JP2007119354A - New carbazole derivative having silyl substituent - Google Patents
New carbazole derivative having silyl substituent Download PDFInfo
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- JP2007119354A JP2007119354A JP2005309623A JP2005309623A JP2007119354A JP 2007119354 A JP2007119354 A JP 2007119354A JP 2005309623 A JP2005309623 A JP 2005309623A JP 2005309623 A JP2005309623 A JP 2005309623A JP 2007119354 A JP2007119354 A JP 2007119354A
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- calbazole
- trimethylsilyl
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- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 title abstract description 5
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 150000001716 carbazoles Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- -1 carbazole compound Chemical class 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 0 Brc1ccc2NC3*=CC(Br)=CC3c2c1 Chemical compound Brc1ccc2NC3*=CC(Br)=CC3c2c1 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- FMSJGXRUJCWSJL-UHFFFAOYSA-N 4-bromo-1-(4-bromophenyl)-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 FMSJGXRUJCWSJL-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は有機電界発光素子の電子輸送層やホスト材料などとして有用なシリル置換基を有する新規カルバゾール誘導体に関する。 The present invention relates to a novel carbazole derivative having a silyl substituent useful as an electron transport layer or a host material of an organic electroluminescence device.
カルバゾール誘導体は有機電界発光素子の材料として注目を集め数多くの研究がなされている。しかし、カルバゾール分子は平面性が高い、溶解性が低い、融点（分解点・昇華点）が低い、製膜性が悪いなどの性質から、素子に応用する際の数多くの問題を現在も抱えている。特許文献１または２にはカルバゾール化合物が開示されているが、シリル置換基を有するカルバゾール化合物は具体的に示されておらず、これまで、シリル置換基を有するカルバゾール化合物は知られていなかった。
本発明は有機電界発光素子の電子輸送層やホスト材料などとして有用な新規な新規カルバゾール誘導体を提供することを課題とする。 An object of the present invention is to provide a novel novel carbazole derivative useful as an electron transport layer, a host material, or the like of an organic electroluminescence device.
本発明者は上記課題を解決すべく鋭意検討を行った。その結果、下記一般式（I）で示される新規カルバゾール誘導体を合成することに成功し、本発明を完成するに至った。 The present inventor has intensively studied to solve the above problems. As a result, the inventors succeeded in synthesizing a novel carbazole derivative represented by the following general formula (I), and completed the present invention.
すなわち、本発明は、下記一般式（Ｉ）で表される化合物を提供する。
下記一般式（Ｉ）で表される化合物。
The compound represented by the following general formula (I).
一般式（I）においては、Ｒ1〜Ｒ6のうち少なくとも２個が-SiRaRbRcで表される基であることが好ましい。また、-SiRaRbRcで表される基においてはＲa、Ｒb、及びＲcが炭素数１〜１０のアルキル基であることが好ましく、メチル基であることがより好ましい。
In general formula (I), it is preferable that at least two of R 1 to R 6 are groups represented by —SiR a R b R c . In the group represented by —SiR a R b R c , R a , R b , and R c are preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.
本発明の化合物は熱安定性および溶解性が高く、性膜性に優れるため加工性が高い。また、本発明の化合物は光吸収効率がよいため、有機電界発光素子の電子輸送層やホスト材料として有用である。
Since the compound of the present invention has high thermal stability and solubility, and excellent in film property, it has high processability. In addition, since the compound of the present invention has good light absorption efficiency, it is useful as an electron transport layer or a host material of an organic electroluminescence device.
以下に本方法を詳しく説明する。 The method will be described in detail below.
本発明の化合物は、下記一般式（I）で表される化合物である。
Ｒa、Ｒb、Ｒcはそれぞれ独立に水素、ヒドロキシル基、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、アリール基から選ばれる基である。アルキル基またはアルコキシ基のアルキル部分は、直鎖でも枝分かれしていてもよく、炭素数１〜４のアルキル基またはアルコキシ基が好ましく、メチル基がより好ましい。また、アリール基としては、フェニル基、トリル基などの置換されたフェニル基、アントリル基、などが挙げられる。なお、Ｒa、Ｒb、Ｒcは互いに同じ置換基であってもよいし、異なるものであってもよい。
Ｒ7は水素、炭素数１〜１０のアルキル基、アリール基から選ばれる基である。アルキル基は直鎖でも枝分かれしていてもよく、炭素数１〜４のアルキル基が好ましい。また、アリール基としては、フェニル基、トリル基などの置換されたフェニル基、アントリル基、などが挙げられる。
R a , R b , and R c are each independently a group selected from hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group. The alkyl part of the alkyl group or alkoxy group may be linear or branched, preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and more preferably a methyl group. Examples of the aryl group include substituted phenyl groups such as a phenyl group and a tolyl group, an anthryl group, and the like. R a , R b , and R c may be the same substituent as each other or different from each other.
