High-molecular compound and light-emitting element using same
09853218 · 2017-12-26
Assignee
Inventors
Cpc classification
C08G61/122
CHEMISTRY; METALLURGY
C09K2211/1059
CHEMISTRY; METALLURGY
H10K85/111
ELECTRICITY
C08G2261/3142
CHEMISTRY; METALLURGY
C09K2211/185
CHEMISTRY; METALLURGY
C08G61/10
CHEMISTRY; METALLURGY
C08G2261/312
CHEMISTRY; METALLURGY
C09K11/025
CHEMISTRY; METALLURGY
H05B33/20
ELECTRICITY
International classification
B32B9/00
PERFORMING OPERATIONS; TRANSPORTING
B32B19/00
PERFORMING OPERATIONS; TRANSPORTING
H05B33/20
ELECTRICITY
C08G61/10
CHEMISTRY; METALLURGY
C09K11/02
CHEMISTRY; METALLURGY
Abstract
A polymer compound has a repeating unit represented by general formula (1): ##STR00001##
wherein R.sup.1a represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, each possibly substituted and the same or different; and X.sup.1a represents a group selected from formulae (1a) to (1c).] ##STR00002##
wherein R.sup.1c represents an aryl group or a monovalent aromatic heterocyclic group, possibly substituted; and R.sup.1d to R.sup.1f represent each independently an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group, an aryloxy group, an aralkyl group, an arylalkoxy group, a substituted amino group, a substituted carbonyl group, a substituted carboxyl group, a fluorine atom or a cyano group; and the pairs R.sup.1d and R.sup.1e, R.sup.1f and R.sup.1g, R.sup.1d and R.sup.1f, and R.sup.1e and R.sup.1g may be mutually linked to form a ring together with a carbon atom to which they are linked.
Claims
1. A polymer compound comprising a group represented by the following general formula (1) as a repeating unit: ##STR00162## in the formula (1), R.sup.1a represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and each of these groups is optionally substituted with a substituent, a plurality of R.sup.1a can be the same or different, X.sup.1a represents a group selected from the group consisting of the following formulae (1a) to (1c): ##STR00163## in the formulae (1a) to (1c), R.sup.1c represents an aryl group or a monovalent aromatic heterocyclic group, and each of these groups is optionally substituted with a substituent, R.sup.1d to R.sup.1f represent each independently an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group, an aryloxy group, an aralkyl group, an arylalkoxy group, a substituted amino group, a substituted carbonyl group, a substituted carboxyl group, a fluorine atom or a cyano group, in the formula (1b), R.sup.1d and R.sup.1e can be mutually linked to form a ring together with a carbon atom to which they are linked, and in the formula (1c), R.sup.1d and R.sup.1e can be mutually linked to form a ring together with a carbon atom to which they are linked, R.sup.1f and R.sup.1g can be mutually linked to form a ring together with a carbon atom to which they are linked, R.sup.1d and R.sup.1f can be mutually linked to form a ring together with a carbon atom to which they are linked, and R.sup.1e and R.sup.1g can be mutually linked to form a ring together with a carbon atom to which they are linked.
2. The polymer compound according to claim 1, wherein the group represented by said general formula (1) is a group represented by the following general formula (1A): ##STR00164## in the formula (1A), R.sup.1a, R.sup.1c and R.sup.1d represent the same meaning as described above.
3. The polymer compound according to claim 1, wherein the group represented by said R.sup.1c is an aryl group.
4. The polymer compound according to claim 1, further comprising as a repeating unit at least one group selected from the group consisting of groups represented by the following general formulae (2) and (3): ##STR00165## in the formula (2), Ar.sup.2a represents an arylene group, a divalent aromatic heterocyclic group, or a divalent group obtained by mutually linking 2 to 10 groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group, and each of these groups is optionally substituted with a substituent, wherein in the group represented by the formula (2), at least one of carbon atoms adjacent to a carbon atom forming a bond to the other repeating unit has an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group as a substituent, the group represented by the formula (2) is different from the group represented by the formula (1): ##STR00166## in the formula (3), Ar.sup.3a represents an arylene group, a divalent aromatic heterocyclic group, or a divalent group obtained by mutually linking 2 to 10 groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group, and each of these groups is optionally substituted with a substituent, wherein the group represented by the formula (3) is different from the group represented by formula (1) and the group represented by formula (2).
5. The polymer compound according to claim 4, wherein the group represented by general formula (2) is a group represented by the following general formula (2A): ##STR00167## in the formula (2A), R.sup.2a represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and each of these groups is optionally substituted with a substituent, and a plurality of R.sup.2a can be the same or different, R.sup.2b represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and each of these groups is optionally substituted with a substituent, and a plurality of R.sup.2b can be the same or different.
6. The polymer compound according to claim 4, wherein the group represented by general formula (2) is a group represented by the following general formula (2B): ##STR00168## in the formula (2B), Y.sup.2 represents a carbon atom or a nitrogen atom, and the carbon atom is optionally substituted with an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and a plurality of Y.sup.2 can be the same or different, R.sup.2c represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and each of these groups is optionally substituted with a substituent, and a plurality of R.sup.2c can be the same or different, R.sup.2d represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and each of these groups is optionally substituted with a substituent, and a plurality of R.sup.2d can be the same or different, Ar.sup.2 represents an aryl group or a monovalent aromatic heterocyclic group, and each of these groups is optionally substituted with a substituent.
7. The polymer compound according to claim 4, wherein the group represented by general formula (3) is a group represented by the following general formula (3A): ##STR00169## in the formula (3A), Y.sup.3 represents a carbon atom or a nitrogen atom, and the carbon atom is optionally substituted with an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and a plurality of Y.sup.3 can be the same or different, Ar.sup.3 represents an aryl group or a monovalent aromatic heterocyclic group, and each of these groups is optionally substituted with a substituent.
8. The polymer compound according to claim 4, wherein the group represented by general formula (3) is a group represented by the following general formula (3B): ##STR00170## in the formula (3B), n.sup.3B represents an integer of 1 to 3, Ar.sup.3B represents an arylene group or a divalent aromatic heterocyclic group, and each of these groups is optionally substituted with a substituent, and when there is a plurality of Ar.sup.3B, these can be the same or different, R.sup.3B represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and each of these groups is optionally substituted with a substituent, and a plurality of R.sup.3B can be the same or different.
9. The polymer compound according to claim 4, wherein the content of the groups represented by formula (3) is 0.1 mol % or more and 50 mol % or less with respect to the total content of repeating units contained in the polymer compound and the groups represented by formula (3) are not mutually substantially adjacent.
10. A composition comprising the polymer compound according to claim 1 and at least one material selected from the group consisting of a hole transporting material, an electron transporting material and a light emitting material.
11. The composition according to claim 10, wherein said light emitting material is a phosphorescent compound.
12. A composition comprising a polymer compound containing a group represented by the following general formula (1B) as a repeating unit, and a phosphorescent compound represented by the following general formula (Ir-1), (Ir-2) or (Ir-3): ##STR00171## in the formula (1B), R.sup.1a represents an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an aralkyl group, and each of these groups is optionally substituted with a substituent, and a plurality of R.sup.1a can be the same or different, R.sup.1h and R.sup.1d represent each independently an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, an alkoxy group, an aryloxy group, an aralkyl group, an arylalkoxy group, a substituted amino group, a substituted carbonyl group, a substituted carboxyl group, a fluorine atom or a cyano group, and R.sup.1h and R.sup.1d can be mutually linked to form a ring together with a carbon atom to which they are linked: ##STR00172## in the formula (Ir-1), R.sup.D1, R.sup.D2, R.sup.D3, R.sup.D4, R.sup.D5, R.sup.D6, R.sup.D7 and R.sup.D8 represent each independently a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent aromatic heterocyclic group or a halogen atom, and each of these groups is optionally substituted with a substituent, wherein at least one of R.sup.D1 , R.sup.D2, R.sup.D3, R.sup.D4, R.sup.D5, R.sup.D6, R.sup.D7 and R.sup.D8 is a group represented by the following formula (Dend-A) or (Dend-B), -A.sup.D1 - - - A.sup.D2- represents an anionic bidentate ligand, and A.sup.D1 and A.sup.D2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom linking to an iridium atom, n.sub.D1 represents 1, 2 or 3: ##STR00173## in the formula (Ir-2), R.sup.D11, R.sup.D12, R.sup.D13, R.sup.D14, R.sup.D15, R.sup.D16 , R.sup.D17, R.sup.D18, R.sup.D19 and R.sup.D20 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent aromatic heterocyclic group or a halogen atom, and each of these groups is optionally substituted with a substituent, wherein at least one of R.sup.D11, R.sup.D12, R.sup.D13, R.sup.D14, R.sup.D15, R.sup.D 16, R.sup.D17, R.sup.D18, R.sup.D19 and R.sup.D20 is a group represented by the following formula (Dend-A) or (Dend-B), -A.sup.D1 - - - A.sup.D2- represents an anionic bidentate ligand, and A.sup.D1 and A.sup.D2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom linking to an iridium atom, n.sub.D2 represents 1, 2 or 3: ##STR00174## in the formula (Ir-3), R.sup.D1, R.sup.D2, R.sup.D3, R.sup.D4, R.sup.D5, R.sup.D6, R.sup.D7, R.sup.D8, R.sup.D11, R.sup.D12, R.sup.D13, R.sup.D14, R.sup.D15, R.sup.D16, R.sup.D17, R.sup.D18, R.sup.D19 and R.sup.D20 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent aromatic heterocyclic group or a halogen atom, and each of these groups is optionally substituted with a substituent, wherein at least one of R.sup.D1, R.sup.D2, R.sup.D3, R.sup.D4, R.sup.D5, R.sup.D6, R.sup.D7, R.sup.D8, R.sup.D11, R.sup.D12, R.sup.D13, R.sup.D14 R.sup.D15, R.sup.D16, R.sup.D17, R.sup.D18, R.sup.D19 and R.sup.D20 is a group represented by the following formula (Dend-A) or (Dend-B), -A.sup.D1 - - - A.sup.D2- represents an anionic bidentate ligand, and A.sup.D1 and A.sup.D2 each independently represent a carbon atom, an oxygen atom or a nitrogen atom linking to an iridium atom, n.sub.D3 represents 1 or 2: ##STR00175## in the formula (Dend-A), G.sup.DA1 represents a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, Ar.sup.DA1, Ar.sup.DA2 and Ar.sup.DA3 each independently represent an arylene group or a divalent aromatic heterocyclic group, T.sup.DA2 and T.sup.DA3 each independently represent an aryl group or a monovalent aromatic heterocyclic group, m.sup.DA1, m.sup.DA2 and m.sup.DA3 each independently represent an integer of 0 or more: ##STR00176## in the formula (Dend-B), G.sup.DA1, G.sup.DA2 and G.sup.DA3 each independently represent a nitrogen atom, a trivalent aromatic hydrocarbon group or a trivalent aromatic heterocyclic group, Ar.sup.DA1, Ar.sup.DA2, Ar.sup.DA3, Ar.sup.DA4, Ar.sup.DA5, Ar.sup.DA6 and Ar.sup.DA7 each independently represent an arylene group or a divalent aromatic heterocyclic group, T.sup.DA4, T.sup.DA5, T.sup.DA6 and T.sup.DA7 each independently represent an aryl group or a monovalent aromatic heterocyclic group, and m.sup.DA1, m.sup.DA2, m.sup.DA3, m.sup.DA4, m.sup.DA5, m.sup.DA6 and m.sup.DA7 each independently represent an integer of 0 or more.
