TW200418865A - Production of iridium complexes - Google Patents

Abstract

The invention relates to a process for producing a trivalent hexadentate ortho-metallated iridium complex with an iridium compound and a coordination compound as starting materials, which is characterized in that a monovalent iridium dinulear complex represented by the following formula (I) is used (wherein A represents a non-conjugated diene compound; and X represents a halogen atom). According to the invention, it is possible to carry out the successive reactions in the same reaction vessel (i.e., one-pot reaction) by using the complex produced in the above process in the next step without isolation and purification.

Description

200418865 Rose, description of the invention [Technical field to which the invention belongs] The present invention relates to a method for manufacturing an ortho-metalized iridium complex as a material of a photoexcitation element. [Prior art] Because tritium excites high-brightness light at a lower voltage, organic electro-excitation light (d == mineseenee; EL) elements are practically used as a display element that includes ultra-thin display and electronic paper under one generation. Attention has been paid to the EL element. The EL element has a response speed of liquid crystal and synchronous excitation. It can form a thin flat display by using an organic EL element without a liquid-moonlight It shape. The organic EL element uses the same reference EL light emitting element as a light emitting diode (LED), and is characterized by using an organic fluorescent substance as a light emitting substance. A variety of light-emitting materials for organic EL elements have been developed, in particular, for example, bis (2-phenyl D than indium based epiethylacetone acetone salt (hereinafter referred to as compound 3)) and ginseng (2 • phenylpyridinyl The trivalent hexabud n-metallized iridium complexes with 丨 2,) iridium (hereinafter referred to as compound 5-1) have attracted attention because of their higher quantum efficiency than fluorescent luminescence and can be changed into three states. The excited state excites phosphorescence, and its light radiation wavelength can be adjusted by changing the chemical structure of the ligand as needed. For example, as discussed below, the light-excitation element of compound 5-1 is used for the external quantum of green light emission 9% of the value of the South (Cang Jian non-patent document ip bis [2_ (2, · benzythienyl) pyridinium iridium (III) acetamidoacetone salt (hereinafter referred to as compound 3 丨) 315064 200418865 : Reported as a red light-filled-excitation material with very high quantum efficiency and color purity (see Non-Patent Document 2). From the previous-), it can be seen from the facts that effective methods for peripheral element design and complex compound synthesis The Office of the Research Institute is being actively carried out and will help the party; its consistent use. In the production method of valence six buds _ metallized iridium complexes, there have been reported a number of methods. For example, 'the peak of chlorination in the presence of silver salt and water at high temperature) water "Do not react with a large number of ligands The manufacturing method (see the example of the recent years of the patent document). According to this manufacturing method, up to 82% of the target product obtained. As in other recent examples, it is known that silver (πι) is brewed in glycerol at high temperature. A method for reacting acetylacetonate with a theoretical amount of ligand (Patent Document 2), wherein the yield of 2 is 75%. Although the yield is medium, the method requires strict reaction conditions, and the method cannot be different Kinds of corpus callosum are introduced into compounds. For example (complex of formula (V)). In the improvement of this step, it is reported that the chlorination is performed according to the so-called Nonya step (see Non-Patent Document 3 for tea). Silver (called a hydrate reacted with a theoretical amount of a ligand to synthesize a trivalent six bud normal, metallized silver dinuclear complex of formula (Π) ', and then in the presence of the fish, it ’s & you Shuangshi The reaction of 6 I-based acetone salt to obtain acetamyl acetone salt complex, and then the theoretical value in glycerol at high temperature The amount of the ligand is reacted to obtain the trivalent hexabud n-metal silver complex of formula 00 (see Non-Patent Documents 4 and 5 and Patent Document 3 of Examples in Recent Years). In this step, the first step is reported The paste is 75% or higher, the second step is 75 to 90%, and the third step is 85% or higher (see Non-Patent Document 5). According to this step, a complex containing different ligands (formula Ii)) The same compound containing the same ligand as 315064 6 200418865 (formula (v)) can be produced separately from the same starting material with good yield. However, there are some problems in that the reaction must be performed in multiple steps and individually Complex intermediates and target compounds require complex isolation and purification steps, which will cause loss of target compounds. (Reference Documents) Patent Document 1: WO 02/02714 Patent Document 2: WO 02/15645 Patent Document 3: JP-A No. 1 05055 Non-Patent Document i ·· Bald0 MA et al ·, APP 丨 · Phys · Lett. , 1999, 75, 4-6 Non-Patent Document 2: Adachi, C. et al., Appl phys _, 2001, 78, 1622-1624 Non-Patent Document 3: M. N_yama, Bull. Chem. Soc. Jpn., 1974, 47 (3), 767-768 Non-Patent Document 4: S. Lamansky, et al ”J. Am. Chem. Soc., 2001, 123, 4304-4312 Non-Patent Document 5: S. Lamansky, et al” Inorg. Chem, 2001, 40, 1704-1711 [Summary of the Invention]

Mb N… L divalent hexabud n-silver metal complexes are used as photoexcitation materials for organic electroluminescence (EL) devices. However, its production method must be complexed by 1 '. Therefore, it is expected to establish more convenient steps for producing high yields of this °, which will help the actual use of the complex as a photoexcitation material. 315064 7 200418865 The purpose of the present invention is _ Convenient and effective method for valence six-bud n-metallized iridium complex of German-made, iL A 1, Tu L, seed coat k as the material of the photo-excitation element. The trivalent hexabud ortho_metallized iridium dinuclear complex shown in (II) The present inventors have devoted research to develop an effective and convenient manufacturing method for producing trivalent hexabud ortho_metal in mild conditions Iridium dinuclear complex. As a result, it was found that under mild conditions, the reaction using the monovalent bi-nuclear complex shown in formula (i) as the starting material will give an effective amount of formula in a short time.

After isolation and purification, the complex of formula IX produced in this step can be applied to the synthesis of other complexes. The present inventors have further devoted themselves to the study of establishing commercially applicable steps for generating epicomplexes, and as a result, have found that the trivalent hexabud n-metallized iridium dinuclear complexes of formula (II) resulting from this reaction are not required With isolation and purification from the reaction mixture, it can be reacted with a compound of formula (VII) or (vm) and a base or a compound of formula (VI) and a silver salt in the same reaction tank, and each can be obtained in a convenient and high yield method. The complex with the same ligand (formula i and a complex with different complexes (formulas (m) and (IV)) 'may be produced separately as needed. Therefore, the present invention has been completed based on the foregoing findings. Therefore, the present invention provides a method for producing a trivalent hexabud ortho-metallized iridium complex with an iridium compound and a coordination compound as starting materials, which is characterized by using a monovalent 铉 dinuclear error represented by the following formula ⑴ As the original iridium di-complex: 315064 8 200418865

(Wherein 'A represents a non-conjugated dilute compound; and X represents a tooth element atom). More specifically, the present invention provides a method for manufacturing a trivalent hexa-metallized iridium dinuclear complex shown by formula ㈤:

(U) (where ring and ^ are optionally substituted aryl or heteroaryl groups; ring c is a nitrogen-containing aryl group to be substituted; ring B and ring c may form a fused ring with each other; as defined above), which Special micro-limb fighting, the effect is to react the monovalent iridium dinuclear complex (VI) compound of formula (I): ^

(VI) (wherein the ring B and the ring c are defined as described above) The manufacturer of the present invention can be simply expressed by the reaction formula of column T. Formula ⑴ + Formula (VI) ~ Formula („) This Maoyue also mentioned (, the species will be the complex of formula (Π) generated in the previous step into the formula (III), (IV) or (V) Trivalent six bud normal-metal silver complex method. In this reaction, the complex of formula (π) does not need to be separated and purified from the reaction mixture. —Main features. Briefly, the present invention provides a complete reaction mixture for each step in the manufacture of a metalized iridium complex. This is a trivalent hexabud that is represented by formula (III):

J = each independently of 11 is alkyl, alkoxy, aryl or heteroaryl; A chlorine atom, an aryl group, or a heteroaryl group; together with the carbon atom adjacent to R2 or R2 and R3, a ring is formed; the definition of ring B and ring C is as described above. The compound is antisense to a compound of formula (VI) while waiting for a compound of formula (II), and then reacting a compound of formula with a compound of formula (vII):

(VII) (wherein R], R2 and R3 are as defined above). The production method of the present invention can be expressed simply by the following reaction formula. Step 1: Formula (I) + Formula (VI)-► Formula (II) Step 2 · Formula (II) + Formula-► Formula (III) The manufacturing method of the present invention can be performed stepwise or continuously. When the reaction is performed continuously, the reaction can be performed in the same reaction tank by adding the compound of the formula (VII) to the reaction mixture in the first step, that is, a single tank reaction. 10 315064 200418865 genus :: = t: trivalent six buds as shown in formula (IV)

(IV) (/, Zhong B and% c are as defined above, and ring D represents a substituted pyridyl group as required. In addition, ring B and ring c may form a condensed ring with each other) It is characterized by the following formula: The monovalent iridium dinuclear complex is reacted with a compound of formula (VI) and then with a compound of formula (VIII):

(Wherein ring D is as defined above) The production method of the present invention can be expressed simply by the following reaction formula. Step 1: Formula (I) + Formula (VI)-► Formula (II) Step 2: Formula (II) + Formula (VIII)-► Formula (IV) The manufacturing method of the present invention can be performed stepwise or continuously. When the reaction is performed continuously, the reaction can be performed in the same reaction tank by adding the compound of the formula (VIII) to the reaction mixture in the step _, that is, a single tank reverse deer. In addition, the present invention also provides / manufacturing method of trivalent six bud n-metal iridium complex shown by formula (V): 315064 11

(V) (Di-bicyclo ^ and ring C are as defined above)

', Zheng Zheng reacts the monovalent iridium dinuclear complex of formula ⑴ with a compound of formula (VI) to produce + 4, TT, i A r% compound, and then reacts with the silver salt and compound of formula (VI) The manufacturing method of this method can be expressed simply by the following reaction formula. = Step. Formula (1) + Formula (VI) —— ►Formula (II) Step = Step: Formula (π) + Silver Salt + Formula (VI) —κ Formula (V) " t month manufacturing method can be gradually Or continuously. When continuously proceeding: the reaction 蚪 'reaction can be performed in the same reaction tank by adding a silver salt to the reaction mixture in the first step, that is, a single tank reaction.