R 7 is a group selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and an aryl group. The alkyl group may be linear or branched, and an alkyl group having 1 to 4 carbon atoms is preferable. Examples of the aryl group include substituted phenyl groups such as a phenyl group and a tolyl group, an anthryl group, and the like.
本発明の化合物の製造方法は、該化合物が得られる限り特に制限されないが、例えば、後述の実施例に示すように、ジハロカルバゾールまたはその誘導体をClSiRaRbRcと反応させることによって本発明の化合物を得ることができる。得られた化合物は、カラムクロマトグラフィーなどの通常の単離操作によって回収することができる。化合物の構造はX線結晶構造解析やNMRなどによって確認することができる。
後述の実施例に示すように、本発明の化合物は、シリル基を有するため、光吸収が向上している。また、耐熱性も上昇している。したがって、有機エレクトロルミネッセンス素
子などの光学材料に応用することができる。
［実施例］
The method for producing the compound of the present invention is not particularly limited as long as the compound can be obtained. For example, as shown in the Examples below, the present method can be used by reacting dihalocarbazole or a derivative thereof with ClSiR a R b R c. The compounds of the invention can be obtained. The obtained compound can be recovered by a normal isolation operation such as column chromatography. The structure of the compound can be confirmed by X-ray crystal structure analysis or NMR.
As shown in the below-mentioned Examples, the compound of the present invention has a silyl group, so that light absorption is improved. Moreover, the heat resistance is also increased. Therefore, it can be applied to an optical material such as an organic electroluminescence element.
[Example]
以下に実施例を示し、本発明をさらに具体的に説明する。もっとも、本発明は下記実施例に限定されるものではない。 The following examples illustrate the present invention more specifically. However, the present invention is not limited to the following examples.
＜シリル置換カルバゾール誘導体の合成＞
1. 3,6-bis(trimethylsilyl)calbazoleの合成
1.1. 3,6-dibromocalbazole の合成
2.674 g) および CH2Cl2 (200 mL) を収め 1.5 時間かけてそれを滴下し、終夜で撹拌した。シリカゲルを濾過で除き、濾液の溶媒を減圧下で除去した。カラムクロマトグラフィーにてポリマー分を除き、ついで再結晶することで、目的化合物である 3,6-dibromocalbazole を淡茶色固体として、収量 1.19 g、収率 51% で得た。
<Synthesis of silyl-substituted carbazole derivative>
1. Synthesis of 3,6-bis (trimethylsilyl) calbazole
1.1. Synthesis of 3,6-dibromocalbazole
2.674 g) and CH 2 Cl 2 (200 mL) were added dropwise over 1.5 hours and stirred overnight. Silica gel was removed by filtration and the solvent of the filtrate was removed under reduced pressure. The polymer component was removed by column chromatography, and then recrystallized to obtain the target compound 3,6-dibromocalbazole as a light brown solid in a yield of 1.19 g and a yield of 51%.