13. A liquid composition comprising the polymer compound according to claim 1 and a solvent.
14. An organic film comprising the polymer compound according to claim 1.
15. A light emitting device having an anode and a cathode and an organic layer disposed between the anode and the cathode, wherein the organic layer contains the polymer compound according to claim 1.
Description
EXAMPLES
(1) The present invention will be illustrated further in detail by examples below, but the present invention is not limited to the following examples.
(2) [Measurement Method]
(3) In the examples below, measurement of number-average molecular weight and weight-average molecular weight, high performance liquid chromatography (HPLC), measurement of NMR, measurement of LC/MS, measurement of glass transition temperature and measurement of triplet energy were carried out as described below.
(4) (Measurement of Number-Average Molecular Weight and Weight-Average Molecular Weight)
(5) Polystyrene-equivalent number-average molecular weight (Mn) and polystyrene-equivalent weight-average molecular weight (Mw) were determined by GPC (manufactured by Shimadzu. Corp., trade name: LC-10Avp). In this operation, the polymer compound to be measured was dissolved in tetrahydrofuran so as to give a concentration of about 0.05 wt % and the solution was injected in an amount of 10 μL into GPC. Tetrahydrofuran was used as the mobile phase of GPC and allowed to flow at a flow rate of 2.0 ml/min. PLgel MIXED-B (manufactured by Polymer Laboratories Ltd.) was used as the column. As the detector, a UV-VIS detector (manufactured by Shimadzu. Corp., trade name: SPD-10Avp) was used.
(6) (High Performance Liquid Chromatography (HPLC))
(7) The value of HPLC area percentage was used as an index of the purity of a compound. This value is a value at 254 nm by high performance liquid chromatography (HPLC, manufactured by Shimadzu Corp., trade name: LC-20A), unless otherwise stated. In this procedure, the compound to be measured was dissolved in tetrahydrofuran or chloroform so as to give a concentration of 0.01 to 0.2 wt %, and the solution was injected in an amount of 1 to 10 μL into HPLC depending on the concentration. As the mobile phase of HPLC, acetonitrile and tetrahydrofuran were used and allowed to flow at a flow rate of 1 ml/min in gradient mode of acetonitrile/tetrahydrofuran=100/0 to 0/100 (volume ratio). As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having the equivalent performance was used. As the detector, a photodiode array detector (manufactured by Shimadzu. Corp., trade name: SPD-M20A) was used.
(8) (Measurement of NMR)
(9) A measurement sample (5 to 20 mg) was dissolved in about 0.5 ml of an organic solvent, and measurement of NMR was performed using NMR (manufactured by Varian, Inc., trade name: MERCURY300).
(10) (Measurement of LC/MS)
(11) A measurement sample was dissolved in a suitable organic solvent (chloroform, tetrahydrofuran, ethyl acetate, toluene and the like) so as to give a concentration of 1 to 10 mg/mL, and LC/MS was measured by LC/MS (manufactured by Agilent Technologies, trade name: 1100 LCMSD) and the measured value was analyzed. As the mobile phase of LC-MS, ion exchanged water, acetonitrile, tetrahydrofuran or a mixed solution thereof was used, and, if necessary, acetic acid was added. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, Japan, internal diameter: 4.6 mm, length: 250 mm, particle diameter: 3 μm) was used.
(12) (Measurement of Energy Level of Lowest Triplet Excitated State (T.sub.1))
(13) The energy level of the lowest triplet excitated state (T.sub.1) of a polymer compound (hereinafter, described as “TH”) was determined by measuring the phosphorescence spectrum of the polymer compound at 77K. Specifically, a toluene solution of the polymer compound (concentration: 8×10.sup.−4 mass %) was used as the measurement sample. As the exciting light source, a xenon lamp was used, and the measurement sample was irradiated with exciting light (exciting wavelength: 300 nm) dispersed using a diffraction grating, and a multi-channel spectrometer PMA-12 manufactured by Hamamatsu Photonics Co., Ltd. was used as the detector and the phosphorescence spectrum of the polymer compound was measured. When the intensity of the maximum peak wavelength (wavelength of the largest intensity) in the phosphorescent spectrum of the polymer compound was 1.0, the value obtained by converting the wavelength at the shortest side showing an intensity of 0.1 into energy was calculated as TH.
(14) The energy level of the lowest triplet excitated state (T.sub.1) of a phosphorescent compound (hereinafter, described as “TM”) was determined by measuring the phosphorescence spectrum of the phosphorescent compound at room temperature. Specifically, a toluene solution of the phosphorescent compound (concentration: 8×10.sup.−4 mass %) was used as the measurement sample. As the exciting light source, a xenon lamp was used, and the measurement sample was irradiated with exciting light (exciting wavelength: 300 nm) dispersed using a diffraction grating, and a multi-channel spectrometer PMA-12 anufactured by Hamamatsu Photonics Co., Ltd. was used as the detector and the phosphorescence spectrum of the phosphorescent compound was measured. When the intensity of the maximum peak wavelength (wavelength of the largest intensity) in the phosphorescent spectrum of the phosphorescent compound was 1.0, the value obtained by converting the wavelength at the shortest side showing an intensity of 0.1 into energy was calculated as TM.
(15) [Synthesis of Raw Material Monomer]
(16) Compounds MM1, MM2, MM3, MM4, MM5, CM1, CM2 and CC1 to CC12 shown below were synthesized by a known method or a synthesis method described later, and subjected to a purification operation such as recrystallization, silica gel column chromatography, sublimation and the like, and those showing a purity of 99.5% or more in terms of the HPLC area percentage value were used as raw material monomers in synthesis of a polymer compound or as raw material compounds in synthesis of a raw material monomer.
(17) ##STR00138## ##STR00139## ##STR00140## ##STR00141##
Example M1
Synthesis of Compound MM1
(18) A compound MM1 was synthesized according to the following first to fourth steps.
(19) ##STR00142##
(First Step)
(20) In a reaction vessel, pyridine (34.70 ml) was added to a compound CM1d (12.22 g, 34.70 mmol), then, benzyltrimethyl ammonium hydroxide (40% pyridine solution) (0.87 ml, preparation thereof is described later) was added at room temperature, and the mixture was heated at 40° C. in an oil bath and stirred for 16 hours while ventilating atmospheric air into the reaction vessel. Thereafter, benzyltrimethyl ammonium hydroxide (40% pyridine solution) (0.87 ml, preparation thereof is described later) was added again, and the mixture was heated in an oil bath at 60° C. and stirred for 8 hours, to obtain a reaction solution. To the resultant reaction solution were added ion exchanged water and acetic acid, to make acidic condition, then, the mixture was stirred at room temperature for 1 hour, and the deposited yellow solid was isolated by filtration and washed with water. The resultant solid was dried, then, dispersed in a mixed solvent composed of tetrahydrofuran and methanol (tetrahydrofuran/methanol=4/30 (v/v)), and the dispersion was stirred for 1.5 hours while heating in an oil bath at 80° C., and cooled down to room temperature, then, the deposited solid was isolated by filtration and dried under reduced pressure, to obtain the targeted compound MM1a (11.87 g) as a yellow solid. The yield was 93.5%. The resultant compound MM1a indicated a HPLC area percentage value (UV 254 nm) of 96.7%.
(21) .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.77 (s, 2H), 7.36 (s, 2H), 2.47 (s, 6H).
(22) LC/MS (APPI (posi)): 364[M].sup.+
(23) (Preparation of Benzyltrimethyl Ammonium Hydroxide (40% Pyridine Solution))
(24) Pyridine (50 ml) was added to benzyltrimethyl ammonium hydroxide (40% methanol solution) (referred to as “TRITON B” in some cases, manufactured by Kanto Chemical Co., Inc., 50 ml), then, the mixture was concentrated to 25 ml or less by an evaporator, and pyridine was again added for dilution to 50 ml. The solution obtained by this operation is called “benzyltrimethyl ammonium hydroxide (40% pyridine solution)”.
(25) (Second Step)
(26) An atmosphere in the reaction vessel was changed to an argon gas atmosphere, then, a solution prepared by dissolving 3,5-di-n-hexyl-1-bromobenzene (compound MM1b, 13.82 g, 42.5 mmol) in tetrahydrofuran (dehydrated product, 324 ml) was cooled using a cool bath of −78° C. while stirring. Thereafter, a hexane solution of n-butyllithium (1.63 mol/L, 25.7 ml) was slowly dropped so that the temperature of the resultant solution was kept at −75° C. or lower, and the mixture was further stirred for 1 hour. Thereafter, a compound MM1a (11.87 g, 32.4 mmol) was added little by little so that the temperature of the resultant solution was kept at −75° C. or lower, and further, the mixture was stirred for 2 hours, then, methanol (about 20 ml) was dropped slowly, then, the cool bath was removed, and the temperature was raised slowly up to room temperature. The solvent of the resultant reaction solution was distilled off by concentration under reduce pressure, then, hexane was added, and the mixture was washed with ion exchanged water, to obtain an oil layer. The resultant oil layer was dried over anhydrous sodium sulfate, insoluble components were separated by filtration, then, the solvent was distilled off by concentration under reduced pressure, and further, the residue was purified by recrystallization (hexane), isolated by filtration and dried under reduced pressure, to obtain the targeted compound MM1c (9.12 g) as a white solid. The yield was 45%. The resultant compound MM1c indicated a HPLC area percentage value (UV254 nm) of 97.9%.