Preparation of three monks of the present invention γ A P, /, g n-Meng silver complex

_Characterized by the use of the formula 干 夕 イ Μ イ I 不 イ 之 不 iridium dinuclear complex as a starting material. The manufacturing method of the invention is also characterized by the unitary aa bis, six teeth, and gold iridium complex, which can use the monovalent depleted-imitation series VIII < as early as, iridium mononuclear complex As

The product is produced in the same reaction tank,. ^ ^ U Wang, that is, the early tank reaction. According to the production method of the present decanonium, it is possible to produce a complex compound containing a polypyridine a complex as an coordination complex, for example, to generate a silver compound, such as the following formula (Π), formula (111), formula ( 1 trivalent hexabud iridium complex ·· shown in (v) 3Ϊ5064 12 200418865

(V)

(Where ring B represents an optionally substituted aryl or heteroaryl group; ring C represents an optionally substituted nitrogen-containing aryl group; ring D represents an optionally substituted pyridyl group; ring B and ring C may form a thick Rings; X represents a halogen atom; R1 and R3 each independently represent an alkyl, alkoxy, aryl, or heteroaryl; R2 represents a hydrogen atom, alkyl, aryl, or heteroaryl; and R] and R2 or R2 And R3 can form a ring together with adjacent carbon atoms). [Embodiment] 13 315064 200418865 First, the monovalent iridium dinuclear complex represented by formula (I), which is the starting compound of the production method of the present invention, will be explained below. " The non-conjugated diene compound of formula A in formula A may be cyclic or: bedding and as long as there is no negative effect, there may be one or more substitutions: ": like dilute compounds include mono Ring, polycyclic, condensed ring, and crosslinked cyclonon. Preferred non-conjugated diene compounds shown by A include, for example, 'has 5 to 20 carbon atoms', preferably 5 to 10 carbon atoms. Special: It is preferably a cyclic non-conjugated dilute compound. Specific examples of preferred non-conjugated diene compounds include, for example, 5_cyclooctadiene (cod) and bicyclic [m] heptene 5- A cyclic compound of a diene (nbd). The halo atom represented by X in formula ⑴ includes, for example, a fluorine atom =, ;; atom, and a moth atom, preferably a chlorine atom. The nuclear complex can be represented by the following formula (IX) or (X): X. ', .d (IX)

(X) (where X is as defined above). Six # TδδH is produced in the present invention by the three stern /, ortho-metalized iridium complexes shown by formulas (II) to (V). In formula (11), the ring B% -A, the aryl group includes one of the aryl group, and the slow substitution: a substituted aryl group or a hetero-square group, a heteroaryl group, and a substituted heteroaryl group. Exemplary radicals are exemplified as "monocyclic", "monocyclic, polycyclic" having 6 to 14 carbon atoms, or 14 315064 200418865 condensed ring aryl. Specific examples of the aryl group include phenyl, naphthyl, and anthracenyl. The heteroaryl group may be exemplified by a 5- or 6-membered monocyclic 'polycyclic or condensed ring aromatic heterocyclic group having 1 to 3 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms. Specific examples of heteroaryl include pyridyl, imidazolyl, thiazolyl, furyl, benzofuranyl, thienyl, benzofluorenyl, and the like. The substituted aryl group includes the aforementioned aryl group and at least one hydrogen atom thereof is substituted with a substituent. "Substituted" groups include the aforementioned heteroaryl groups and at least one of the hydrogen atoms is replaced by a substituent. Eight substituents in these groups include alkyl, alkenyl, alkynyl, aryl, and arylalkanes Oxy, thio, cyano, acid, alkoxy, nitro, halogen, alkylenediGxy, etc. The alkyl group can be a straight bond or a branched or% -like alkyl group, and There are, for example, i to 5 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, Isobutyl, third butyl, n-fluorenyl, 2-pentyl, third pentyl, 2-fluorenylbutyl, 3-fluorenylbutyl, 2,2-dimethylpropyl, n-hexyl, 2. Hexyl, 3-hexyl, third hexyl, 2-hexylpentyl: 3-fluorenylpentyl, 4-fluorenylpentyl, 2-methylpentyl, cyclopropyl, cyclobutyl,% pentyl Group, cyclohexyl group, etc. The alkenyl group may be a straight chain or a branched alkenyl group, and has, for example, 2 to 6 carbon atoms. Specific examples of the alkenyl group include a vinyl group, a propenyl group, a 1-butenyl group, and a 2-butenyl group. , Pentenyl, hexenyl, etc. The alkynyl can be straight chain or ammonium The alkynyl group has, for example, 2 to 5 carbon atoms. Specific examples of the alkynyl group include an ethynyl group, a K propynyl group, a 3-propynyl group, a butyrynyl group, a 3-butynyl group, a pentynyl group, and the like. The aryl group may be a linear or branched aryl group having, for example, a monocyclic, polycyclic, or condensed ring aryl group having 6 to 4 carbon atoms. Specific examples of the aryl group include a benzyl group, 315064 200418865 naphthyl group, anthracenyl group, etc. Heteroaryl may be a straight-chain or bi-chain heteroaryl containing 5 to 6 member members, such as nitrogen, oxygen, sulfur, and other heteroatoms. The cyclic group is specifically a pyridyl group, an imidazolyl group, a thiazolyl group, a furyl group, a benzofuryl group, a thienyl group, a benzothienyl group, etc. The alkoxy group may be a straight chain having 1 to 6 carbon atoms or Specific examples of oxy groups include methoxy, ethoxy, n-propoxy, 2-propoxy, n-butoxy, second butoxy, third butoxy, pentyloxy, and hexane. The 1thio group such as an oxy group may be a straight bond or a branched alkylthio group having 6 carbon atoms such as U. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, and a 2-propylthio group. , N-butylthio, Dibutylthio, tertiary butylthio, pentylthio, hexylthio, etc. The alkynyl group can be a straight or branched chain or a cyclic alkynyl group, such as a derivatyl group derived from a carbon atom of ... carbon atoms. Specific examples of the group include methyl group: acetate group, propyl group, butyl group, sulfonyl group, hexanoic acid group, and benzoyl group. The alkoxycarbonyl group includes, for example, a branched alkoxycarbonyl group having 2 to 7 carbon atoms. Some examples of alkoxy groups that are hetero-straight bonds or M-groups include fluorenyloxycarbonyl, propoxyl, n-butoxyquinyl, tertiary butoxyquinyl, ^ 0 atomic atoms including 'for example' fluorine atoms, Chlorine, bromine, and iodine. The butanedioxy group includes, for example, three to three, and specifically, for example, an butanedioxy group: propanedioxy group, and the like. Methylethane, lactyl, or heteroaryl means that the ring contains at least one nitrogen atom as ... II may further contain 1 or 2 impurities such as nitrogen atom, oxygen atom or ^, including 5_ or 6_ ^ ^ Even framed or condensed 315064 16 At least one nitrogen member of the two-W heterocyclyl group is coordinated with an iridium atom. Lice fragrant containing 6 Λ ,,, earth, for example, pyridyl, quinolyl and the like. The octyl group in ring C may be substituted, and at least one hydrogen atom in the substituted nitrogen-containing aryl group may be substituted by a substituent. The substituents 歹 'are the same as the substituted aryl and heteroaryl groups in Frame B.

Jade TO ^ and% c can be combined to form a ring, including, for example, a fused ring of benzoquinoline. 0 Preferred examples of the triiridium complex of formula (II) produced by the method of the present invention include the following formula (XI As shown

R: alkenyl, alkynyl, aryl, and Rn each independently represent a hydrogen atom, an alkyl group, (wherein R8, R! Heteroaryl, alkoxy, alkylthio, cyano, fluorene: k-oxylate , Nitro, or dentin atom; χ epidentin atom; meaning of ring B,% Β can form a ring with a pyridine ring bound to ring B). The alkynyl, dilute, and fast radicals represented by R, R9, R] 0, and R11 in j (XI) can effectively form substituents or thiol, thiol, acid, and alkynyl. As the substituents, there may be exemplified the substituted aryl or heteroaryl groups as described in the formula (I). The halogen atom represented by X in the formula (XI) is also the same as described above. Preferred rings B include benzyl, substituted phenyl, naphthyl, substituted naphthyl 315064 200418865, furanyl, substituted furanyl, benzofuranyl, substituted benzopyranyl, thienyl , Substituted thienyl, benzothienyl, substituted benzothienyl, and the like. Examples of substituents on substituted phenyl, substituted naphthyl, substituted sulfanyl, substituted benzofluorenyl, substituted thienyl, and substituted benzothienyl are Those mentioned as substituted aryl or heteroaryl in formula (II). Specific examples of the trivalent hexabud n-metallated iridium complex shown by the formula (II) include the following compounds (Π-i) to (Π-xvi).

