500MHz, C6D6): δ7.96-7.34(m,16H),3.64-3.53(m,1H),1.81-1.72(m,1H),1. 38-1.29(m,48H),1.05(d,3H),0.91-0.84(m,39H),0.82-0.76(m,24H),0.55(d,3H)

[0667] Comparative Synthesis Example 2: Synthesis of the Ligand Compound Represented by Formula 15

[0668] 5.5mmol (0.5 equivalent) cyclohexylamine, 22mmol (2 equivalents) triethylamine and 10ml dichloromethane were introduced into a dry flask under a nitrogen atmosphere and stirred. Subsequently, the mixture was cooled to 0°C, and then 11mmol (1 equivalent) of chlorobis (4-cyclohexylphenyl) phosphine was slowly introduced therein. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and then the compound represented by Formula 15 was obtained by column chromatography.

[0669] [Formula 15]

[0670]

[0671] N-(Bis(4-cyclohexylphenyl)phosphino)-N-cyclohexyl-1,1-bis(4-cyclohexylphenyl)phosphinamide

[0672] 1 H NMR (500MHz, C6D6): δ7.58(br.s,8H),7.08(d,8H),3.47(pent,1H),2.35(t, 4H),2.21-2.11(m,2H),1.80(d,8H),1.71-1.56(m,16H),1.44-1.11(m,24H)

[0673] Comparative Synthesis Example 3: Synthesis of the Ligand Compound Represented by Formula 16

[0674] 5.5mmol (0.5 equivalent) cyclohexylamine, 22mmol (2 equivalent) triethylamine and 10ml dichloromethane were introduced into a dry flask under a nitrogen atmosphere and stirred. Subsequently, the mixture was cooled to 0°C, and then 11mmol (1 equivalent) of chlorobis (4-phenylphenyl) phosphine was slowly introduced therein. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and then the compound represented by Formula 16 was obtained by column chromatography.

[0675] [Formula 16]

[0676]

[0677] 1,1-Bis([1,1'-biphenyl]-4-yl)-N-cyclohexyl-N-(bis([1,1'-biphenyl]-4-yl)phosphino)phosphine

[0678] 1 H NMR (500MHz, C6D6): δ7.92-7.42(m,24H),7.17(t,8H),7.10(t,4H),3.58(pent,1H),2.28 -2.17(m,2H),1.84-1.77(m,2H),1.67-1.60(m,2H),1.48-1.42(m,1H),1.18-1.07(m,3H)

[0679] Comparative Synthesis Example 4: Synthesis of the Ligand Compound Represented by Formula 17

[0680] 5.5mmol (0.5 equivalent) of cyclohexylamine, 22mmol (2 equivalents) of triethylamine and 10ml of dichloromethane were introduced into a dry flask under a nitrogen atmosphere and stirred. Subsequently, the mixture was cooled to 0°C, and then 11mmol (1 equivalent) of chlorobis (3,5-dimethylphenyl) phosphine was slowly introduced therein. After the reaction was completed, the precipitated solid was removed by a filter, the solvent was removed under reduced pressure, and then a compound represented by Formula 17 was obtained by column chromatography.

[0681] [Formula 17]

[0682]

[0683] N-(Bis(3,5-dimethylphenyl)phosphino)-N-cyclohexyl-1,1-bis(3,5-dimethylphenyl)phosphinamine

[0684] 1 H NMR (500MHz, C6D6): δ7.38(br.s,8H),6.79(s,4H),3.63(pent,1H),2.24-2.13(m, 2H),2.10(s,24H),1.77(d,2H),1.60(d,2H),1.45-1.39(m,1H),1.19-1.00(m,3H)

[0685] Examples and Comparative Examples

[0686] Example 1

[0687] Under an argon atmosphere, 0.5 mmol of tetrahydrofuran chromium (III) chloride (Cr (THF) 3 Cl 3), 0.5 mmol of the ligand compound represented by Formula 2-1 according to Synthesis Example 1, and 0.5 mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) as a co-catalyst were placed in a flask, and then 30 ml of dichloromethane was introduced therein, stirred for 1 hour, and the solvent was removed using a vacuum. Thereafter, the mixture was dissolved in methylcyclohexane and filtered, and then the solvent was removed using a vacuum again, and dissolved in methylcyclohexane to prepare a 0.15 mM (Cr-based) catalyst solution.