(27) LC/MS (ESI (posi)): 610[M].sup.+
(28) (Third Step)
(29) A gas in a reaction vessel was changed to an argon gas atmosphere, then, a compound MM1c (9.12 g, 14.89 mmol), triethylsilane (4.53 ml, 59.6 mmol) and hexane (39 ml) were mixed, and trifluoroacetic acid (4.5 ml, 59.6=01) was dropped while heating at 70° C. in oil bath, then, and the mixture was further stirred for 3 hours with heating, to obtain a reaction solution. The resultant reaction solution was cooled down to room temperature, then, a 10 wt % potassium phosphate aqueous solution was added, and further, the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, insoluble components were separated by filtration, then, the solvent was distilled off by concentration under reduced pressure and drying under reduced pressure, to obtain an oily substance (8.9 g) containing a compound M1d. The resultant oily substance was used in the next step without performing further purification.
(30) LC/MS (ESI (posi)): 594[M].sup.+
(31) (Fourth Step)
(32) A gas in a reaction vessel was changed to an argon gas atmosphere, then, N,N-dimethylformamide (74 ml) was added to an oily substance (8.9 g) containing a compound MM5d, to obtain a uniform solution. The resultant solution was bubbled with argon for 15 minutes, then, the mixture was cooled to 5° C. or lower using an ice bath. Potassium hydroxide (2.76 g, 49.1 mmol) was dissolved in ion exchanged water (2.4 ml), then, a potassium hydroxide aqueous solution bubbled with argon was prepared separately, and added to the solution obtained above. Thereafter, methyl iodide (6.34 g, 44.7 mmol) was dropped, and the mixture was stirred at 0 to 5° C. for 4 hours. The ice bath was removed, then, ion exchanged water was added, and further, the mixture was extracted with hexane, to obtain an oil layer. The resultant oil layer was dried over anhydrous sodium sulfate, insoluble components were separated by filtration, the solvent was distilled off, then, the residue was purified by medium pressure silica gel column chromatography (developing solvent: hexane). Fractions containing the targeted material MM1 were combined, concentrated, then, purified by recrystallization (a mixed solvent of hexane and isopropanol), and the resultant crystal was isolated by filtration and dried under reduced pressure, to obtain the targeted compound MM1 (7.10 g) as a white solid. The yield was 77%. The resultant compound MM1c had a HPLC area percentage value (UV 254 nm) of 99.9% or more.
(33) .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.57 (s, 2H), 7.35 (s, 2H), 6.83 (s, 1H), 6.71 (s, 2H), 2.50-2.44 (m, 10H), 1.79 (s, 3H), 1.54-1.45 (m, 4H), 1.34-1.17 (m, 12H), 0.84 (t, 6H).
(34) LC/MS (ESI (posi)): 608[M]+
Example M2
Synthesis of Compound MM2
(35) A compound MM2 was synthesized according to the following step.
(36) ##STR00143##
(37) A gas in a reaction vessel was changed to an argon gas atmosphere, then, a mixture of bis(pinacol)diboron (9.10 g, 35.9 mmol), potassium acetate (7.04 g, 71.7 mmol), 1,4-dioxane (36 ml) and a dichloromethane complex of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Pd (dppf)Cl.sub.2.CH.sub.2Cl.sub.2, CAS number: 95464-05-4, manufactured by Sigma-Aldrich Co. LCC, 0.293 g, 0.36 mmol) was stirred with heating in oil bath at 115° C., and a solution prepared by dissolving the compound MM1 (7.13 g, 11.9 mmol) synthesized separately by the above-described method in 1, 4-dioxane (36 ml) was dropped over a period of 2 hours while stirring, then, the mixture was stirred for about 18 hours at the same temperature, to obtain a reaction solution. The resultant reaction solution was cooled down to room temperature, then, diluted by adding toluene, then, allowed to pass through a Celite and silica gel pad, to remove insoluble components and polar components. The resultant solution was dried over anhydrous sodium sulfate, insoluble materials were separated by filtration, then, the solvent was distilled off by concentration under reduced pressure, then, toluene was added to obtain a uniform solution. To the resultant solution was added activated carbon, and the mixture was stirred for 30 minutes while heating in an oil bath of 70° C., and cooled down to room temperature, then, insoluble materials were removed by filtration through Celite, the resultant solution was concentrated, then, purified by recrystallization (developing solvent: a mixed solvent of toluene and acetonitrile), the resultant crystal was isolated by filtration and dried under reduced pressure, to obtain the targeted compound MM2 (6.94 g) as a white solid. The yield was 82%. The resultant compound MM2 indicated a HPLC area percentage value (UV254 nm) of 99.9% or more.
(38) .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.64 (s, 2H), 7.55 (s, 2H),6.81 (s, 2H), 6.77 (s, 1H), 2.62 (s, 6H), 2.48-2.42 (m, 4H), 1.85 (s, 3H), 1.55-1.45 (m, 4H), 1.31 (s, 24H), 1.31-1.17 (m, 12H), 0.83 (t, 6H).
(39) LC/MS (ESI (posi)): 704[M]%
Example M3
Synthesis of Compound MM3
(40) A compound MM3 was synthesized according to the following first to fourth steps.
(41) ##STR00144##
(First Step)
(42) An atmosphere in a reaction vessel was changed to an argon gas atmosphere, then, to a compound (MM3a) (85 g, 108 mmol) was added tetrahydrofuran (dehydrated product, 1290 ml) to dissolve the compound, and the solution was cooled using an ice bath. Under condition of a temperature in the reaction vessel kept at 6° C. or lower, tert-butoxypotassium (24 g, 216 mmol) was added bit by bit while stirring. Thereafter, under condition of a temperature in the reaction vessel kept at 6° C. or lower, the mixture was stirred for 1 hour. Thereafter, n-octanoyl chloride (25 g, 216 mmol) was dropped over a period of 30 minutes. Thereafter, under condition of a temperature in the reaction vessel kept at 6° C. or lower, the mixture was stirred for 2 hours. Thereafter, an ammonium chloride aqueous solution was added to complete the reaction. To the resultant reaction solution were added toluene and ion exchanged water, the resultant organic layer was washed with ion exchanged water three times, then, dried over anhydrous magnesium sulfate. The resultant reaction solution was allowed to pass through a silica gel pad to separate insoluble materials by filtration, and the resultant solution was concentrated. Thereafter, the concentrated product was purified by silica gel column chromatography (developing solvent: hexane), to obtain the targeted compound (MM3b) (63 g, 104 mmol) as an oily substance. The resultant compound (MM3b) indicated a HPLC area percentage value (UV254 nm) of 90.0%.
(43) LC/MS (ESI (posi)): 720[M].sup.+
(44) (Second Step)
(45) An atmosphere in a reaction vessel was changed to an argon gas atmosphere, then, to a compound (MM3b) (58 g, 72 mmol) was added cyclopentylmethyl ether (dehydrated product, 1 L) to dissolve the compound, and the solution was cooled using an ice bath. Under condition of a temperature in the reaction vessel kept at 6° C. or lower, lithium aluminum hydride (1 g, 36 mmol) was added bit by bit while stirring. Thereafter, under condition of a temperature in the reaction vessel kept at 6° C. or lower, the mixture was stirred for 2 hours. Thereafter, an ammonium chloride aqueous solution was added to complete the reaction. The resultant organic layer was washed with ion exchanged water twice, then, dried over anhydrous magnesium sulfate. The resultant reaction solution was filtrated, and concentrated. Thereafter, the concentrated product was purified by medium pressure silica gel column chromatography (developing solvent: a mixed solvent of hexane and chloroform). Fractions containing the targeted compound (MM3c) were combined, concentrated, then, purified by recrystallization (a mixed solvent of hexane and methanol), to obtain the targeted compound (MM3c) (34 g, 47 mmol) as a white solid. The resultant compound (MM3c) indicated a HPLC area percentage value (UV254 nm) of 99.3%.
(46) LC/MS (ESI (posi)): 722 [M].sup.+
(47) (Third Step)
(48) An atmosphere in a reaction vessel equipped with a reflux condenser was changed to an argon gas atmosphere, then, to a compound (MM3c) (33 g, 46 mmol) was added toluene (dehydrated product, 330 ml). Diphosphorus pentaoxide (26 g, 182 mmol) was added while stirred at room temperature. Thereafter, the mixture was stirred for 2.5 hours while heating the reaction vessel in an oil bath set at 80° C., and cooled down to room temperature. The resultant reaction solution was poured into ice water, thereby decomposing excess diphosphorus pentaoxide, to complete the reaction. The resultant organic layer was washed with ion exchanged water three times, then, dried over anhydrous magnesium sulfate. The resultant reaction solution filtrated, and concentrated. The resultant oily substance was dissolved toluene, and the solution was allowed to pass through a silica gel pad, and the resultant toluene solution was concentrated. Thereafter, the concentrated product was purified by silica gel column chromatography (developing solvent: hexane), and fractions containing the targeted compound (MM3d) were combined, and concentrated, to obtain the targeted compound (MM3d) (26 g, 37 mmol) as an oily substance. The resultant compound (MM3d) indicated a HPLC area percentage value (UV 254 nm) of 99.7%.
(49) LC/MS (ESI (posi)): 704 [M].sup.+
(50) (Fourth Step)
(51) An atmosphere in a reaction vessel was changed to an argon gas atmosphere, then, potassium acetate (0.8 g, 8.5 mmol), bispinacolatodiboron (1.1 g, 1.4 mmol) and dioxane (dehydrated product, 5 ml) were added. While stirring at room temperature, 1,1′-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane complex (0.04 g, 0.4 mmol) was added. Thereafter, a compound (MM3d) (1 g, 1.4 mmol) dissolved in dioxane (dehydrated product, 5 ml) was dropped over a period of 30 minutes while heating the reaction vessel in an oil bath set at 115° C., and the mixture was stirred further for 14 hours. Thereafter, the mixture was cooled down to room temperature to complete the reaction. To the resultant reaction solution were added toluene and ion exchanged water, and the resultant organic layer was washed with ion exchanged water three times, then, dried over anhydrous magnesium sulfate. The resultant reaction solution was filtrated, the concentrated. The resultant oily substance was dissolved in toluene, then, activated carbon was added and the mixture was stirred for 30 minutes. Thereafter, the mixture was allowed to pass through a Celite and silica gel pad, and the resultant toluene solution was concentrated. Thereafter, purification by medium pressure silica gel column chromatography (developing solvent: a mixed solvent of hexane and chloroform) was repeated, and fractions containing the targeted compound (MM3) were combined and concentrated, to obtain the targeted compound (MM3) (0.4 g, 0.6 mmol) as an oily substance. The resultant compound (MM3) indicated a HPLC area percentage value (UV254 nm) of 99.3%.