18 315064 200418865 (IH) (lHi)

(IHii) (IHv), .N? .0 rV ^ Cl 'rV' Cl \ X S 2 2 2 \ = J (H-v) (Π-vi)

---_ _ cx / Λ vs v Ι ^ ι] > < 〇! > < S 〇s C " χ ρ vs () = {u ———— 2 1 1 2 1 1 2 1 One

(Il-vii)

(1 b viii) ~~ 1 (Λΐ m > IrCC, > < w Cl Yy 19 315064 200418865 (ϊΗχ)

(I 卜 x) rS An " yV U V _ _ 2 F

(Π-xi)

(Π-χίί)

(Il-xiii) f 0 〇2NtS i ^ Y ^ CH3 Ϋ Ύ rV Cl Η3〇γΛ ^ 0 0 J (ΙΙ-χν)

(Π-xiv)

In the trivalent hexabud n--metallization of formula (III) produced by the present invention 20 315064 200418865 iridium complex:

(Wherein Ring B and C, b R, R, and H 3 are each as defined above), each group, that is, ring B, ring Γ p and γ-L, :): member group, alkoxy group, aryl group, It is the same as the heteroaryl group described in Formula (II). These groups may be substituted with a substituent or a substituent described in a substituted aryl or heteroaryl group of formula (II). Preferred substituents include, for example, turtles; 5 ^ ^ ^ ^ chaotic atoms, gas atoms and bromine atoms of the halogen atom, the substituents can be, for example, Nan, P Qi. ^ Ge ® said, haloalkoxy, ii aromatic A radical, and || heteroaryl 0, fluorene (I) is represented by a trans, a rule, and a calcined group may be a straight or branched chain or a cyclic group, for example, a calcined group of 1 to 6 carbon atoms. Specific examples of alkyl groups: fluorenyl, ethyl, n-propyl, 2-propyl, n-butyl 'second butyl, co-butyl, tert-butyl, n-pentyl, 2-pentyl & Tripentyl, 2-methylbutyl, 3 / fluorenylbutyl, 2 = 2-difluorenylpropyl, n-hexyl, 2-hexyl, 3.hexyl-hexyl, 2-hexylpentyl, 3_ Fluorenylpentyl, 4-fluorenylpentyl, fluorenylfluoren-3-yl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The halogenated alkyl group includes, for example, the aforementioned alkyl group (e.g., fluorinated, gasified, brominated, I, halogenated) containing 1 to 6 carbon atoms and halogenated with 2 or 5 halogen atoms. Halogenation :): Specific examples of the elementary group include chlorofluorenyl, bromofluorenyl, trifluorofluorenyl 2-aminoethyl, 3-aminopropyl, 3-methoxypropyl '3,3,3_trioxypropyl Wait. Aryl includes, for example, 'aryl groups containing 6 to 14 carbon atoms. Specific aryl groups 315064 21 Basic, naphthyl, ¥ and so on. x or polycyclic aromatic hetero " ’is a 5- or 6-membered monocyclic atom and /… Yes, for example, 1 to 3 nitrogen atoms, oxygen I :::: heteroatom. Specific examples of the heteroaryl group include a batch. When the ring is singular, the basic ring, the sulfanyl group, and the ring can be single or ring together with " 3, such as-,., Morning clothes or evening nucleus, and preferably 5_ or 6 _ Member system is cyclopentane, cyclohexane and so on. The formed fixtures include the preferred examples of the trivalent six-bud n-metal silver complex shown by =). The brackets are represented by the following formula (XII) ...

(Wherein R, R9, R] °, Rn, R1, R2, R3, and ring b are each as defined above and% B may form a ring together with a pyridyl group bound to ring B). Ring B of Cheryl 4 includes benzyl, substituted phenyl, naphthyl, substituted g-group D-furanyl, substituted fluoranyl, benzofuranyl, substituted benzofluorin Group, thienyl, substituted thienyl, benzothienyl, substituted benzothienyl, and the like. Substituents on substituted phenyl, substituted naphthyl, substituted amino, substituted benzofuranyl, substituted thienyl, and substituted benzothienyl can be exemplified as Those mentioned as substituted aryl or heteroaryl in formula (II). Specific examples of the trivalent hexabud n-_metallized iridium complex shown by formula (π)) 29 315064 200418865 include the following compounds (III-i) to (III-xvi). (ΠΗ)

ChU CH, (IIHi)

(ΙΠ-iv)

(Ilhv)

(III-vi)

(IIb viii)

'' 1 23 315064 200418865 (ΙΠΗχ)

(ΙΙΙ-χ)

—1 2

(ΙΙΙ-χί) (ΠΙ-χϋ)

(ΙΙΙ-xiii)

(ΙΙΙ-xiv)

24 315064 200418865 In the trivalent hexabud ortho-metalized iridium complex shown by formula (IV) produced by the manufacturing method of the present invention:

(Which is the same as ring C with the foregoing definition; ring 0 is optionally substituted with formula two :; ring B and ring C may form a fused ring with each other), and 胄 B is the same as defined in ring C (U). 3 A fused ring or a condensed ring, which may be a monocyclic ring, a multi-dimensional ring, or an ancient ring, or a plurality of hydrogen atoms may be substituted by a substituent. Take the wrong Hachiman system. Martial arts (IV) does not have a negative response to the manufacture of trivalent six buds positive metallized iridium box mouthpieces. ^ Λ ^ rr, the fruit holder ^ is acceptable. Such substituents may be exemplified by those mentioned in the formula (II) which are substituted by a aryl group or a heteroaryl group. Specific examples of the trivalent 丄 τ Α Xiang Xiangshan, /, ortho-metallized iridium complexes represented by formula (IV) include the complexes represented by the following formula (XIII):

(Where R4, R5, R6 and Han 7 each have A ^^^^^^ surface hydrogen atom, alkyl, alkenyl, fluorenyl, aryl, heterosexyl, alkane 1 ^^^^. , Cyano, fluorenyl, :); castanyl, nitro, or halogen atom · M,,, R, R9, R〗 〇, Rn and ring B (as described by Ke Ko). 315064 25 200418865 In formula (XIII), an alkyl group, a dilute group, an alkynyl group, an aryl group, a heteroaryl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkynyl group, an aryl group, an alkoxy group, The thio group, the fluorenyl group, and the alkoxycarbonyl group are the same as described above. These groups may have addition substituents or substituents, and examples of the substituents are those mentioned as substituted aryl or heteroaryl groups in formula (II). Preferred ring B includes phenyl, substituted phenyl, naphthyl, substituted naphthyl, furanyl, substituted furanyl, benzofuranyl, substituted benzofuranyl, thienyl, Substituted thienyl, benzothienyl, substituted benzothienyl, and the like. Examples of substituents on substituted phenyl, substituted naphthyl, substituted furanyl, substituted benzofuranyl, substituted thienyl, and substituted benzothienyl are in the formula: References to substituted aryl or heteroaryl in (II). Specific examples of the trivalent hexabud orthometalated iridium complex shown by the formula (IV) are the following compounds (IV-i) to (IViiii).

26 3] 5064 200418865 (IV-i)

(IV-iii)

(IV-v)

(IV-vii)

OVHi)

In the trivalent six buds represented by formula (V) produced by the manufacturing method of the present invention 27 315064 In the '' metalized iridium complex:

(Wherein ring B, m, and L are each as defined above), and ring B and ring C are as defined above. The heavier di-α-dipyridine hexa-n-metallated iridium complex of formula (V) includes By the following formula (XIV):

(Wherein R, R9, R] 0, Rn and ring B are each as defined above; ring B f and pyridyl bonded to ring B form a ring). Fortunately, B is phenyl, substituted naphthyl, naphthyl, substituted naphthyl, furanyl, substituted furanyl, benzofuranyl, substituted benzofluoranyl, thiophene Group, substituted thienyl, benzothienyl, substituted benzothienyl, and the like. Substituents on substituted phenyl, substituted naphthyl, substituted furanyl, substituted benzofuranyl, substituted thienyl, and substituted benzothienyl can be exemplified by the formula References to substituted aryl or heteroaryl in (II). 28 3] 5064 200418865 Specific examples of the trivalent hexabud n-metallated iridium complex represented by the formula (V) are the following compounds (V-i) to (V-X). (VH) (VHi) / = \ j 1 γ- ： Tr ＞ Ir cV y j 3 3 (V-iii) (VHv)

"3

(V-v) (V-vi) fa Λ Λ Ti ^ > Ir iV ifV — — 3 1 — — (VHx)

(V-vii) (V,)

The use of compounds represented by formulae (VI) to (VIII) as starting materials in the method of the present invention will be explained below. The complex compound in the production method of the present invention means a compound containing a chemical structure capable of forming an iridium complex ligand. These compounds include coordination compounds that can all become complex ligands of the epi-complex, or a part of atoms or atomic groups left in the coordination compound for use in silver complex formation ligands. 315064 29 Deca OOUJ) Deca OOUJ) is used in the compound of formula (VI) in the method of the present invention.

Ή (VI) Ring B and ring C are as defined above. The compound represented by the following formula (XV) (where ring B and ring C are each as defined above). Preferred examples of compounds not represented by formula (VI) include

(XV) American, Chinese R, R ° and R " each independently represent a hydrogen atom, an alkyl group, an alkenyl :: group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, a cyano group, a fluorenyl group,氡% nitro group, or halo atom; ring B represents optionally substituted aryl or heteroaryl; or ring B may form a ring with a pyridyl group linked to ring 3), Λ j (XV) R8, R9, R] 0 and R " alkyl, alkenyl, alkynyl, aryl, heteroaryl, xyloxy "thiol, S! Group, and thiol are strongly substituted Or a plurality of substituents, and examples of the substituents are those mentioned as substituted aryl or heteroaryl in formula (H). Preferred ring B includes phenyl, substituted phenyl, naphthyl , Substituted naphthyl, furanyl, substituted furanyl, benzofuranyl, substituted benzofuranyl, thienyl, substituted thienyl, benzothienyl, substituted benzothienyl, etc. Substituents on substituted phenyl, substituted zeenyl, disubstituted fluoranyl, substituted benzofuranyl, substituted thienyl, and substituted benzothienyl may be Examples are those mentioned in formula (Π) by 30 315064 200418865 substituted aryl or heteroaryl. Specific examples of compounds represented by formula (VI) are the following compounds (VI-i) to (VI-xxvii) 〇31 315064 200418865

(VI-V)

(VI-vi) (VI-vii) (VI-viii) (VI-ix) (VI-x)

32 315064 200418865 (vhxi)

Me〇

Cl

(V BU xxvi)

Me〇2c

CFa

MeO (V 卜 χχνϋ)

Used in the compound represented by formula (vn) in the method of the present invention: R1

(VH) (wherein R], p 2 4 * and R3 have the same definitions as above, alkyl group, alkoxy group, square group and heteroaryl group each have π, and there is one addition substituent or multiple substituents, These substituents may be the same as those mentioned in formula (III). In addition, in the compound represented by formula (VII), the group represented by R] and R3 may be the same as those mentioned in (III). Examples of the compound represented by the formula (VII) used in the present invention are acetamylacetone, 1ethylammonylcyclohexanone, 2-trifluoroacetamylcyclopentanone, Benzodipropylpropane, 2,2 , 6,6 • Tetramethyl-3,5 · heptanedione,% methyl 4, cardiopentane

勹 勹 JO 315064 200418865 ketone, 1, M, 5,5,5-hexafluoro ^ ^ ^ 2,4 "pentanedione, phenylphenyl-1,3-butanedione, [monofuranyl-1 , 3-butadiene, etc. It is used in the compound represented by formula (VIII) of the present invention.