[0688] Preparation capacity is the Parr reactor of 600ml and evacuates 2 hours at 120 ℃, then uses argon replacement reactor interior and temperature is reduced to 70 ℃.Then, inject methylcyclohexane 180ml and 2ml as 725μmol diisobutylaluminum hydride of activator, inject 5ml (Cr of 0.75μmol) catalyst solution thereto again.After stirring two minutes under 1000rpm, open the valve of the ethylene pipeline that is set as 40 bar, to fill reactor with ethylene, then stir 60 minutes under 1000rpm.Close the ethylene pipeline valve, and use dry ice / acetone bath that reactor is cooled to 0 ℃, then slowly discharge unreacted ethylene, and add 0.5ml nonane (GC internal standard) wherein.After stirring 10 seconds, take out the liquid portion of 2ml reactor, quench with water, filter gained organic part with PTFE injection filter to prepare GC-FID sample. Then, the distribution of the liquid product was analyzed by GC (Agilent, 6890N, Alltech AT-5 (30m×0.32mm ID×0.25μm; Serial No. 12446). In addition, 400ml of ethanol / HCl (10% by volume of a 12M HCl aqueous solution) was added to the remaining reaction solution, stirred, and filtered to analyze the amount of the solid product. The resulting polymer was dried in a vacuum oven at 80°C overnight.

[0689] Examples 2 to 116 and Comparative Examples 1 to 4

[0690] Examples 2 to 116 and Comparative Examples 1 to 4 were performed in the same manner as the above-mentioned Example 1-1, except that the catalyst type was changed as shown in Table 4 below.

[0691] [Table 4]

[0692]

[0693]

[0694]

[0695]

[0696]

[0697]

[0698]

[0699] Experimental example

[0700] The results of the ethylene oligomerization reactions according to the above Examples and Comparative Examples are shown in Table 5 below.

[0701] *Catalytic activity (tons / mol·Cr / hour): The catalytic activity was calculated from the total product weight (tons) of the sum of the weight (tons) of the obtained liquid product and the weight (tons) of the obtained solid product.

[0702] *1-C6 and 1-C8 selectivity (weight %): From the results of analyzing the distribution of the liquid product by GC, the contents of 1-hexene (1-C6) and 1-octene (1-C8) were calculated to calculate the weight % of 1-hexene or 1-octene relative to the total weight of the product.

[0703] *Solids (wt%): The weight % of solid product relative to the total weight of the product is calculated. This indicates the extent to which polyethylene having a carbon number of about 40 or more is produced as an insoluble solid that does not dissolve in the solvent.

[0704] [Table 5]

[0705]

[0706]

[0707]

[0708]

[0709]

[0710]

[0711]

[0712] As shown in Table 5 above, when ethylene oligomerization reaction was carried out using the catalyst composition comprising the ligand compound according to the present invention, it was confirmed that the phenyl group located at the terminal of the diphosphinoamino moiety had a specific substituent at the ortho position, and had an alkyl group having a specific carbon number, or a silyl group substituted with an alkyl group having a specific carbon number as a substituent at each of the meta and para positions, and it was also confirmed that the catalytic activity, selectivity and stability were improved by controlling the steric strain around the PNP functional group by the substituent substituted on the nitrogen atom.

[0713] From the above results, it can be confirmed that when ethylene oligomerization is carried out using an organic chromium compound and a catalyst composition including the ligand compound of the present invention, linear α-olefins with high selectivity for 1-hexene and 1-octene can be produced while having excellent productivity due to high catalytic activity.

Claims

1. A ligand compound represented by the following formula 1: [Formula 1] In the above formula 1, R 1 is a halogen group, an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkoxy group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylthio group having 1 to 10 carbon atoms which may be substituted by a halogen group, an alkylsulfonate group having 1 to 10 carbon atoms which may be substituted by a halogen group, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), or R 6 bonded to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, wherein if R 6 and R 1 are not bonded to each other to form a monocyclic or polycyclic aromatic hydrocarbon ring or a monocyclic or polycyclic heterocyclic ring, then R 6 It is hydrogen, R 2 To R 4 are each independently hydrogen, an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an arylalkoxyalkyl group having 7 to 30 carbon atoms, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 10 carbon atoms), wherein R 2 To R 4 are not both hydrogen, and R 5 It is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused with an aryl group having 6 to 10 carbon atoms.