(52) .sup.1H-NMR (300 MHz, CDCl3): δ (ppm)=8.57 (s, 1H), 8.51 (s, 1H), 8.45 (s, 1H), 7.77 (s, 1H), 7.03 (s, 1H), 6.91 (d, 2H), 2.86 (t, 2H), 2.80 (s, 3H), 2.73 (s, 3H), 2.64 (t, 4H), 1.64 (m, 6H), 0.87 to 1.40 (m, 63H).
(53) LC/MS (ESI (posi)): 786[M].sup.+
Example M4
Synthesis of Compound MM4
(54) A compound MM4 was synthesized according to the following first to fifth steps.
(55) ##STR00145##
[in the formula, the wavy line means that a compound attached with this wavy line is a geometric isomer mixture.]
(First Step)
(56) Into a reaction vessel equipped with a stirrer were added a compound MM4a (35.31 g) and methanol (1100 ml), then, an atmosphere in the reaction vessel was changed to an argon gas atmosphere. Thereafter, dimethyl 1,3-acetonedicarboxylate (34.65 g) was added to this bit by bit, then, sodium methoxide (5 mol/L methanol solution) (67.62 g) was dropped bit by bit. Thereafter, the mixture was thermally insulated at room temperature for 2 hours, and the temperature was raised up to 60° C. Thereafter, the mixture was stirred for 6 hours while thermally insulating at 60° C. The resultant reaction solution was cooled down to room temperature, and 35% hydrochloric acid (37.41 g) was added. Thereafter, water and toluene were added, and the mixture was stirred at room temperature. Thereafter, the aqueous layer was separated, and the resultant organic layer was washed with a saturated sodium chloride aqueous solution. To the resultant organic layer was added sodium sulfate, and the mixture was filtrated and concentrated, to obtain the targeted compound MM4b (60.1 g) as an oily substance. The resultant compound MM4b indicated a HPLC area percentage value (UV254 nm) of 42%.
(57) (Second Step)
(58) Into a reaction vessel equipped with a stirrer were added a compound MM4b (60.10 g), acetic acid (450 ml) and ion exchanged water (60 ml), and an atmosphere in the reaction vessel was changed to an argon gas atmosphere. Thereafter, the temperature was raised up to 100° C., and the mixture was stirred for 5 hours while thermally insulating at 100° C. The resultant reaction solution was cooled down to room temperature, then, water and toluene were added, the aqueous layer was separated, and the resultant organic layer was washed with a saturated sodium chloride aqueous solution. To the resultant organic layer was added sodium sulfate, and the mixture was filtrated and concentrated, to obtain a coarse product of the targeted compound MM4b. The resultant coarse product was purified by silica gel column chromatography (developing solvent: a mixed solvent of hexane and ethyl acetate), to obtain the targeted compound MM4c (19.5 g) as a white solid. The resultant compound MM4c indicated a HPLC area percentage value (UV254 nm) of 94.9%.
(59) LC/MS (APCI, positive): [M+H].sup.+457
(60) (Third Step)
(61) Into a reaction vessel equipped with a stirrer was added heptyltriphenylphosphonium bromide (82.29 g), and an atmosphere in the reaction vessel was changed to an argon gas atmosphere. Thereafter, toluene (520 ml) was added, and the mixture was cooled to 5° C. or lower. Thereafter, potassium tert-butoxide (20.92 g) was added, the temperature was raised up to room temperature, then, the mixture was stirred for 3 hours while thermally insulating at room temperature. To the resultant red slurry was added a compound MM4c (18.0 g), and the mixture was stirred for 6.5 hours while thermally insulating at room temperature. To the resultant reaction solution was added acetic acid (7.2 g), and the mixture was stirred for 15 minutes, then, water and hexane were added, and the mixture was stirred at room temperature, then, the aqueous layer was separated, and the resultant organic layer was washed with a saturated sodium chloride aqueous solution. To the resultant organic layer was added sodium sulfate, and the mixture was filtrated and concentrated, to obtain a coarse product of the targeted compound MM4d. The resultant coarse product was purified by silica gel column chromatography (developing solvent: hexane), to the resultant hexane solution was added activated carbon, and the mixture was stirred for 1 hour while thermally insulating at 50° C. Thereafter, the mixture was cooled down to room temperature, and filtrated using a filtering apparatus pre-coated with Celite, the resultant residue was washed with hexane several times, and the resultant filtrates were combined and concentrated, to obtain the targeted compound MM4d (18.8 g) as a colorless transparent liquid. The resultant compound MM4d indicated a HPLC area percentage value (UV254 nm) of 98.2%.
(62) LC/MS (APCI, positive): [M+H].sup.+621
(63) (Fourth Step)
(64) Into a reaction vessel equipped with a stirrer were added a compound MM4d (18.6 g), ethyl acetate (165 ml) and ethanol (150 ml), and an atmosphere in the reaction vessel was changed to a nitrogen gas atmosphere. Thereafter, 5 wt % Pd/C (about 50 wt % hydrous product) (3.7 g) was added, then, an atmosphere in the reaction vessel was changed to a hydrogen gas atmosphere. Thereafter, the mixture was stirred for 49 hours while thermally insulating at 50° C., and cooled down to room temperature. Thereafter, the mixture was filtrated using a filtering apparatus pre-coated with Celite, the resultant residue was washed with ethyl acetate several times, the resultant filtrates were combined and concentrated, to obtain the targeted coarse product. The resultant coarse product was purified by silica gel column chromatography (developing solvent: hexane), to the resultant hexane solution was added activated carbon, and the mixture was stirred for 1 hour while thermally insulating at 50° C. Thereafter, the mixture was cooled down to room temperature, and filtrated using a filtering apparatus pre-coated with Celite, the resultant residue was washed with hexane several times, and the resultant filtrates were combined and concentrated, to obtain the targeted compound MM4e (17.6 g) as a colorless transparent solution. The resultant compound MM4e indicated a HPLC area percentage value (UV254 nm) of 99.0%.
(65) LC/MS (APCI, Positive): [M+H].sup.+625
(66) (Fifth Step)
(67) Into a reaction vessel equipped with a stirrer was added a compound MM4e (17.0 g), and an atmosphere in the reaction vessel was changed to an argon gas atmosphere. Thereafter, chloroform (230 ml) and trifluoroacetic acid (22 ml) were added, and the mixture was cooled to 5° C. or lower. Thereafter, the whole body of the reaction vessel was light-shielded, a mixture of bromine (8.9 g) and chloroform (45 ml) was dropped over a period of 15 minutes, then, the mixture was stirred for 3 hours while thermally insulating at 5° C. or lower. To the resultant reaction solution was added a 10 wt % sodium sulfite aqueous solution, then, the temperature was raised up to room temperature. The aqueous layer was separated from the resultant reaction solution, and the resultant organic layer was washed with water, a 5 wt % sodium hydrogen carbonate aqueous solution and water in this order. The resultant organic layer was dried over magnesium sulfate, and filtrated and concentrated, to obtain a coarse product of the targeted compound MM4. The resultant coarse product was purified by silica gel column chromatography (developing solvent: hexane), to the resultant hexane solution was added activated carbon, and the mixture was stirred for 1 hour while thermally insulating at 50° C. Thereafter, the mixture was cooled down to room temperature, and filtrated using a filtering apparatus pre-coated with Celite, the resultant residue was washed with hexane several times, and the resultant filtrates were combined and concentrated. This operation was further repeated twice, to obtain the targeted compound MM4 (19.3 g) as a colorless transparent solution. The resultant compound MM4 indicated a HPLC area percentage value (UV254 nm) of 99.7%.
(68) LC-MS (APCI, positive): [M+H].sup.+781
(69) .sup.1H-NMR (CDCl.sub.3, 300 MHz) δ (ppm): 0.91 (12H, m), 1.18 to 1.43 (36H, m), 1.56 to 1.77 (8H, m), 2.15 to 2.33 (4H, m), 2.70 to 2.75 (4H, m), 7.39 to 7.53 (2H, m), 7.61 to 7.66 (2H, m).
Example M5
Synthesis of Compound MM5
(70) A compound MM5 was synthesized according to the following step.
(71) ##STR00146##
(72) Into a reaction vessel equipped with a stirrer was added dehydrated tetrahydrofuran (210 ml), and it was cooled down to −70° C. or lower. Thereafter, n-butyllithium (1.6M hexane solution) (70 ml) was dropped over a period of 30 minutes or more, and the mixture was stirred for 30 minutes while thermally insulating at −70° C. or lower. Thereafter, a compound MM4 (18.2 g) and dehydrated tetrahydrofuran (210 ml) were dropped over a period of 30 minutes or more, and the mixture was stirred for 1 hour while thermally insulating at −70° C. or lower.
(73) Thereafter, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (32 ml) was dropped over a period of 10 minutes or more. Thereafter, the temperature was raised up to room temperature, and the mixture was stirred for 4 hours while thermally insulating. Thereafter, toluene was added to dilute the resultant reaction solution, then, water was added and the mixture was stirred at room temperature. Thereafter, the aqueous layer was separated, and the resultant organic layer was washed with a saturated sodium chloride aqueous solution. To the resultant organic layer was added sodium sulfate, and the mixture was filtrated and concentrated, to obtain a coarse product of the targeted compound MM5. The resultant coarse product was purified by silica gel column chromatography (developing solvent: a mixed solvent of hexane and ethyl acetate). Thereafter, recrystallization was performed using a mixed solvent of toluene and acetonitrile, to obtain a compound MM5 (14.6 g) as a white solid. The resultant compound MM5 indicated a HPLC area percentage value (UV254 nm) of 99.8%.