(VIII) The same is preferred (wherein ring D is the same as the delayed acid or a derivative of the compound represented by formula (VIII) :) Ring D is the same as those mentioned in formula (IV). Examples include the following formula (XVI As shown

R6

R5 R4 (XVI) (wherein R, R, R6 and R7 each independently represent a hydrogen atom, alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkylthio, cyano, fluorenyl, Alkoxycarbonyl, nitro, or halogen). In R4, R5, R6 and R7 of the formula (XVI), the alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, alkylthio, fluorenyl, and alkoxycarbonyl groups are the same as described above. These groups may have an addition substituent or a plurality of substituents, and the substituents may be exemplified by those mentioned as substituted aryl or heteroaryl groups in formula (II). Specific examples of the compound represented by the formula (VIII) are the following compounds (VIn_i) to (VIIl: vii) 0 315064 34 200418865

(vm — i) (VIH-ii) (VIH—iii) (VIH—iv)

(VIII-vi) (VIHiii) (VIH-v)

The method of the present invention will be described based on the reaction schemes 1 to 4 and the following items 1) to 4). 1) Figure 1 illustrates the reaction formula of a method of producing a trivalent hexabud n-metallated iridium dinuclear complex of formula (II) using the monovalent iridium dinuclear complex of formula (I) as a starting compound. [Thumbnail 1]

The monovalent iridium dinuclear complex represented by formula (1) is reacted with a compound represented by formula (VI) in the presence or absence of a suitable solvent and, if necessary, in an inert atmosphere, and 35 315064 418865 easily produces the formula (II) What is shown. j Bayliuya orthometallized iridium dinuclear is mismatched with respect to the amount of the mask & depleted substance represented by formula (I), relative to the compound of formula α s and compound (VI) represented by formula (VI) The monovalent iridium dinuclear complex of Huaren'7 compound, the formula "/ 1" is generally used in the amount of 1, but preferably from ... Equivalent, better two ::: Amount 2 ... _ in, = square: preferably performed in the presence of a solvent at this step ► Solvents used in the mouth, for example, such as N- or -methyl its ^ in monomethyl Methylamine, formamidine, compounds; such as 1ΨΘ 7 Hexonitrile-containing cyano-organic o-dichlorobenzene: 2, 2-dichloroethane, chloroform, carbon tetrachloride, or- Toothed hydrocarbons; such as pentane, hexane, heptane, octane aliphatic hydrocarbons, such as cages, Tian # 戍 六 烧 测, benzyl, or xylene aromatic hydrocarbons; such as diethyl ', isopropyl Ether, third butyl fluorenyl ether, dimethoxy. Nanxun Dioxin Luyuan or 13_1 & f (13d known, tetrahydrocoated if not flying i, 3 a lactam ^ (1,3-dlox〇 丨 a) ie) ether. Such as Clan or methyl Ketones of ethyl ketones; such as nail fighters, _ ^. Shame 2. Propanol, I-hand, tertiary butanol, or 1 ethoxy ethanol alcohols; such as a 3K containing a ^ island,- , 1,2-propanediol, or glycerol polyhydric alcohol; or water. 誃 w star bucket, human, ΠΛ 4 gluten can be used, 3, 5, and 2 or more. Among these solvents, preferred Alcohols such as methanol, ethanol, 'propanol, n-butanol, tertiary or 2-ethoxyethanol; alone or octane 2 or more; for example, ethylene glycol, propylene glycol " , Or glycerol polyhydric alcohol; and water, as long as the reaction can be satisfactorily promoted, the use of solvents | to the sub-Asian unlimited 'with respect to 1 part of the monovalent iridium dinuclear complex shown in formula ⑴, complex — use denier + / 、 Generally, it is 1 to 200 parts, preferably about 5 to 50 parts. 315064 36 200418865 In the obliteration step, the reaction is preferably performed in an inert atmosphere. As an inert gas, for example, Use nitrogen, argon, etc. The reaction can also be performed in combination with an ultrasonic generator. ° The reaction temperature is usually selected from the range from 25t to 300t, preferably from 60C to 200 ° C, and more preferably from 80 ° c to 1500c. The reaction time is usually selected The free range is from 10 minutes to 72 hours, preferably from 30 minutes to μ hours, more preferably from 1 to 6 hours. The product obtained from vermiculite is preferably used in subsequent reactions without post-treatment, but can also be carried out if necessary. Treatment of isolation and purification. It can be carried out: for example, extraction and precipitation of reaction products; Dian Guoji, eruption at M, etc. These operations can be performed separately or combined ^ Combined such as column chromatography, recrystallization, sublimation, etc., Or 2) Sketch 2 shows the reaction formula for the method of producing the bivalent 丄 a, '(a / complex) represented by formula (III) from a single starting material represented by formula (I). 七 牙 正- Silver metallized complex 315064 37 200418865 [schema 3

* Bai Xian, according to the method shown in Figure 1, in the presence or absence of an appropriate solvent J and necessary% in a passive atmosphere, the monovalent dinuclear iridium complex shown in formula (1) and formula (VI) The compound reacts to easily produce a trivalent hexabud n-metallated iridium dinuclear complex represented by the formula (Π). 4 妾 1 In the presence or absence of a suitable solvent and if necessary in the presence of a base and in a pure gas environment, the trivalent hexabud positive-silver metal dinuclear obtained in the formula (II) can be dissociated The compound is reacted with a compound represented by the formula (νπ) to obtain a trivalent hexabud n-metallated iridium dinuclear complex represented by the formula (III). In this step, the trivalent six bud positive-metallized iridium dinuclear represented by formula (11) is said. After the product is processed, separated and purified, it reacts with the chemical compound of formula (νίΙ). However, in this method, it is suitable to carry out the compound represented by formula (11) and the formula (VII) in a single hafnium trough without any post-treatment, etc. Compound reaction (ie, single 315064 38 200418865 tank reaction). Compounds of formula (v ^) and) can be added to the reaction medium separately, or the μ-butyl compound can be added to the reaction medium after reacting with the base. When the formula (VII) is modified, the r ° page is first reacted with a base described later, for example, sodium acetoacetone, 2-ethyl ethyl ring is known to ~, potassium benzylacetone, etc. Derivatives of compounds not represented by formula (VII). Once, the monovalent iridium dinuclear complex not represented by () and the compound represented by formula (VI); > face, compared to the monovalent iridium dinuclear complex represented by formula ⑴, the compound not represented by formula The amount used is suitably selected from the range of 2 to 50 equivalents, preferably 3 to 20 equivalents, and more preferably 4 to 6 equivalents. Compared with the monovalent iridium dinuclear complex shown by formula (I), the compound of formula (Vn) A 2 is generally used in an amount of about 1 to 20 equivalents, preferably κ5 to 1 () in reserve, and more preferably 2 to 3 equivalents. In this method, the reaction is preferably performed in the presence of a base. As a rule, two 'can be exemplified by inorganic bases and organic bases. Inorganic bases include sodium hydroxide, gas, carbon dioxide, sodium carbonate, sodium carbonate, sodium bicarbonate, tritium carbonate, and metal hydrides such as sodium hydride. Organic bases include alkali metal oxides such as formazan, sodium alkoxide, lithium alkoxide, sodium ethoxide, and potassium tert-butoxide; and for example, triethylamine, diisopropylethylamine, N, N • di Methylbenzene, hexahydropyridine, pyridine, cardiobiaminoaminopyridine, 1,5 ~ diazabifluorene [4.3.0] non-5-ene, diazabicyclo [5.4.0] ten Mono-7, di-, n-butylamine and N-fluorenyl morpholine organic amines. With respect to the compound of formula (VII), the general amount of base used is suitably selected from 0.5 to 10 equivalents, preferably 0.8 to 2 equivalents, and more preferably 39 315064 200418865 to 1 to 1.2 Equivalent range. For example, nitrogen can be used in this method. The reaction is preferably carried out in an inert atmosphere or argon. Furthermore, the reaction can be performed using an ultrasonic generator. In this method, a solvent is suitably used. In terms of solvents, the example given in Figure 1 is sketched. The reaction temperature is generally selected from a temperature range of 25 ° C to 300 V 〇1, Che Jia Jia Tuoshi from 60. 0 to 200. (:, And more preferably from 80.50 to 50. The reaction time is generally selected from 笳 R λ Yan m from 3 minutes to 48 hours] orbital, preferably from 10 minutes to 24 hours , More preferably 30 minutes to J hours. Next, the obtained formula _ is shown as the trivalent hexa bud positive _ metallized silver wrong ^ after processing as described in Figure 1, single isolation and purification to provide disc 〇) Sketch 3 shows the reaction sequence of a method for producing a trivalent hexabud n-silver metal complex represented by formula (IV) using the monovalent iridium dinuclear complex represented by formula (I) as a starting material. 315064 40 200418865

First, according to the method shown in Fig. 1, a monovalent iridium dinuclear complex of the formula (I) and a compound of the formula (VI) are mixed with a suitable solvent in the presence or absence of a suitable solvent and, if necessary, an inert atmosphere. Reaction, and easily produces a trivalent hexabud n-metallized iridium dinuclear complex represented by formula (II). Next, in the presence or absence of a suitable solvent and, if necessary, in the presence of a base and, if necessary, in an inert atmosphere, the obtained trivalent hexabud n-silver metal dinuclear complex represented by the formula (II) and The compound represented by formula (VIII) reacts gently to obtain a trivalent hexabud n-metallated iridium dinuclear complex represented by formula (IV). In this step, the trivalent hexabud n-metallated europium dinuclear complex represented by the formula (II) is subjected to the aforementioned post-treatment, isolation and purification, and then reacted with the compound represented by the formula (VIII). However, in this method, it is suitable to carry out the compound of formula (II) and the compound of formula (VIII) successively in a single tank without any post-treatment of the trivalent hexabud n-metalized iridium dinuclear complex. Reaction (also 41 315064 200418865 ie single-tank reaction). The compound represented by formula (VIII) can be added to the reaction medium separately from the test, or the compound represented by formula (VIII) can be added to the reaction medium after reacting with the test. When the compound represented by formula (VIII) is first tested with the following, for example, methylpyridine, 3 -gas D ratio σ fixed _ 2-slow acid sodium, 5-phenyl D ratio bite-2 · slow acid _, etc. During the reaction, it can be used as a derivative of the compound represented by the formula (VIII). In terms of the amount of the monovalent silver dinuclear complex represented by formula (VII) and the compound represented by formula (V), the compound represented by formula (VI) is relative to the monovalent iridium dinuclear complex represented by formula (VI) The amount used is suitably selected from the range of 2 to other equivalents, preferably 3 to 20 equivalents, and more preferably 4 to 6 equivalents. Relative to the monovalent iridium dinuclear complex represented by formula (I), the compound represented by formula (νΙΠ) is generally used in an amount of about i to 20 equivalents, preferably i 5 to ι0 equivalents', and more preferably 2 To 3 equivalents. In this method, the reaction is preferably performed in the presence of a test. As a rule of thumb, the example shown in Figure 2 can be used. ... F The reaction in this method is preferably carried out in a pure gas such as I gas, argon gas or the like. The reaction can also be performed in combination with an ultrasound generator. Second, it is suitable to use solvents. For the solvent :: The example as shown in Fig. 1 can be used.