2. The ligand compound according to claim 1, wherein R 1 is fluorine, an alkyl group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkoxy group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylthio group having 1 to 5 carbon atoms which may be substituted by fluorine, an alkylsulfonate group having 1 to 5 carbon atoms which may be substituted by fluorine, or a trialkylsilyl group (the alkyl groups of the trialkylsilyl group are each independently an alkyl group having 1 to 5 carbon atoms), or R 6 The bonds form a monocyclic or polycyclic heterocyclic ring.

3. The ligand compound according to claim 1, wherein R 1is a fluoro group, a trifluoromethyl group, a methoxy group, a methyl group, a trifluoromethoxy group, a trifluoromethylthio group, a methylthio group, a methylsulfonate group or a trimethylsilyl group, or 6 Bonding forms furan or dibenzofuran.

4. The ligand compound according to claim 1, wherein R 2 To R 4 are each independently hydrogen, an alkyl group having 8 to 12 carbon atoms, a tripropylsilyl group or a tributylsilyl group, wherein R 2 To R 4 Not hydrogen at the same time.

5. The ligand compound according to claim 1, wherein R 2 To R 4 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

6. The ligand compound according to claim 1, wherein R 2 is hydrogen, and R 3 and R 4 Each is independently n-decyl, tripropylsilyl or tributylsilyl.

7. The ligand compound according to claim 1, wherein R 5 It is an alkyl group having 3 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted by an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms fused to an aryl group having 6 to 10 carbon atoms.

8. The ligand compound according to claim 1, wherein the ligand compound represented by the above formula 1 is represented by any one of the following formulas 2 to 9: [Formula 2] [Formula 3] [Formula 4] [Formula 5] [Formula 6] [Formula 7] [Formula 8] [Formula 9] In the above formulas 2 to 9, R1 To R 6 Each is the same as defined in claim 1.

9. The ligand compound according to claim 1, wherein the ligand compound represented by the above Formula 1 is represented by any one of the following Formulas 2-1 to 2-96 and 9-1 to 9-20: 10 . An organic chromium compound comprising the ligand compound according to claim 1 and chromium bidentiated with the ligand compound. 11 . The ligand compound according to claim 10 , wherein in the ligand compound represented by the above Formula 1, a non-shared electron pair of one or more of N and two Ps is bidentiated with the chromium.

12. A catalyst composition comprising the ligand compound according to claim 1, chromium and a promoter.

13. The catalyst composition of claim 12, wherein the chromium is derived from a chromium source, wherein the chromium source comprises one or more selected from chromium (III) acetylacetonate, chromium (III) chloride tetrahydrofuran, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) valerate, chromium (III) laurate, chromium (III) tris(2,2,6,6-tetramethyl-3,5-heptanedioate) and chromium (III) stearate.

14. The catalyst composition according to claim 12, wherein the co-catalyst is one or more selected from the compounds represented by the following formula 10 to formula 13: [Formula 10] -[Al(R 13 )-O] a - In the above formula 10, R 13 are each independently a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and a is an integer greater than 2, [Formula 11] E(R 14 )3 In the above formula 11, E is aluminum or boron, and R 14are each independently hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a halogen group, and [Formula 12] [LH] + [G(Y)4] - [Formula 13] [L] + [G(Y)4] - Wherein in the above formulas 12 and 13, L is a neutral or cationic Lewis acid, [LH] + is a Brønsted acid, G is a Group 13 element, and Y is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and here, if the alkyl group or aryl group is substituted, the substituent is a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.

15. A method for preparing linear α-olefins, the method comprising (S10) oligomerizing ethylene in the presence of the catalyst composition according to claim 12.

16. The process of claim 15, wherein the linear alpha-olefin is 1-hexene, 1-octene, or a mixture thereof.

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