(74) LC/MS (APCI, positive): [M+H].sup.+877
(75) .sup.1H-NMR (CD.sub.2Cl.sub.2, 300 MHz) δ (ppm): 0.94 (12H, m), 1.27 to 1.44 (60H, m), 1.64 to 1.74 (8H, m), 2.25 to 2.45 (4H, m), 2.94 (4H, m), 7.67 to 7.82 (4H, m).
Synthesis Example CM1
Synthesis of Compound CM1
(76) A compound CM1 was synthesized according to the following first to fourth steps.
(77) ##STR00147##
(First step)
(78) A gas in a reaction vessel equipped with a reflux condenser was changed to an argon gas atmosphere, then, a mixture of 3-bromo-4-chlorotoluene (compound CM1a, 30.82 g, 150 mmol), 2,5-dimethylphenylboronic acid (compound CM1b, 24.75 g, 165 mmol), anhydrous potassium carbonate (124.39 g, 900 mmol), palladium(II) acetate (0.67 g, 6 m mol), tricyclohexylphosphine (1.68 g, 12 mmol), dimethylacetamide (dehydrated product, 600 ml) and pivalic acid (15.32 g, 150 mmol) was stirred for 10 hours while heating in an oil bath set at 150° C. Thereafter, the mixture was diluted with toluene (500 ml), then, and washed with ion exchanged water and liquid-separated three times. Thereafter, to the resultant oil layer was added activated white earth (manufactured by Wako Pure Chemical Industries, Ltd., 60 g) and the mixture was stirred for 2 hours, then, an operation of removing insoluble components by passing through a Celite and silica gel pad was repeated twice. The solvent was removed from the resultant solution by concentration under reduced pressure, then, the residue was purified by recrystallization (developing solvent: a mixed solvent of chloroform and ethanol), and the deposited crystal was isolated by filtration and dried under reduced pressure, to obtain the targeted compound CM1c (35.5 g) as a pale yellow to white solid. The yield was 51%. The resultant compound CM1c indicated a HPLC area percentage value of 99.3% (UV254 nm).
(79) (Second Step)
(80) A gas in a reaction vessel was changed to an argon gas atmosphere, then, to a compound CM1c (14.58 g, 75 mmol) were added trifluoroacetic acid (11.15 ml, 150 mmol) and chloroform (dehydrated product, 400 ml) and a uniform mixture was prepared, and the mixture was cooled to 5° C. or lower using an ice bath. Bromine (8.46 ml, 165 mmol) was slowly added while keeping the temperature of the resultant mixture at 5° C. or lower, then, the ice bath was removed, and the mixture was stirred at room temperature for 4 hours, to obtain a reaction solution. To the resultant reaction solution was added a saturated aqueous solution of sodium dithionite, excess bromine was decomposed, then, the mixture was concentrated under reduced pressure to remove the solvent, thereby obtaining a solid. To the resultant solid was added tetrahydrofuran (1 L), the mixture was stirred at 70° C. for 1 hour, then, cooled down to room temperature, water was added, the deposited inorganic salt was dissolved, then, concentrated under reduced pressure again to remove tetrahydrofuran, thereby obtaining a solid-liquid mixture. The deposited solid was isolated by filtration, toluene was added to this to dissolve the solid, then, the resultant toluene solution was concentrate by passing through a silica gel short column, to obtain a solid. An operation of purifying the resultant solid by recrystallization using a mixed solvent of toluene and isopropanol was repeated, to obtain the targeted compound CM1d (22.3 g). The yield was 84%. The resultant compound CM1d indicated a HPLC area percentage value (UV254 nm) of 99.9% or more.
(81) .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.67 (s, 2H), 7.58 (s, 2H), 3.79 (s, 2H), 2.48 (s, 6H).
(82) (Third Step)
(83) A gas in a reaction vessel was changed to an argon gas atmosphere, then, a compound CM1d (5.00 g, 14.2 mmol), potassium hydroxide (3.51 g, 62.5 mmol), potassium iodide (236 mg, 1.4 mmol), dimethyl sulfoxide (dehydrated product, 60 ml) and tetrahydrofuran (dehydrated product, 80 ml) were mixed, then, 1-bromooctane (12.20 g, 62.5 mmol) was added at room temperature over a period of 10 minutes, then, the mixture was stirred for 3.5 hours while heating in an oil bath at 70° C., to obtain a reaction solution. The resultant reaction solution was cooled down to room temperature, then, toluene and ion exchanged water were added, the resultant oil layer was washed with ion exchanged water three times, then, dried over anhydrous sodium sulfate. Insoluble components were separated by filtration by passing through a silica gel pad, the resultant solution was concentrated, then, purified by medium pressure silica gel column chromatography (developing solvent: hexane), and fractions containing the targeted compound were combined and concentrated, then, purified by recrystallization (a mixed solvent of chloroform and ethanol), to obtain the targeted compound CM1 (7.13 g) as a white solid. The yield was 87.1%. The resultant compound CM1 indicated a HPLC area percentage value (UV254 nm) of 99.9% or more.
(84) .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.50 (s, 2H), 7.44 (s, 2H), 2.47 (s, 6H), 1.89-1.84 (m, 4H), 1.23-1.04 (m, 20H), 0.83 (t, 6H), 0.66-0.55 (m, 4H).
Synthesis Example CM2
Synthesis of Compound CM2
(85) A compound MM4 was synthesized according to the following step.
(86) ##STR00148##
(87) A gas in a reaction vessel was changed to an argon gas atmosphere, then, a mixture of a compound CM1 (2.34 g, 4.07 mmol), bis(pinacol)diboron (3.10 g, 12.21 mmol), a dichloromethane complex of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Pd(dppf)Cl.sub.2.CH.sub.2Cl.sub.2, CAS number: 95464-05-4, manufactured by Sigma-Aldrich Co. LLC, 0.100 g, 0.12 mmol), 1,1′-bis(diphenylphosphino)ferrocene (referred to as “dppf” in some cases, 0.068 g, 0.12 mmol), potassium acetate (2.39 g, 24.4 mmol) and 1,4-dioxane (dehydrated product, 33 ml) was stirred for about 18 hours while heating in an oil bath at 110° C., then, insoluble components were removed by passing through a Celite and silica gel pad. The resultant solution was dried over anhydrous sodium sulfate, insoluble components were separated by filtration, then, the solvent was distilled off, to obtain a solid. The resultant solid was dissolved in toluene, activated carbon was added to the solution, the mixture was stirred for 1 hour while heating in an oil bath at 70° C., then, insoluble components were removed by filtrating through Celite, then, the solvent was distilled off, to obtain a solid. The resultant solid was purified by medium pressure silica gel column chromatography (developing solvent: hexane), and further, purified by recrystallization (a mixed solvent of chloroform and acetonitrile), isolated by filtration and dried under reduced pressure, to obtain the targeted compound CM2 (1.00 g). The yield was 37%. The resultant compound CM2 indicated a HPLC area percentage value (UV254 nm) of 99.7%.
(88) .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=7.66 (s, 2H), 7.49 (s, 2H), 2.61 (s, 6H), 1.96-1.91 (m, 4H), 1.37 (s, 24H), 1.19-1.02 (m, 20H), 0.81 (t, 6H), 0.68-0.52 (m, 4H).
(89) LC/MS (ESI (posi)): 670 [M]′
Synthesis Example CC5
Synthesis of Compound CC5
(90) ##STR00149##
(91) An atmosphere in a reaction vessel was changed to an argon gas atmosphere, then, 4-hexylbenzoyl chloride (11.24 g, 50 mmol), dichloromethane (90 ml) and molecular sieves 3A (manufactured by Wako Pure Chemical Industries, Ltd., 10 g) were added, and cooled down to 0° C., then, antimony pentachloride (14.7 g, 49 mmol) was dropped over a period of 10 minutes. Thereafter, the mixture was stirred at 0° C. for 20 minutes, then, 4-bromo-3-methylbenzonitrile (19.6 g, 100 mmol) dissolved in dichloromethane (60 ml) was dropped over a period of 1 hour. Thereafter, the mixture was stirred at room temperature for 30 minutes, then, stirred for 2 hours under reflux with heating. The mixture was allowed to stand still at room temperature overnight, then, a 25% ammonia aqueous solution (22 g) was dropped under condition keeping −10° C. After completion of dropping, the mixture was stirred at room temperature for 5 hours, then, chloroform (500 ml) was added, and the mixture was stirred for 1 hour under reflux with heating, then, a solid was removed by hot filtration, the resultant filtrate was washed with ion exchanged water (200 ml) three times, washed with 15 wt % saline (200 ml) once, and the resultant organic layer was dried over anhydrous sodium sulfate, the solid was separated by filtration, then, the resultant filtrate was concentrated under reduced pressure, to obtain an orange oily substance. The resultant oily substance was purified by conducting recrystallization (a mixed solvent of chloroform and methanol), recrystallization (a mixed solvent of toluene and ethanol), medium pressure silica gel column chromatography (developing solvent: a mixed solvent of hexane and chloroform) twice and recrystallization (a mixed solvent of chloroform and hexane) in series, and the resultant solid was dried under reduced pressure, to obtain the targeted compound CC5 (3.97 g) as a white solid. The resultant compound indicated a HPLC area percentage value of 99.6% or more.
(92) .sup.1H-NMR (300 MHz, THF-d.sub.8): δ (ppm)=8.63 (d, 4H), 8.43 (d, 2H), 7.73 (d, 2H), 7.40 (d, 2H), 2.76 (t, 2H), 2.54 (s, 6H), 1.73 (m, 2H), 1.43 (m, 6H), 0.93 (t, 3H).
(93) .sup.13C-NMR (75 MHz, THF-d.sub.8): δ (ppm)=173.7, 172.8, 150.3, 140.2, 137.6, 135.5, 134.6, 132.9, 131.7, 131.0, 130.6, 129.8, 37.9, 33.8, 33.3, 31.1, 24.7, 24.3, 15.6.