From the 6th generation to 2E, and more preferably from 80. (: To 15Qt〇U reaction time is generally selected from 3 minutes. Λ 10 ^ 4- 5, * to 8 hours, preferably from 24 to 24 hours, more preferably from 30 minutes to " Next, the obtained compound of formula (IV) —one of 0 ~ μ 彳 /, orthodontic—metallized iridium 315064 42 200418865 is subjected to post-treatment as described in the sketch, separated and purified to provide a phosphorescent substance.) Each figure 4 _ shows a reaction of a method for producing a trivalent hexabud n-metallized iridium complex represented by formula (V) using the monovalent iridium dinuclear complex represented by formula (I) as a starting material. [Schematic 4]

First of all, according to the method shown in Fig. 1, the monovalent iridium dinucleotide c-formula (VI) represented by formula (VI) is reacted in the presence or absence of an appropriate dissolve and in an inert atmosphere, if necessary, The trivalent hexabud n-metal silver dinuclear complex shown in formula (i) is easily produced.

Then ^ Λ it ^ A in a suitable solvent or " ,, & suitable solvent, and in the presence of a base, if necessary, and in the environment of lice, the obtained trivalent six buds represented by formula (II) are _ Gold 'iridium dinuclear complexes react with the compound represented by formula (VI) to obtain 43 315064 200418865 to trivalent hexabud n-metallated iridium complexes represented by formula (V). Iri :: In the step, the trivalent hexabud positive-metallized rhenium nucleus II shown in the formula (i) is subjected to the aforementioned post-treatment, isolation, and purification, and (VI) the AC is shown to react from the °. "And in this method, it is suitable to feed the trivalent hexabud orthometallized plutonium-4-'' tank into the ~ ^ complex without any post-processing, etc., followed by a single (ie, the compound shown and the compound The silver salt to the reaction tank is reacted in the early cell reaction.) The reaction silver salt includes gy, such as silver nitrate, silver acetate, and silver trifluoroarsonate. Then, the compound is first reacted with the compound represented by formula (VI). "In the reaction, and then add the compound represented by formula (VI) and continue gas silver acetate, silver pyroxanthate, and silver trifluoroacetate or trifluoromethane stone relative to formula 1 to 20 equivalents f For the compounds shown above, the general usable amount of silver salt is i equivalent, preferably i · 5 to M equivalent, and more preferably 2 to 3 In this reaction, 1 as n is mainly 6 equivalent. In this method Φ. The reaction is preferably in the range of, for example, nitrogen, argon, etc., with respect to the amount of the monovalent 铉 dinuclear complex shown in formula ⑴: the amount of the compound is appropriately selected from 4 to 100 equivalents. In addition, it is preferably 6 to 40 equivalents' and more preferably 8 to 12; it is represented by formula (VI) with respect to formula (1). When the compound is added again after the silver salt is added, the amount is suitable: for the compound, the compound represented by formula (VI) is generally free and preferably 2 to 50 equivalents, preferably 3 to 5). When I, the purity is 315 (54 44 200418865). The reaction can also be performed in combination with an ultrasonic generator. In this method, a solvent is suitable. As for the solvent, it can be used as shown in Figure 1. No. The reaction temperature is generally selected from the temperature range M to 300 ° C, preferably from 60t: to 200t, and more preferably from 8 ° to u ° C. The reaction time is generally selected from 10 minutes The range is from 72 to 72 hours, preferably from ^ minutes to 48 hours, and more preferably from i hours to 6 hours. Then, the obtained trivalent hexabud n-_metallized iridium complex represented by the formula (V) is obtained. The post-treatment, isolation, and purification as described in the schematic diagram i are performed to provide a linko substance. The method of the present invention is characterized by using a monovalent iridium dinuclear complex. Therefore, formula (Π), ⑽), (IV) or ⑺ So the trivalent six-bud positive _ metallized epi-complex can produce a high cross rate, and may not be in the material. II) Trivalent hexabud ortho-metallized dinuclear complex complex intermediates to produce these complexes. The method of the present invention is characterized by the following.) The Xibu step can be reacted in the same reaction tank and the same solvent 2) No complicated operations such as solvent recovery, post-treatment, isolation, and purification are generally required after the synthesis of intermediates.) The physical loss of intermediates caused by what is known in 2) can be minimized. 4 ) For reasons ⑽3), the cost of intermediates and final products can be reduced. The trivalent hexabud n-metal silver complex produced by the method in April is used as a phosphor. 315064 45 200418865 (Example) This The following examples will be described in more detail without intending to limit the present invention. In each case, the volume ratio of the S / S surface solvent to the initial monovalent iridium dinuclear complex weight i is expressed in units of ml / g. φExample 1 Manufacture of bis (IIm) (bis (2-benzylpyridinyl-N, C2,) iridium chloride dimer) was prepared at Schlenk's, equipped with a reflux condenser. ) (1,5-octadiene) iridium osmium chloride dimer (2.0 g, 2% millimolar, 1 s) was placed in the flask, and the inside of the flask was replaced with nitrogen. After successively adding 2-ethoxyethanol (20 ml, s / s: = 10) and 2-phenylpyridine (2.56 ml, ΐ7.88 mmol, 6.0 equivalents), the mixture was placed in a nitrogen atmosphere. The mixture was stirred at reflux (135t :). Immediately after adding the ligand (2-phenylpyridine), the red suspension was turned to yellow-brown, and when the ligand was dissolved by heating, it turned to reddish, and a yellow suspension was obtained after stirring. After stirring for 3 hours, the solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane / methanol = 10/1). After liquid separation on a concentrating column, the obtained yellow solid was recrystallized from hexane / dichloromethane to obtain the title compound (114), 3.06 g, as a yellow powder, with a yield of 95.8%. 46 315064 200418865 ln NMR (500MHz, CD2C12): δ 5 · 8 7 (dd, J = ll, 7 · 8Ηζ, 4H), 6.60 (dt, J = i.2, 7 · 8Ηζ, 4H), 6.79-6.85 (m, 8H), 7.56 (dd, J = 1.3, 7.8Hz, 4H), 7.80 (dt, J = 1.6, 7.8Hz, 4H), 7.94 (df J = 7.8Hz, 4H), 1.25 (dd, J = 0.8, 5.7Hz, 4H). 3ljfe Example 2 Compound (2-1〇) (bis [2- (2,4-difluorobenzyl) pyridinyl-N, C2,] iridium (III) chloride salt di Manufacture of (polymer) In a Schleich flask equipped with a reflux condenser, (1,5-cyclooctadiene) iridium (I) chloride salt dimer (2.0 g, 2.98 mmol) , 1 equivalent) and the inside of the flask was replaced with nitrogen. Successively add 2-ethoxyethanol (20 ml's / s = 10) and 2- (2,4-difluorophenyl) anhydropyridine (3.42 g, 17.88 millimoles' 6 · After 0 eq.), The mixture was stirred under reflux (135 it) under a nitrogen atmosphere. Immediately after adding the ligand (2- (2,4_difluorophenyl) cyclopyridine), the pale red suspension turned gray, and when the ligand was dissolved by heating, it turned dark red. A lemon yellow suspension was obtained. After stirring for 3 hours, the solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel tube chromatography (eluent · dichloromethane / methanol = 10/1). After liquid separation on a concentrating column, the obtained shell-colored solid was recrystallized from hexane / dichloromethane to obtain the title compound 10) ^. 53 g as a yellow-green powder with a yield of 974%. 47 315064 200418865 αΗ NMR (500MHzx CD2C12): δ 5.29 (dd, > 2.5, 9 · 1Ηζ, 4H), 6.38 (ddd, ^ 2 · 5, 9 山 12 · 5Ηζ 4Η), 6.87 (ddd, J = 1.5, 5.8, 7.2Hz, 4Η), 7.87 (ddd, J = 1.5, 5.8, 7.2Ηζ, 4Η), 8.33 (ddd, J = 0.7, 1.5, 8.1Hz, 4Η), 9.12 ( ddd, J = 0.7, i.5a 5.8Hzr 4H). The compound (2-9) (bis [2_ (4_methylphenyl) hexyl group_chloride monopolymer) is manufactured on a reflux condenser A Schleich flask was charged with (i, 5-cyclodiluted) silver sulfonium chloride dimer (500 mg, 0.744 mmol, "equivalent). ^ The inside of the flask was replaced with nitrogen. After successively adding 2-ethoxyethanol (5 mmol, 'Γ〇 =! ^ 2- (4-methylphenyl) D specific bite (504 mg, 2 · 976 mmol 4.0 · ®), Stir and mix under reflux (135t) in a nitrogen environment. ◎ Add the ^ site (2- (4-methylphenyl) Hou. Fixed) immediately after the light red suspended ', brown, although the ligand is dissolved by heating Turn to dark red, Block :: After! To a yellow precipitate. After stirring for 3 hours, remove the solvent from the anti: substance under reduced pressure, and the residue is purified by silica gel column chromatography (washing station_main milk Mw methanol = 100/1 to 20 / 〇. After liquid separation in the concentration column, the color compound was recrystallized from hexane / dichloromethane to obtain the title compound ~) 34 g was yellow powder. Recrystallized The mother liquor was taken in the same way and reprocessed outside the celebrity, and the daily product was 60 * g. Total yield: 794 mg (94.6%) 〇48 315064 200418865 Chemical NMR (500MHz, CD2C12): δ 1.96 (s , 12H), 5.66 (d, J = 0.7HZ / 4H), 6.61 — 6.64 (ία, 4H) f 6.77 (ddd, J = 1.5, 5.7, 7.4Hzf 4H) f 7.44 (df J = 7.8Hz, 4H) f 7.75 (ddd, J = 1.5, 7.4, 8.1Hz, 4H), 7-87 (ddd, J = 0.7, 1.5 , 8.1Hz, 4H), 9-19 (ddd, J = 0.7, 1.5, 5,7Hz, 4H). Example 4 Compound (2-12) (bis [2- (4-methoxyoxyphenyl)- Manufacture of 5v trifluoromethyl 0-based ingot base · N5C2 '] iridium (III) chloride salt dimer) Put in (i, 5-cyclooctadiene) in a Schleich flask equipped with a reflux condenser Iridium phosphonium chloride dimer (200 mg, 0.298 mmol, equivalent) and 2- (4-fluorenylphenyl) -5-trifluoromethyl D specific bite (302 mg, 1192 mmol) Ear, 4.0 equivalents), and the inside of the flask was replaced with nitrogen. After adding 2 • ethoxyethanol (5 ml, s / s = 10), the mixture was stirred under reflux (135 t :) under a nitrogen atmosphere. The ligand was added (2- (4-Methoxybenzyltrifluoropyridylpyridine)) and the pale red suspension obtained after dissolving by heating gives a bright * color / melon after mixing. After stirring for 3 hours, the pressure is reduced. The solvent was distilled off from the reaction mixture, and the residue was purified by silica gel column chromatography (eluent: dichloromethane / formamidine -100/0 to 100/1). After concentrating the tube, the resulting orange was separated The solid was recrystallized from hexane / dichloromethane to give the title compound (2_) 2) 394 mg Bright yellow powder, yield 90.3%. 