Synthesis Example CC6
Synthesis of Compound CC6
(94) ##STR00150##
(First Step)
(95) A gas in a reaction vessel was changed to an argon gas atmosphere, then, a mixture of a compound CC7 (41.77 g, 120 mmol), bis(pinacol)diboron (91.9 g, 362 mmol), a dichloromethane complex of
(96) [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1:1) (Pd(dppf)Cl.sub.2.CH.sub.2Cl.sub.2, CAS number: 95464-05-4, manufactured by Sigma-Aldrich Co. LLC, 5.096 g, 6.24 mmol), potassium acetate (70.67 g, 720 mmol) and 1,4-dioxane (commercially available dehydrated product, 500 ml) was stirred for about 8 hours while heating in an oil bath at 80° C., then, diluted with toluene (500 ml) and the solution was allowed to pass through a Celite and silica gel pad to remove insoluble components, then, the solvent was distilled off, to obtain a solid. To the resultant solid was added methanol (750 ml), and the mixture was stirred well, then, the solid was isolated by filtration, and dried under reduced pressure, to obtain a solid (57 g). The resultant solid was dissolved in hexane, activated carbon was added, and the mixture was stirred for 1 hour while heating in an oil bath at 60° C., then, insoluble components were removed by filtration through Celite, then, the solvent was distilled off, to obtain a shite solid. To the resultant solid was added methanol (750 ml), and the mixture was stirred for 1 hour while heating at 50° C., then, cooled down to room temperature, and the deposited solid was isolated by filtration, and dried under reduced pressure, to obtain a compound CC6a (40.59 g). The yield was 76%. The resultant compound CC6a indicated a HPLC area percentage value (UV254 nm) of 99.9% or more.
(97) .sup.1H-NMR (300 MHz, CDCl.sub.3): δ (ppm)=8.75 (d, 2H), 8.68 (d, 2H), 8.06 (d, 2H), 7.39 (d, 2H), 2.73 (t, 2H), 1.71-1.60 (m, 2H), 1.50-1.20 (m, 46H), 0.88 (t, 3H).
(98) TLC/MS (dART, posi): [M+H].sup.+=730.49
(99) (Second Step)
(100) A gas in a reaction vessel was changed to an argon gas atmosphere, then, a mixture of a compound CC6a (25.54 g, 35 mmol), 5-iodo-2-bromo-m-xylene (32.65 g, 105 mmol), toluene (210 ml), tert-butanol (140 ml), tetrahydrofuran (105 ml), ion exchanged water (70 ml), a 20 wt % tetraethyl ammonium hydroxide aqueous solution (103.1 g, 140 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.45 g, 2.12 mmol) was stirred for 40 hours while heating in an oil bath set at 40° C., then, cooled down to room temperature, toluene (140 ml) and ion exchanged water (140 ml) were added, and the organic layer was obtained by liquid-separation. The resultant organic layer was washed with 5 wt % saline, then, dried over anhydrous magnesium sulfate, the resultant solid was removed by filtration, then, the solvent was distilled off by concentration under reduced pressure, to obtain a brown oily substance (37 g). The resultant brown oily substance was diluted with toluene and the solution was allowed to pass through a silica gel short column, the solvent was distilled off by concentration under reduced pressure, to obtain a yellow oily substance. The resultant yellow oily substance was purified by medium pressure silica gel column chromatography (hexane), fractions containing the targeted compound were concentrated under reduced pressure, then, purified by recrystallization (a mixed solvent of toluene and methanol), and the resultant solid was dried under reduced pressure, to obtain a compound CC6 (6.15 g). The yield was 21%. The resultant compound CC6 indicated a HPLC area percentage value of 99.9% or more.
(101) H-NMR (300 MHz, CD.sub.2Cl.sub.2): δ (ppm)=8.86 (d, J=8.3 Hz, 4H), 8.72 (d, J=8.3 Hz, 2H), 7.43 (d, J=8.3 Hz, 2H), 7.37 (d, J=8.3 Hz, 4H),7.32 (s, 4H), 2.75 (t, J=7.7 Hz, 2H), 2.07 (s, 12H), 1.75-1.66 (mult, 2H), 1.42-1.22 (mult, 18H), 0.88 (t, J=6.6 Hz, 3H).
(102) TLC/MS (dART, posi): [M+H].sup.+=842.27
Production of Polymer Compound
Example P1
Synthesis of Polymer Compound P1
(103) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound MM1 (1.3388 g), a compound MM2 (1.1600 g) and toluene(39 ml) was heated at about 80° C., then, bis[tris(2-methoxyphenyl)phosphine]palladium dichloride (1.65 mg) and a20 wt % tetraethyl ammonium hydroxide aqueous solution (6.7 g) were added, and the mixture was stirred for about 7.5 hours under reflux of an argon gas.
(104) Thereafter, phenylboronic acid (46.8 mg), bis[tris(2-methoxyphenyl)phosphine]palladium dichloride (1.67 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (6.7 g) were added, and the mixture was further stirred for about 15.5 hours under reflux of an argon gas. Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (0.54 g) in ion exchanged water (11 ml) was added, and the mixture was stirred for about 2.5 hours while heating at 85° C.
(105) The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water four times, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound (1.554 g, polymer compound P1). The polymer compound P1 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=4.7×10.sup.4 and Mw=1.3×10.sup.5, respectively. The polymer compound P1 had a TH of 2.67 eV.
(106) The polymer compound P1 is estimated to be a polymer compound composed of the following repeating unit, based on the charging ratios of raw material monomers.
(107) ##STR00151##
Example P2
(108) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound CC1 (1.2767 g), a compound MM1 (1.0948 g), a compound CC7 (0.4884 g) and toluene (38 ml) was heated at about 80° C., then, dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (2.23 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (9.0 g) were added, and the mixture was stirred for about 6.5 hours under reflux of an argon gas.
(109) Thereafter, 2-isopropylphenylboronic acid (84.9 mg), dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (2.33 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (9.0 g) were added, and the mixture was further stirred for about 16.5 hours under reflux of an argon gas.
(110) Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (0.72 g) in ion exchanged water (14 ml) was added, and the mixture was stirred for 2 hours while heating at 85° C.
(111) The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water four times, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound (1.686 g, polymer compound P2). The polymer compound P2 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=6.5×10.sup.4 and Mw=1.9×10.sup.5, respectively. The polymer compound P2 had a TH of 2.74 eV.
(112) The polymer compound P2 is estimated to be a polymer compound having the following repeating units and mole fractions and in which a repeating unit of (PA) and a repeating unit selected from (PB) are alternately polymerized, based on the charging ratios of raw material monomers.
(113) ##STR00152##
Example P3
Synthesis of Polymer Compound P3
(114) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound CC1 (1.1788 g), a compound MM1 (0.5776 g), a compound CC5 (0.8223 g) and toluene (33 ml) was heated at about 80° C., then, dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (2.12 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (8.4 g) were added, and the mixture was stirred for about 10 hours under reflux of an argon gas.
(115) Thereafter, 2-isopropylphenylboronic acid (78.4 mg), dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (2.07 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (8.4 g) were added, and the mixture was further stirred for about 14 hours under reflux of an argon gas.
(116) Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (0.67 g) in ion exchanged water (13 ml) was added, and the mixture was stirred for 4.5 hours while heating at 85° C.
(117) The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water four times, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound (1.471 g, polymer compound P3). The polymer compound P3 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=4.4×10.sup.4 and Mw=1.6×10.sup.5, respectively. The polymer compound P3 had a TH of 2.79 eV.
(118) The polymer compound P3 is estimated to be a polymer compound having the following repeating units and mole fractions and in which a repeating unit of (PA) and a repeating unit selected from (PB) are alternately polymerized, based on the charging ratios of raw material monomers.
(119) ##STR00153##
Example P4
Synthesis of Polymer Compound P4
(120) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound CC1 (1.1213 g), a compound MM1 (0.8791 g), a compound CC6 (0.6834 g) and toluene (38 ml) was heated at about 80° C., then, dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (1.97 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (8.0 g) were added, and the mixture was stirred for about 11 hours under reflux of an argon gas.
(121) Thereafter, phenylboronic acid (55.4 mg), dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (2.03 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (8.0 g) were added, and the mixture was further stirred for about 12 hours under reflux of an argon gas.
(122) Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (0.63 g) in ion exchanged water (13 ml) was added, and the mixture was stirred for 2 hours while heating at 85° C.
(123) The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water four times, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound (1.569 g, polymer compound P4). The polymer compound P4 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=4.2×10.sup.4 and Mw=1.1×10.sup.5, respectively. The polymer compound P4 had a TH of 2.78 eV.
(124) The polymer compound P4 is estimated to be a polymer compound having the following repeating units and mole fractions and in which a repeating unit of (PA) and a repeating unit selected from (PB) are alternately polymerized, based on the charging ratios of raw material monomers.
(125) ##STR00154##
Example P5
Synthesis of Polymer Compound P5
(126) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound CC1 (1.0369 g), a compound CM1 (0.9595 g), a compound CC7 (0.2644 g) and toluene (31 ml) was heated at about 80° C., then, dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (1.84 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (11.1 g) were added, and the mixture was stirred for about 6.5 hours under reflux of an argon gas.
(127) Thereafter, phenylboronic acid (51.2 mg), dichlorobis(tris(2-methoxyphenyl)phosphine)palladium (1.84 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (11.1 g) were added, and the mixture was further stirred for about 17 hours under reflux of an argon gas.
(128) Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (0.59 g) in ion exchanged water (12 ml) was added, and the mixture was stirred for 3.5 hours while heating at 85° C.
(129) The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water six times, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound (1.303 g, polymer compound P5). The polymer compound P5 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=5.8×10.sup.4 and Mw=1.6×10.sup.5, respectively. The polymer compound P5 had a TH of 2.72 eV.
(130) The polymer compound P5 is estimated to be a polymer compound having the following repeating units and mole fractions and in which a repeating unit of (PA) and a repeating unit selected from (PB) are alternately polymerized, based on the charging ratios of raw material monomers.
(131) ##STR00155##
Synthesis Example CP1
Synthesis of Polymer Compound CP1
(132) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound CC1 (2.2425 g), a compound CC3 (2.3202 g), a compound CC7 (0.5719 g) and toluene (70 ml) was heated at about 80° C., then, bis[tris(2-methoxyphenyl)phosphine]palladium dichloride (3.97 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (15.9 g) were added, and the mixture was stirred for about 6 hours under reflux of an argon gas.
(133) Thereafter, phenylboronic acid (0.1109 g), bis[tris(2-methoxyphenyl)phosphine]palladium dichloride (4.00 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (15.9 g) were added, and the mixture was further stirred for about 16.5 hours under reflux of an argon gas.
(134) Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (1.27 g) in ion exchanged water (25 ml) was added, and the mixture was stirred for about 2 hours while heating at 85° C.
(135) The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water four times, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound CP1 (2.729 g). The polymer compound CP1 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=8.2×10.sup.4 and Mw=2.1×10.sup.5, respectively. The polymer compound CP1 had a TH of 2.65 eV.
(136) The polymer compound CP1 is estimated to be a polymer compound having the following repeating units and mole fractions and in which a repeating unit of (PA) and a repeating unit selected from (PB) are alternately polymerized, based on the charging ratios of raw material monomers.
(137) ##STR00156##
Synthesis Example CP2
Synthesis of Polymer Compound CP2
(138) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound CC1 (2.7651 g), a compound CC2 (1.7943 g), a compound CC12 (0.7363 g) and toluene (58 ml) was heated at about 80° C., then, palladium acetate (1.31 mg), tris(2-methoxyphenyl)phosphine (7.75 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (19.6 g) were added, and the mixture was stirred for about 8.5 hours under reflux of an argon gas.
(139) Thereafter, 2-isopropylphenylboronic acid (0.1366 g), palladium acetate (1.28 mg), tris(2-methoxyphenyl)phosphine (7.79 mg) and a 20 wt % tetraethyl ammonium hydroxide aqueous solution (19.6 g) were added, and the mixture was further stirred for about 15.5 hours under reflux of an argon gas.
(140) Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (1.56 g) in ion exchanged water (31 ml) was added, and the mixture was stirred for about 2 hours while heating at 85° C.
(141) The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with 2.5 wt % ammonia water twice and with ion exchanged water four times, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound (2.732 g, polymer compound CP2). The polymer compound CP2 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=6.6×10.sup.4 and Mw=2.9×10.sup.5, respectively. The polymer compound CP2 had a TH of 2.95 eV.
(142) The polymer compound CP2 is estimated to be a polymer compound having the following repeating units and mole fractions and in which a repeating unit of (PA) and a repeating unit selected from (PB) are alternately polymerized, based on the charging ratios of raw material monomers.
(143) ##STR00157##
Synthesis Example IP1
Synthesis of Polymer Compound IP1
(144) A gas in a reaction vessel was changed to a nitrogen gas atmosphere, then, a mixture of a compound CC8 (21.218 g), a compound CC9 (5.487 g), a compound CC10 (16.377 g), a compound CC11 (2.575 g), methyltrioctyl ammonium chloride (trade name: Aliquat (registered trademark) 336, manufactured by Sigma-Aldrich Co. LLC) (5.17 g) and toluene (400 ml) was heated at about 80° C., then, bistriphenylphosphinepalladium dichloride (56.2 mg) and a 17.5 wt % sodium carbonate aqueous solution (109 g) were added, and the mixture was stirred for about 6 hours under reflux of an argon gas.
(145) Thereafter, phenylboronic acid (0.49 g) was added, and the mixture was further stirred for about 2 hours under reflux of an argon gas.
(146) Thereafter, a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (24.3 g) in ion exchanged water (240 ml) was added, and the mixture was stirred for 2 hours while heating at 85° C.
(147) The resultant organic layer was washed with ion exchanged water twice, with 3 wt % acetic acid twice and with ion exchanged water twice, in series. The resultant organic layer was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a solid. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol to cause generation of a precipitate, which was isolated by filtration, and dried, to obtain a polymer compound (26.23 g, polymer compound IP1). The polymer compound IP1 had a polystyrene-equivalent number-average molecular weight (Mn) and a polystyrene-equivalent weight-average molecular weight (Mw) of Mn=7.8×10.sup.4 and Mw=2.6×10.sup.5, respectively.
(148) The polymer compound IP1 is estimated to be a polymer compound having the following repeating units and mole fractions and in which a repeating unit of (PA) and a repeating unit selected from (PB) are alternately polymerized, based on the charging ratios of raw material monomers.
(149) ##STR00158##
Preparation of Light Emitting Material
Synthesis Example EM1
Synthesis of Phosphorescent Compound EM1
(150) ##STR00159## ##STR00160##
<Stage1>
(151) In a reaction vessel, 6.92 g (31.5 mmol) of 3-bromobenzoyl chloride and 4.95 g (32.6 mmol) of ethyl butylimidate hydrochloride were weighed, and 150 ml of chloroform was added, then, a gas in the reaction vessel was changed to a nitrogen gas atmosphere. Thereafter, 20 ml of a chloroform solution containing 8.0 ml (60 mmol) of triethylamine was dropped, and the mixture was stirred at room temperature for 15 hours under a nitrogen gas atmosphere. The resultant solution was concentrated and suspended in dichloromethane, and the suspension was placed in a separating funnel and washed. The resultant oil layer was concentrated and dried, to obtain 9.47 g of a compound (E1a) as a colorless liquid. The results of .sup.1H-NMR analysis are shown below.
(152) .sup.1H-NMR (400 MHz/CDCl.sub.3): δ (ppm)=8.14 (t, 1H), 7.93 (dd, 1H), 7.65-7.63 (m, 1H), 7.31 (t, 1H), 4.29 (Q,2H), 2.36 (t, 2H), 1.60 (td,2H), 1.37 (t, 3H), 0.88 (t, 3H).
(153) <Stage2>
(154) In a reaction vessel, 9.0 g (30 mmol) of a compound (E1a) was dissolved in 100 ml of chloroform, then, a gas in the reaction vessel was changed to a nitrogen gas atmosphere. Thereafter, 15 ml of a chloroform solution containing 1.52 g (33 mmol) of methylhydrazine and 0.6 ml of water was dropped, and the mixture was stirred at room temperature for 7 hours under a nitrogen gas atmosphere. Into the resultant reaction solution, 100 ml of water was poured, and the solution was placed in a separating funnel and washed. The resultant oil layer was recovered and concentrated, and allowed to pass through a silica gel column. The product was separated and purified using a mixed solvent of dichloromethane and ethyl acetate, to obtain 5.8 g (21 mmol) of a compound (E1b) as a pale yellow liquid with a yield of 69%. The results of .sup.1H-NMR analysis are shown below.
(155) .sup.1H-NMR (400 MHz/CDCl.sub.3): δ (ppm)=7.85 (d, 1H), 7.60 (m, 2H), 7.37 (dd, 1H), 3.93 (s, 3H), 2.72 (t, 2H), 1.81 (m, 2H), 1.01 (t, 3H).
(156) <Stage3>
(157) In a reaction vessel, 1.3 g (4.6 mmol) of a compound (E1b), 2200 mg (4.7 mmol) of 3,5-di(4-tertiary-butylphenyl)phenylboronic acid pinacol ester and 1250 mg (11.6 mol) of sodium carbonate were weighed, and 5 ml of ethanol, 10 ml of water and 10 ml of toluene were added, then, a gas in the reaction vessel was changed to a nitrogen gas atmosphere. Thereafter, 260 mg (0.23 mmol) of tetrakistriphenylphosphinopalladium(0) was added, and the mixture was placed again under a nitrogen gas atmosphere. The resultant reaction mixture was heated at 80° C. for 15 hours. After left to cool, water and toluene were poured and washing was performed. The resultant oil layer was recovered, then, concentrated, to obtain a coarse product. The resultant coarse product was allowed to pass through a silica gel column and separated and purified with a mixed solvent of dichloromethane and ethyl acetate. A compound (E1c) (2.18 g, 4.0 mmol) was obtained as a white powder with a yield of 88%. The results of .sup.1H-NMR analysis are shown below.
(158) .sup.1H-NMR (400 MHz/(CD.sub.3).sub.2CO): δ (ppm)=8.19 (t, 1H), 7.98 (dt, 1H), 7.93 (d, 2H), 7.91 (t, 1H), 7.80 (t, 1H), 7.77 (dt, 4H), 7.66 (t, 1H), 7.54 (dt, 4H), 4.01 (s, 3H), 2.63 (t, 2H), 1.76 (td, 2H), 1.36 (s, 18H), 0.98 (t, 3H).
(159) <Stage4>
(160) In a reaction vessel, 226 mg (0.64 mmol) of iridium chloride and 760 mg (1.4 mmol) of a compound (E1c) were weighed, and 2 ml of water and 6 ml of 2-butoxyethanol were added, then, a gas in a reaction vessel was changed to a nitrogen gas atmosphere, and the mixture was refluxed with heating for 17 hours. After left to cool, water and dichloromethane were poured, and the resultant oil layer was washed. The resultant oil layer was concentrated and dried, to obtain 840 mg of a compound as a brownish-yellow amber-colored solid. In a reaction vessel, 840 mg of the resultant brownish-yellow amber-colored solid and 1300 mg (2.4 mmol) of a compound (E1c) were weighed, a gas in the reaction vessel was changed to an argon gas atmosphere, then, 165 mg (0.64 mmol) of silver trifluorosulfonate was added. Thereafter, 1.25 ml of diethylene glycol dimethyl ester was added, and the mixture was refluxed with heating for 15 hours under an argon gas atmosphere. After left to cool, dichloromethane was poured, and the resultant suspension was filtrated under suction. The resultant filtrate was placed in a separating funnel and washed, and the resultant oil layer was recovered, then, concentrated, to obtain a coarse product. The resultant coarse product was allowed to pass through a silica gel column and separated and purified with a mixed solvent of dichloromethane and ethyl acetate. The resultant yellow solid was recrystallized using a mixed solvent of dichloromethane and methanol, then, recrystallized using a mixed solvent of dichloromethane and hexane. A phosphorescent compound (EM1) [fac-tris(1-methyl-3-propyl-5-(5-(3,5-di(4-tertiary-butylph enyl)phenyl)phenyl)-1H-[1,2,4]-triazolato-N,C2′)iridium(III)] (850 mg, 0.48 mmol) was obtained as a yellow powder with a yield of 73%. The results of .sup.1H-NMR analysis are shown below. The phosphorescent compound EM1 had a TM of 2.77 eV.
(161) .sup.1H-NMR (400 MHz/CDCl.sub.3): δ (ppm)=7.82 (d, 3H), 7.75 (d, 6H), 7.72 (d, 3H), 7.62 (d, 12H), 7.48 (d, 12H), 7.20 (dd, 3H), 6.87 (d, 3H), 4.27 (s, 9H), 2.26 (ddd, 3H), 1.96 (ddd, 3H), 1.37 (s, 54H), 1.05 (m, 6H), 0.73 (t, 9H).
Synthesis Example EM2
Synthesis of Phosphorescent Compound EM2
(162) A phosphorescent compound EM2 was synthesized according to a synthesis method described in WO 2002/066552. The phosphorescent compound EM2 had a TM of 2.52 eV.