2H NMR (500MHzn CD2C12): δ 49 315064 200418865 3.40 (S / 12H), 5.22 (d, J = 2.5Hz, 4H), 6.49 (dd, J = 2.5, 8.6Hz , 4H), 7.58 (d, J = 8.6Hz, 4H), 7.90-7.95 (m, 8H), 9.57 (s, 4H). Example 5 Compound (bis (2-phenylpyridinyl-N, c2 ') Manufacturing of iridium (III) acetamidinium acetone salt) Q (1) Put a (1,5-cyclooctadiene) iridium phosphonium chloride dimer in a Schleich flask equipped with a reflux condenser (500 mg, 0.744 mmol, 1 equivalent) and the inside of the flask was replaced with nitrogen. After successively adding 2-ethoxyethanol (5 ml, s / s = 10) and 2-phenylpyridine (468 µl, 3.274 mmol, 4.4 equivalents), the mixture was refluxed under a nitrogen atmosphere (135 ° C) The mixture was stirred for 3 hours. The resulting yellow suspension was cooled to room temperature, and then acetone (2) 0 µl, 2.232 mmol, 3.0 eq.) And sodium carbonate (237 mg, 2.232 emoll, 30 eq.) Were successively added. It was added thereto, and then refluxed for another 2 hours to obtain a redundant kappa color% floater. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane). After liquid separation in a concentrating column, 720 mg of the title compound (III-i) was obtained as recrystallized from hexane / dichloromethane, and the yield was 80.7%. 50 315064 200418865 XH NMR (500MHzn CD2C12): δ 1 · 79 (s, 6H), 5.23 (s, lH), 6.23 (dd, 7 · 3Ηζ, 2H), 6.68 (^, ^ = 1.3, 7.3Hz , 2H), 6.84 (ddd, J = 1.2, 7.3, 7.7Hz, 2H), 7.19 (ddd, J = 1.6, 5 · 7, 7 · 5Ηζ, 2H), 7.57 (dd, J = 1.3 , 7 · 7Ηζ, 2H), 7.77 (ddd, J = 1.6, 7 · 5, 8 · 2Ηζ, 2H), 7.88 (ddd, J = 0.8, 1.6, 8.2Hz / 2H), 8.49 (ddd, J = 0.8, 1.6, 5.7Hz, 2H). (2) Perform the same operation on a large scale. The reaction used (1,5-cyclooctadiene) iridium osmium chloride salt dimer (5.00 g, 7.44 mmol, 1.0 equivalent), 2-phenylpyridine (4.7 ml, 32.74 mmol, 4 · 4 equivalents), acetoacetone (2.3 ml, 22.32 millimoles, 3.0 equivalents), sodium carbonate (2 37 grams, 22.32 house mole '3.0 equivalents), and 2-ethoxyethanol ( 50 ml, s / s = 10) was used as a starting material to obtain 803 g of the title compound (Hi) in a yield of 900%. The appearance, physical properties and spectral data of the product were the same as those in Example 5 (丨). Since the yield of Example 5 (1) is 80.7%, it can be seen that the method of the present invention is suitable for large-scale production. Example 6 Production of Compound (3-10) (Bis (2- (24--ϋ Dream 0.8, V, 4 Yiranbenzyl) stilbenyl) Iridium (ΠΙ) Ethyl acetone salt) A Schleich flask equipped with a reflux condenser was charged with (I, 5-cyclooctadiene) iridium (I) chloride salt dimer (500 mg, 0% "Mole, Gong 315064 51 Gu 2. The inside of the bottle was replaced with nitrogen. 2-Ethoxyethanol (5 strokes's / s = i0, ^ 0 j "" _ (5-diphenyl) phenyl) (626 mg, 3.274) Milli-Ears' 4.4 When I, you jl ^ ^)) under a nitrogen atmosphere reflux (135t :), stir and mix before cooling the cup of lemon yellow suspension to room temperature, and then, Ethyl acetone (230 π j (Chuanxiong liter, 2.232 millimoles, jo equivalent sodium carbonate (237 g, 2 23 wood ^ ^ ^ ^ ^ ^ Mao Tang, 3.0 pang)) Among them, and then refluxed for another 2 hours to obtain the general color-卞 /, 巳 suspension liquid. The residue was purified from Shixi gel column chromatography under reduced pressure (eluent: dichloromethane). ，） / 辰 '、, couple & column The title was recrystallized from alkane / dichloromethane. The product (3 10) 8 96 g was a lemon yellow powder with a yield of 97.9%. H NMR (500MHzn CD2C12): ζ Worker Shoulder 6Η), 5.31 (s, 1Η), 55〇⑽, μ ″, 8., π), 6.38 (ddd, J = 2.4, 93, κι, 2η), 7 · 24 (_ 'J = 1 · 5, 5.7, 7.3Ηζ, 2Η ), (ddt, J- ^ 0.6, 1.6, 7.3Ηζ, 2Η), 8.22-8.28 (m, 2Η), (ddd, > 0 · 8, u, 5. · 7Ηζ, 2η) · U) The scale is the same. The reaction uses (1,5-cyclooctadiene) iridium osmium gas salt dimer (5.0 g, 7.44 millimoles, 10 equivalents), 2_ (2,4 one mouse Phenyl) pyridine (6.00 grams, 32.74 millimoles, 4; 2 equivalents), acetamidine (2.3 pen liters, 22.32 millimoles, 3.0 equivalents), sodium carbonate (2.37 grams, 22.32耄 Mor, 3.0 equivalents) and 2-ethoxyethanol (50 ml, s / s = 10) as starting materials to obtain the title compound (3_1〇) 8.53 g as a lemon yellow powder as the first product And 0.57 g of yellow powder with a purity of 95.5% is the second product. The total yield is 90.5¼. The product's appearance, physical properties and spectral data are 52 315064 200418865, which are all the same as in Example 6 (1). Same. Since Example 6 (1) The yield was 78.9%, the known method of the present invention suitable for large scale manufacture. Production of compound (3-9) (bis [2- (4-fluorenylphenyl) sulfonyl-N, cniridium (111) acetamidinone)) in a Schleich flask equipped with a reflux condenser A (1,5-cyclooctadiene) iridium (I) gas salt dimer (500 mg, 0.744 mmol, i equivalent) was placed in the flask, and the inside of the flask was replaced with nitrogen. After successively adding 2-ethoxyethanol (5 ml 'S / S = 10) and 2- (t-methylphenyl) orbitalidine (504 mg, 2.976 mmoles' 4.0 equivalents), in a nitrogen atmosphere (135Ct) The mixture was stirred for hr. The yellow suspension was cooled to room temperature, and then ethylacetone (230 μl, 2.232 mmol, 3.0 equivalents) and sodium carbonate (237 mg, 2 2 3 2 ΐ · w 续) were successively added. , 旲 耳, 3.0 equivalents), and then stir for 3 hours to get steam "Tajimado" 県, 糸, Heng, and Zuo Xin Ye. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by chromatography (h2, ") (eluent: dichloromethane). After the liquid was concentrated in the column, the title compound (3-9) 7 3 6 mg was obtained from hexane, ρ & From the recrystallization mother liquor, a recrystallized crystal (27 mmol, + a) was obtained in the same manner as the extra product. Total yield: 763 mg (81.7%). 315064 53 200418865 XH NMR (500MHzn CD2C12): δ 1.78 (s, 6H), 2.06 (s, 6H), 5.26 (s, 1H), 6.04 (s, 2H), 6.67 (d , J = 7.9Hz, 2H), 7.14 (ddd, 5 · 8, 7.2Hz, 2H), 7.46 (d, J = 7.9Hz, 2H), 7.74 (ddd, J = 1.6, 7 · 2 , 8 · 3Η2, 2H), 7.82 (ddd, J = 0.8, 1.6, 8 · 3Ηζ, 2H), 8.45 (ddd, J = 0.8, 1.6, 5.8Hz, 2H), Example 8 Compound ( 3-11) (bis [2- (4-methoxyphenyl) -5-trifluoroamidinopyridinyl-N, C2 '] iridium (III) acetamidoacetone) A Schleich flask of a condenser was charged with (1,5 · cyclooctadiene) iridium osmium chloride dimer (500 mg, 0.744 mmol, 1 equivalent) and 2- (4-fluorenoxybenzene ) -5_trifluorofluorenylpyridine (754 mg, 2.976 millimoles' 4.0 equivalents), and the inside of the flask was replaced with nitrogen. After the addition of 2-ethoxyethane (5: 1 liter, s / s = 10), the mixture was stirred under reflux (135.0) under a nitrogen atmosphere, and the mixture was successively mixed with carbonic acid, and then the oxane was distilled off. The alkane re-crystallizes the product of the mother hour. The resulting withered yellow suspension was cooled to room, and ethylacetoacetone (230 microliters, 2.232 millimoles, 30 equivalents) sodium (237 mg, 2.232 millimoles, 30 equivalents) was added thereto, Search for 3 hours to obtain an orange suspension. The solvent was mixed from the reaction under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloro concentration column separation. The obtained orange solid was obtained from hexane / dichloroformite to obtain the title compound (3 -11) 920 mg is a light-colored powder. An additional total yield of recrystallized crystalline milligram (mg) obtained from the re-liquid in the same way: 980 pens (82. 8%). 315064 54 200418865 1H NMR (500MHzn CD2C12): δ 1.82 (s, 6H), 3.54 (s, 6H), 5.33 (s, 1H), 5.71 (d, J = 2.5Hz, 2H), 6.51 (dd, J = 2.5, 8 · 7Ηζ, 2H), 7.60 (d, J = 8.7Hz, 2H), 8.67 (d, J == 2.2Hz, 2H). Example 9 Compound (3-7) (double [ Manufacture of 2- (2, -benzothienyl) pyrene-N, C3 '] iridium (HI) acetamidine & acetone salt) (1) In a Schleich flask equipped with a reflux condenser Place (1,5-looxacin dilute) silver (1) gas salt dimer (500 mg, 0.744 mmol, 1 field) and 2- (2, benzothienyl) roar bite (629 mg , 2.976 millimoles, 4.0 equivalents), and the inside of the flask was replaced with nitrogen. After adding 2-ethoxyethanol (5 5 | wool, s / s == 10), the mixture was stirred under reflux (135 ° C) in a nitrogen environment to add a solvent, and the resulting pale red suspension was heated to turn into Dark red, liquid and stirred to get a reddish brown precipitate. The resulting vermilion suspension was two-folded to room temperature, and then acetoacetone (230 microliters, 2.232 ′ ears 3.0 °) and sodium carbonate (237 mg, 2.232 millimoles, 30%, and then 3 hours. The residue was purified from Shixi gel column chromatography (eluent ·· dichloro, 兀) under reduced pressure from the syringium and yttrium residues. ≫ After the column was separated for separation The obtained solid was colored hexane / di " Fan Zai, Ό " Fan Zai, Ό crystals to obtain the title compound (3-7) 743 Gu i & a, yield 70.]%. 315064 55 200418865 NMR (500MHzn CD2C12): § 1-81 (s, 6H), 5.35 (s, 1H), 6.18 (d, ^ 8.2Ηζ, 2H), 6.83 (ddd, Sheshan 7.2, 8.2HZ, 2H) , 7〇5_7ii ㈨ 4h), 7.62-7.68 (m, 4H), 7.82 (ddd, J = 1.5, 7.5, 8.1Hz, 2H), 8-45 (ddd, J = 0-8, i.5 / 5.7 Hz, 2H). (2) Perform the same operation for large scale. The reaction used (i, 5-cyclooctadiene) iridium (I) chloride salt dimer (3.29 g, 4.90 mmol, 10 equivalents), 2 (2, _ benzothienyl) pyridine (4.35 G, 20.59 millimoles, 42 equivalents), acetone acetate (1.5 liters, 14.70 millimoles, 3.0 equivalents), sodium carbonate (156 grams of 14.70 moles, 3.0 equivalents) and 2-B Oxyethanol (⑴ml, 仏 = ⑺) was used as starting material to obtain 5.23 g of the title compound (3_7) as the first product of light reddish brown powder, and 17 g of additional light reddish brown powder as the second product. The total yield was 77.4%. The product shape, physical properties and spectral data were all the same as those in Example 9 (1). Since the yield of Example 9 (1) | 70.1%, it can be seen that the method of the present invention is suitable for large-scale production. Example 10