(163) ##STR00161##
Example D1
Fabrication and Evaluation of Light Emitting Device D1
(164) On a glass substrate carrying thereon an ITO film with a thickness of 45 nm formed by a sputtering method, a polythiophene-sulfonic acid type hole injecting agent AQ-1200 (Manufactured by Plextronics. Inc.) was spin-coated to form a film with a thickness of 35 nm, which was dried on a hot plate at 170° C. for 15 minutes. Next, a polymer compound IP1 was dissolved at a concentration of 0.6 wt % in xylene. The resultant xylene solution was used and spin-coated at a rotating rate of 1600 rpm to form a film of the polymer compound IP1 with a thickness of 20 nm on the above-described film, then, the film was dried at 180° C. for 60 minutes under a nitrogen gas atmosphere in which the oxygen concentration and the moisture concentration were 10 ppm or less (by weight). Next, the polymer compound P2 and the phosphorescent compound EM1 were dissolved each at a concentration of 2.0 wt % in xylene, and the solutions were mixed so that the weight ratio of polymer compound P2:phosphorescent compound EM1=60:40, to fabricate a composition D1. The resultant composition D1 was spin-coated at a rotating rate of 1860 rpm to form a film with a thickness of about 75 nm on the film of the above-described polymer compound IP1, then, the film was dried at 130° C. for 10 minutes under a nitrogen gas atmosphere in which the oxygen concentration and the moisture concentration were 10 ppm or less (by weight), to obtain a light emitting layer. Next, the pressure was reduced to 1.0×10.sup.−4 Pa or less, then, sodium fluoride was vapor-deposited with a thickness of about 3 nm, as a cathode, on the film of the composition D1 and aluminum was vapor-deposited with a thickness of about 80 nm on the sodium fluoride layer. After vapor deposition, sealing was attained using a glass substrate, to fabricate a light emitting device D1. When voltage was applied to the resultant light emitting device D1, EL light emission showing an emission spectrum peak at 475 nm was obtained from this device, and blue light emission of CIE chromaticity coordinate (0.154, 0.319) was observed. The maximum current efficiency was 7.20 cd/A, the driving voltage in light emission at 1000 cd/m.sup.2 was 7.53 V. The results are shown in Table 2.
(165) The light emitting device D1 obtained above was driven at constant current after setting the current value so that the initial luminance was 400 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 11.2 hours. The results are shown in Table 2.
Example D2
Fabrication and Evaluation of Light Emitting Device D2
(166) A light emitting device D2 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound P3 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM1 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition D2 so that the weight ratio thereof was polymer compound P3:phosphorescent compound EM1=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 1500 rpm, in Example D1. When voltage was applied to the resultant light emitting device D2, EL light emission showing an emission spectrum peak at 475 nm was obtained from this device, and blue light emission of CIE chromaticity coordinate (0.152, 0.321) was observed. The maximum current efficiency was 11.63 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 6.88. The results are shown in Table 2.
(167) The light emitting device D2 obtained above was driven at constant current after setting the current value so that the initial luminance was 400 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 17.9 hours. The results are shown in Table 2.
Example D3
(168) A light emitting device D3 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound P4 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM1 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition D3 so that the weight ratio thereof was polymer compound P4:phosphorescent compound EM1=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 1350 rpm, in Example D1. When voltage was applied to the resultant light emitting device D3, EL light emission showing an emission spectrum peak at 475 nm was obtained from this device, and blue light emission of CIE chromaticity coordinate (0.154, 0.330) was observed. The maximum current efficiency was 12.63 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 6.92 V. The results are shown in Table 2.
(169) The light emitting device D3 obtained above was driven at constant current after setting the current value so that the initial luminance was 400 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 37.7 hours. The results are shown in Table 2.
Comparative Example CD1
(170) A light emitting device CD1 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound CP1 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM1 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition CD1 so that the weight ratio thereof was polymer compound CP1:phosphorescent compound EM1=60:40 and this composition was used, in Example D1. When voltage was applied to the resultant light emitting device CD1, EL light emission showing an emission spectrum peak at 475 nm was obtained from this device, and blue light emission of CIE chromaticity coordinate (0.169, 0.329) was observed. The maximum current efficiency was 1.98 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 10.51 V. The results are shown in Table 2.
(171) The light emitting device CD1 obtained above was driven at constant current after setting the current value so that the initial luminance was 400 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 6.0 hours. The results are shown in Table 2.
Example D4
Fabrication and Evaluation of Light Emitting Device D4
(172) A light emitting device D4 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound P1 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM2 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition D4 so that the weight ratio thereof was polymer compound P1:phosphorescent compound EM2=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 1750 rpm, in Example D1. When voltage was applied to the resultant light emitting device D4, EL light emission showing an emission spectrum peak at 520 nm was obtained from this device, and green light emission of CIE chromaticity coordinate (0.301, 0.640) was observed. The maximum current efficiency was 33.65 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 8.09 V. The results are shown in Table 3.
(173) The light emitting device D4 obtained above was driven at constant current after setting the current value so that the initial luminance was 12000 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 19.6 hours. The results are shown in Table 3.
Example D5
Fabrication and Evaluation of Light Emitting Device D5
(174) A light emitting device D5 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound P2 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM2 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition D5 so that the weight ratio thereof was polymer compound P2:phosphorescent compound EM2=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 1900 rpm, in Example D1. When voltage was applied to the resultant light emitting device D5, EL light emission showing an emission spectrum peak at 520 nm was obtained from this device, and green light emission of CIE chromaticity coordinate (0.301, 0.636) was observed. The maximum current efficiency was 37.01 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 6.68 V. The results are shown in Table 3.
(175) The light emitting device D5 obtained above was driven at constant current after setting the current value so that the initial luminance was 12000 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 10.1 hours. The results are shown in Table 3.
Example D6
Fabrication and Evaluation of Light Emitting Device D6
(176) A light emitting device D6 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound P3 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM2 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition D6 so that the weight ratio thereof was polymer compound P3:phosphorescent compound EM2=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 1610 rpm, in Example D1. When voltage was applied to the resultant light emitting device D6, EL light emission showing an emission spectrum peak at 520 nm was obtained from this device, and green light emission of CIE chromaticity coordinate (0.307, 0.637) was observed. The maximum current efficiency was 24.38 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 6.83 V. The results are shown in Table 3.
(177) The light emitting device D6 obtained above was driven at constant current after setting the current value so that the initial luminance was 12000 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 7.4 hours. The results are shown in Table 3.
Example D7
Fabrication and Evaluation of Light Emitting Device D7
(178) A light emitting device D7 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound P4 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM2 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition D7 so that the weight ratio thereof was polymer compound P4:phosphorescent compound EM2=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 1550 rpm, in Example D1. When voltage was applied to the resultant light emitting device D7, EL light emission showing an emission spectrum peak at 520 nm was obtained from this device, and green light emission of CIE chromaticity coordinate (0.299, 0.640) was observed. The maximum current efficiency was 29.13 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 7.31 V. The results are shown in Table 3.
(179) The light emitting device D7 obtained above was driven at constant current after setting the current value so that the initial luminance was 12000 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 18.4 hours. The results are shown in Table 3.
Example D8
Fabrication and Evaluation of Light Emitting Device D8
(180) A light emitting device D8 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound P5 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM2 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition D8 so that the weight ratio thereof was polymer compound P5:phosphorescent compound EM2=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 1850 rpm, in Example D1. When voltage was applied to the resultant light emitting device D8, EL light emission showing an emission spectrum peak at 520 nm was obtained from this device, and green light emission of CIE chromaticity coordinate (0.309, 0.636) was observed. The maximum current efficiency was 47.80 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 8.60 V. The results are shown in Table 3.
(181) The light emitting device D8 obtained above was driven at constant current after setting the current value so that the initial luminance was 12000 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 3.44 hours. The results are shown in Table 3.
Comparative Example CD2
Fabrication and Evaluation of Light Emitting Device CD2
(182) A light emitting device CD2 was fabricated in the same manner as in Example D1 excepting that a solution of a polymer compound CP2 dissolved at a concentration of 2.0 wt % in a xylene solvent and a solution of a phosphorescent compound EM2 dissolved at a concentration of 2.0 wt % in a xylene solution were mixed to prepare a composition CD2 so that the weight ratio thereof was polymer compound CP2:phosphorescent compound EM2=60:40 and the rotating rate of spin coating using the composition was changed from 1860 rpm to 2900 rpm, in Example D1. When voltage was applied to the resultant light emitting device CD2, EL light emission showing an emission spectrum peak at 520 nm was obtained from this device, and green light emission of CIE chromaticity coordinate (0.309, 0.636) was observed. The maximum current efficiency was 51.96 cd/A, and the driving voltage in light emission at 1000 cd/m.sup.2 was 10.53 V. The results are shown in Table 3.
(183) The light emitting device CD2 obtained above was driven at constant current after setting the current value so that the initial luminance was 12000 cd/m.sup.2, and the time change of luminance was measured. As a result, luminance was attenuated to 60% of the initial luminance after 0.1 hour. The results are shown in Table 3.
(184) TABLE-US-00002 TABLE 2 Polymer Formula Formula Formula LT60 compound (1) (2) (3) [hrs] Example D1 P2 MM1 CC1 CC7 11.2 Example D2 P3 MM1 CC1 17.9 CC5 Example D3 P4 MM1 CC1 CC6 37.7 Comparative CP1 CC1 CC3 6.0 Example CD1 CC7
(in the table, LT60 represents time until luminance reduces to 60% with respect to the initial luminance when a light emitting device is driven at constant current.)
(185) TABLE-US-00003 TABLE 3 Polymer Formula Formula Formula LT60 compound (1) (2) (3) [hrs] Example D4 P1 MM1 19.58 MM2 Example D5 P2 MM1 CC1 CC7 10.13 Example D6 P3 MM1 CC1 7.38 CC5 Example D7 P4 MM1 CC1 CC6 18.41 Example D8 P5 CM1 CC1 CC7 3.44 Comparative CP2 CC1 0.08 Example CD2 CC2
(in the table, LT60 represents the same meaning as described above.)
INDUSTRIAL APPLICABILITY
(186) The present invention is a polymer compound as a host material for a phosphorescent compound, which is useful for production of a light emitting device excellent in luminance life.