Manufacture of compound (4-2) (bis [2_ (2, cardiodifluorophenyl) pyridinyl_N, C pyridine salt)-Place in a Schleich flask equipped with a reflux condenser (ι , 5-Cyclo'sin) silver phosphonium chloride monopolymer (500 mg, 0.744 mmol, ^ equivalent) and the inside of the flask was replaced with nitrogen. ▲ Ί Ί 卜 '' Bu '罝 谀 罝 谀 Add ethoxy ethanol (5 ml' s / s-1〇) and 2_ (2,4_difluorophenyl) Oh bite (626 mg, gw imo 315064) 56 200418865 Ear '4: Equivalent' Stir the mixture under reflux (135t) in a nitrogen atmosphere 3 λ! 4 The beech lemon yellow suspension was cooled to room temperature sodium pyridinium (324 mg, 2.232 millimoles, 3.0 animal) Add to it, and then simmer for 3 hours under reflux. With the progress of the reaction, the feed liquid slowly turns to a plate color. The solvent is distilled off from the reaction mixture under reduced pressure, and the residue is purified by Shixi gel column chromatography (washing Extraction solution: dichloromethane / methanol = 20/1). After liquid separation in a concentrated column, the obtained yellow solid was recrystallized from hexane / methylene chloride to obtain 967 mg of the title compound (4-2) as a lemon yellow powder. Yield, 93.6%. 1H NMR (500MHzn CD2C12): δ 5.62 (dd, J = 2.4, 8.7HZ / 1H), 5.85 (dd, J = 2.4, 8.7Hz, 1H), 6.44 (ddd, j = 2.4, 9.2, 12.6Hz, 1H), 6.50 (ddd, j ^ .4, 9.2f 12.6Hz, 1H), 7.02 (ddd, 5.9f 7.4Hz, 1H), 7.21 (ddd, j = i.5, 5.9 / 7 4Ηζ, iH), 7.40 (ddd, 5.4, 7.6Hz, lH), 7.46 (ddd, J = 0.8, 1.6, 5.9 Hz, 1H), 7.75-7.86 (in, 3H), 7.94 (dt, J = 1.5, 7.6Hz; 1H), 8.20-8.28 (ΙΠΛ2Η), 8.28-8.37 (πι, 1H), 8.69 (ddd, J = 〇.7, 1.6f 5.9Hzf 1H). Example 1 1 Compound (Vm) (see (2-phenylpyridinyl_N, C2 :) iridium (m)) is manufactured in the history of equipped with reflux condenser (1,5-cyclooctane-diluted) tritium salt dimer (500 mg, 0.744 mmol,] equivalent) was placed in a Lek flask, and the inside of the flask was replaced with nitrogen. Add 2 successively -After ethoxyethanol (5 ml, s / S = 10) and 2-phenylpyridine (46 s microliter, 3.274 millimoles, 4.4 when placed) 'under reflux under nitrogen (1 3 5 (:) The mixture was stirred for 3 hours. The resulting yellow suspension was cooled to room temperature, and silver (1) trifluoromethanesulfonate (573 mg, 2,232 mmol, 3.0 equivalents) was added thereto, and then again Stir at room temperature for 10 minutes to obtain a dark brown suspension. Add an additional amount of 2_ ethoxyethanol (7 mL, s / s = 14), add 2-phenylpyridine (638 μl, 4.464 mmol, 6.0 equivalents) dropwise, and stir under reflux The mixture was allowed to stand for 3 hours to give a tan suspension. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane). After the liquid was concentrated on the column, the obtained yellow solid was recrystallized from hexane / dichloromethane to obtain 837 mg of the title compound (V_i) as a yellow powder with a yield of 8 5.9%. αΗ NMR (50 0MHzn CD2C12): δ 6.72-6.81 (m / 6H), 6.85-6.93 (m, 6H), 7.56 (ddd, J = 0.8, 1.6, 5.5Hz, 3H), 7.62-7.69 (m , 6H), 7.89-7 · 94 (m, 3H). Example 1 2 The compound ^ 乂 参 参 ^ ethyl anion difluorophenyl sulfonium base based on the process ^ iridium ⑴… in the history of equipped with a reflux condenser A Lek flask was charged with (1,5-cyclooctadiene) silver hafnium dimer (500 mg, 0.744 mmol, 1 equivalent), and the inside of the flask was replaced with nitrogen. Successively add 2-ethoxyethanol (5 mmol 58 315064 2004 18865 liters, s / s = 10) and 2_ (2,4_difluorophenyl) pyridine (626 mg, 3274 mmoles' 4 · 4 equivalents ) 'Under reflux in a nitrogen environment (135. 0 3% of the mixture was decanted. The resulting yellow-green suspension was cooled to room temperature, and silver (1) trifluoromethanesulfonate (573 mg, 2 232 mmol) Ear, 30 equivalents) was added to it, and then agitated under reflux for 1G minutes to obtain a dark brown suspension, resulting in a brown precipitate. An additional amount of 2-ethoxyethanol (8.5 ml, s / s) was added. = i7), and then add 2_ (2,4 • diphenyl) to the bite ratio (853 mg, 4 milli-ears '6.0 one equivalent)' by dripping, and then administer the mixture under reflux for 3 hours. Kappa brown heart sweat was obtained. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by Shixi gel column chromatography (eluent: dichloromethane). After the concentration of the column, the resulting solution was yellow-green The solid was recrystallized from hexane / methylene chloride to obtain 983 mg of the title compound (5-6) as a yellow-green powder with a yield of 866%.

aH NMR (50 MHz MHz CD2C12): δ 6.23 (dd, c: Q • ^ 9.2Hz, 3H), 6.41 (ddd, J = 2.5 / 9.2, 13.1Hz, 3H), 6.97 (ddd, α,! .3 / 5.6, 7.2Hz, 3H), 7.50 (ddd, ㈣8, u, 5.6Ηζ, 3h), 7.70-m (m, 3h), m34 (m, 3h) 1 3 oxybenzyl) stilbyl cr] silver (In)) · compound (5-7) (see [2- ('manufactured in a Schleich flask equipped with a reflux condenser, (1, 5. · octadiene) silver phosphonium chloride salt-polymer (2 mg, 0 ·]% millimolar, 1 杳 j 3 J 5064 59 200418865 and 2- (4-methoxyphenyl) hexidine (222 mg , 1311 millimoles, 4.4 equivalents), and the inside of the flask was replaced with nitrogen. After adding 2-ethoxyethanol (2 ml, s / s = 10), the mixture was refluxed under a nitrogen atmosphere (135.0 stirring). The mixture was allowed to cool for 3 hours. The resulting yellow suspension was cooled to room temperature, and silver (1) trifluoromethanesulfonate (230 mg, 0.894 mmol, 3.0 equivalents) was added thereto, followed by stirring under reflux for 1 hour. A brown precipitate was obtained in 0 minutes. An additional amount of 2-ethoxyethanol (2 ml, s / s = 10) was added followed by 2- (cardimethoxymethoxybenzyl) pyridine (252 mg, 1490 mmol). Ear, 5.0 equivalent), and then the mixture was stirred under reflux for 3 hours. The solvent was distilled off from the reaction mixture under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: dichloromethane). Concentrated After column separation, the obtained lemon yellow solid was recrystallized from hexane / dichloromethane to obtain the title compound (5-7) 3. 16 mg was a yellow-green powder with a yield of 761%. 2H NMR (500HHzn CD2C12): δ 3.55 (s, 9H) / 6.31 (d, J = 2.7HZ / 3H), 6.46 (dd, j = 2/7, 8.6Hz, 3H), 6.83 (ddd, J = 1.3, 5.6, 7.2Hz, 3H) f 7.58 (ddd, J = 1.6, 7.2, 8.3Hz, 3H), 7.60 (d, J = 8.6Hz, 3H), 7-78 (ddd, J = 0.8, 1.3, 8.3 · ζ, 3H) · Example 14 Two-step production of compound (vi) (refer to (2: phenylpyridinyl_N, c2,) iridium (III)) Put the compound produced in Example 1 in a Schleich flask ( π_i) (bis (2-phenylpyridinyl · N, Cr) iridium (III) gas salt dimer) (200 mg, 0.187 mmol, 1 equivalent) and silver trifluoromethanesulfonate Tritium (144 mmol 315064 60 200418865 g, 0.561 mmol, 3.0 equivalents), and the inside of the flask was replaced with nitrogen. After adding 2-ethoxyacetic acid (1 liter's / s = 5) and 2-phenyl D specific bite (163 μl 1 · 1 2 2 mol, 6 · 0 equivalent), under reflux (13 5 ° C) for 3 hours. The resulting yellow-brown suspension was concentrated, and the residue was purified by column chromatography (eluent: dichloroamidine;): end). After the liquid was concentrated on the column, the solution was recrystallized from hexane / dichloromethane to obtain the title compound (V-i) 208 mg as a yellow powder with a yield of 83.4¾. The NMR data of the product were the same as in Example 11. The total yield from Example 1 was 79.9%. When this step was performed in a single tank, the total yield of Example 11 was 85.9% (refer to Example n). It has been shown that the method according to the invention is advantageously carried out in a single tank. Comparative Example 1 Compound (5-6) was produced according to the method described in wo 02/02714 (Patent Document # 1) (see [2- (2,4-difluorophenyl residue intyl_n, c6,] silver文 One, two, and two mills were placed in a foreigner's flask of the social culture; Zumi, 1.42 millimoles, 1 equivalent), a toilet factory, silver dimethymethanesulfonate (1) (1.09 g, 4.26 millimoles, 3 · 0 equivalent), and the plant was red and the inside of the bottle was replaced with nitrogen. Add 2- (2, heart-rat base) Mouth fixed (2 bucket / 〇Λ. Mao Sheng 'S / S == 4) After mixing with water (1 ml, s / s = 2), heat the mixture # 八 物 in a 200 C oil bath and wish to stir for 3 hours. The resulting black mixture was dried to dryness, and the residue? ^^ Jin, Erxi Take g 桎 chromatographic purification (eluent: dichloro hydrazone). After concentrating the column for liquid separation, the outsider 仏 / c tianji 垸 / dichloromethane is recrystallized to obtain the title compound (5-6) 5 71 mg ^ NMP ^, H 4 color powder, yield 52.7%. The NMR data of the product is the same as in Example 12. 315064 61 200418865 According to the method of the present invention, a variety of trivalent six buds can be effectively provided in the traditional manner. Metalized iridium complexes, and these complexes As the material for the element of the excitation light. 62315064

Claims (1)

200418865 The scope of patent application: 1. A method for producing a trivalent hexabud n-metallized iridium complex, which uses the iridium complex and a coordination compound as starting materials, including the use of the following formula (I) The monovalent iridium dinuclear complex shown is used as the starting material: (Where A represents a non-conjugated diene compound; and X represents a halogen atom). 2. The manufacturing method according to item 1 of the scope of patent application, wherein the trivalent hexabud n-metallized iridium complex is a compound represented by the following formula (II), (III), (IV) or (V) ... (II) (IV) 63 315064 200418865 (Where ring B represents an optionally substituted aryl or heteroaryl group; ring C represents an optionally substituted nitrogen-containing aryl group; ring D represents an optionally substituted pyridyl group; ring B and ring C may form a thick Rings; X represents a halogen atom; R1 and R3 each independently represent an alkyl group, alkoxy group, aryl group, or heteroaryl group; R2 represents a hydrogen atom, alkyl group, aryl group, or heteroaryl group; R] and R2 or R2 and R3 can form a ring with adjacent carbon atoms). 3. —Manufacturing method of trivalent hexabud n-metallated iridium complex shown by formula (II): (Where ring B represents an optionally substituted aryl or heteroaryl group; ring C represents an optionally substituted nitrogen-containing aryl group; ring B and the ring (: can form a fused ring with each other; and X represents a halogen atom) the The method includes a monovalent iridium dinuclear complex represented by formula (I): 64 315064 200418865 (Where A represents a non-co-I dilute compound, and X represents a halogen atom) reacting with a compound represented by formula (VI): (Where ring B represents an optionally substituted aryl or heteroaryl group; ring c represents an optionally substituted nitrogen-containing aryl group; ring B and ring c may form a fused ring with each other). 4. A method for producing a trivalent hexabud n-metallized iridium complex shown by formula (ΠΙ): (Where ring B represents an optionally substituted aryl or heteroaryl group; ring c represents an optionally substituted nitrogen-containing aryl group; ring B and ring c may form a ring with each other; Ri and V each independently surface alkyl group , ⑥oxy, aryl or hetero: radical; R 2 represents a hydrogen atom, a radical, an aryl or a heteroaryl; R, and R 2 or ^ and R 3 may form a ring together with an adjacent carbon atom) 3 ^ 5〇64 65 〇〇418865 This method includes changing the monovalent iridium dinuclear complex of formula (I): (Where A represents a non-conjugated diene compound; and X represents a prime atom) After the reaction of the compound represented by formula (VI): (Where ring B represents a substituted aryl or heteroaryl group; ring c represents a substituted nitrogen-containing aryl group; 'ring B and ring C may form a fused ring with each other), and then with formula (VII) Compound reaction: 〇〇 (VII) (where R] and R3 each independently represent alkyl, alkoxy, aryl or heteroaryl; R2 represents a hydrogen atom, alkyl, aryl or heteroaryl; R1 and R2 Or R2 and R3 may form a ring together with adjacent carbon atoms). • 5. The manufacturing method according to item 4 of the scope of patent application, which comprises, in a single sample, ^ reacting the monovalent iridium dinuclear complex represented by formula ⑴ with an eighth compound represented by formula (VI), and then reacting with The compound represented by the formula (VII) is reacted. 3] 5064 66 200418865 6 · —Manufacturing method of trivalent hexabud n-metallized iridium complex shown by formula (IV): "2 (where ring B represents an optionally substituted aryl or heteroaryl group; ring C represents an optionally substituted nitrogen-containing aryl group; ring D represents an optionally substituted amidinyl group; and ring B and ring C These can form fused rings with each other.) This method includes converting a monovalent iridium dinuclear complex of formula (I): (Wherein A represents a non-conjugated diene compound; and X represents a halogen atom) After reacting with a compound represented by formula (VI): (Where ring B represents an optionally substituted aryl or heteroaryl group; ring C represents an optionally substituted nitrogen-containing aryl group; ring B and ring C may form a fused ring with each other), and then with formula (VIII) Indicative compound reaction: 67 315064 200418865 (Where ring D represents optionally substituted pyridyl). 7. The manufacturing method according to item 6 of the scope of patent application, which comprises reacting a monovalent iridium dinuclear complex represented by the formula (I) with a compound represented by the formula (VI) in a single tank, and then reacting with the formula ( VIII) The compounds shown are reacted. 8. —Manufacturing method of trivalent hexabud n-metallated iridium complex shown by formula (V): (Where ring B represents an optionally substituted aryl or heteroaryl group; ring C represents an optionally substituted nitrogen-containing aryl group; and ring B and ring C may form a condensed ring with each other) The method includes combining formula (I The monovalent iridium dinuclear complex shown by): (Wherein A represents a non-conjugated diene compound; and X represents a halogen atom) After reacting with a compound represented by formula (VI): 68 315064 200418865 (Where ring B represents an optionally substituted aryl or heteroaryl group; ring C represents an optionally substituted nitrogen-containing aryl group; and ring B and ring C may form a fused ring with each other), and then with a silver salt and formula (VI) The compound shown is reacted. 9. The manufacturing method according to item 8 of the scope of patent application, which comprises reacting a monovalent iridium dinuclear complex represented by formula (I) with a compound represented by formula (VI) in a single tank, and then with a silver salt. And a compound represented by formula (VI). 69 315064 200418865 柒. Designated Representative Map: There is no schema in this case (I) The designated representative map in this case is: (). (2) Brief description of the component representative symbols of this representative map: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: (II) -2 4 3] 5064