1.2. 3,6-bis(trimethylsilyl)calbazoleの合成
mL） を滴下し、2 時間撹拌した。Me3SiCl (420 mg) を滴下後、−78°Cのまま 30 分撹拌し、徐々に室温に戻し、終夜で撹拌した。再び氷浴にし、5% 塩酸水溶液を 5 mL 入れた。飽和塩化アンモニウム水溶液と Et2O で洗浄、分液し、有機相を無水硫酸マグネシウムで乾燥した。硫酸マグネシウムを除去後、溶媒を減圧下で除去した。ポリマー分を除去し、リサイクル型高速液体クロマトグラフィーにて分取することで目的化合物である 3,6-bis(trimethylsilyl)-calbazole を白色固体として、収量 57.4 mg、収率 29% で得た。MS（質量分析） (EI, 70 eV) m/z (%) 311 (M+, 67), 296 (100), 73 (10)
IR（赤外吸収スペクトル） (KBr) cm-1 3416, 3028, 2951, 2893, 1614, 1595, 1462, 1279, 1259, 1244, 1223, 1204, 1144, 1096, 1074, 837, 808, 758, 737, 691
1H NMR （核磁気共鳴スペクトル）(500 MHz, CDCl3) δ 0.35 (s, 18H), 7.41 (d, 2H), 7.54 (d 2H), 8.00 (s, 1H), 8.25 (s, 2H) ppm
13C NMR (126 MHz, CDCl3) δ -0.57, 110.13, 122.92, 122.34, 129.84, 130.68, 139.91 ppm
29Si NMR (99 MHz, CDCl3) δ -3.7 ppm
1.2. Synthesis of 3,6-bis (trimethylsilyl) calbazole
mL) was added dropwise and stirred for 2 hours. After dropwise addition of Me 3 SiCl (420 mg), the mixture was stirred at −78 ° C. for 30 minutes, gradually returned to room temperature, and stirred overnight. It was made into an ice bath again, and 5 mL of 5% hydrochloric acid aqueous solution was put. The organic phase was washed with a saturated aqueous ammonium chloride solution and Et 2 O and separated, and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the solvent was removed under reduced pressure. The polymer content was removed and fractionated by recycle high performance liquid chromatography to obtain the target compound 3,6-bis (trimethylsilyl) -calbazole as a white solid in a yield of 57.4 mg and a yield of 29%. MS (mass spectrometry) (EI, 70 eV) m / z (%) 311 (M + , 67), 296 (100), 73 (10)
IR (infrared absorption spectrum) (KBr) cm -1 3416, 3028, 2951, 2893, 1614, 1595, 1462, 1279, 1259, 1244, 1223, 1204, 1144, 1096, 1074, 837, 808, 758, 737 , 691
1 H NMR (nuclear magnetic resonance spectrum) (500 MHz, CDCl 3 ) δ 0.35 (s, 18H), 7.41 (d, 2H), 7.54 (d 2H), 8.00 (s, 1H), 8.25 (s, 2H) ppm
13 C NMR (126 MHz, CDCl 3 ) δ -0.57, 110.13, 122.92, 122.34, 129.84, 130.68, 139.91 ppm
29 Si NMR (99 MHz, CDCl 3 ) δ -3.7 ppm
1.3. 3,6-bis(trimethylsilyl)calbazoleのＸ線結晶構造解析
3,6-bis(trimethylsilyl)calbazoleのＸ線結晶構造解析を行った。結果を図１に示す。シリル基の導入によりカルバゾール環の上下にメチル基が大きく張り出していることから、カルバゾール同士のスタッキングが阻害されるものと考えられる。
1.3. X-ray crystallographic analysis of 3,6-bis (trimethylsilyl) calbazole
X-ray crystal structure analysis of 3,6-bis (trimethylsilyl) calbazole was performed. The results are shown in FIG. It is considered that stacking between carbazoles is hindered because methyl groups are greatly extended above and below the carbazole ring by introduction of silyl groups.
1.4. 3,6-bis(trimethylsilyl)calbazoleの紫外吸収スペクトル
3,6-bis(trimethylsilyl)calbazoleおよびcalbazoleの紫外吸収スペクトルを ジクロロメタン中、室温で測定した結果を図２に示す。いずれのピークに関しても、シリル基の導入により長波長シフトしていることがわかる。
1.4. UV absorption spectrum of 3,6-bis (trimethylsilyl) calbazole
The ultraviolet absorption spectra of 3,6-bis (trimethylsilyl) calbazole and calbazole measured in dichloromethane at room temperature are shown in FIG. It can be seen that any of the peaks is shifted by a long wavelength due to the introduction of the silyl group.
1.5. 3,6-bis(trimethylsilyl)calbazoleの蛍光発光スペクトル
3,6-bis(trimethylsilyl)calbazoleおよびcalbazoleの蛍光スペクトルをジクロロメタン中、室温、励起波長 299 nm で測定した結果を図３に示す。蛍光極大は 347 nm、 362 nm であり、calbazoleの対応する蛍光極大よりも長波長シフトしていることがわかる。
1.5. Fluorescence emission spectrum of 3,6-bis (trimethylsilyl) calbazole
The fluorescence spectra of 3,6-bis (trimethylsilyl) calbazole and calbazole measured in dichloromethane at room temperature and excitation wavelength of 299 nm are shown in FIG. The fluorescence maxima are 347 nm and 362 nm, indicating that the wavelength shift is longer than the corresponding fluorescence maxima of calbazole.
1.6. 3,6-bis(trimethylsilyl)calbazoleの熱重量減少の測定
さらに、3,6-bis(trimethylsilyl)calbazoleおよびcalbazoleをそれぞれ窒素雰囲気下で加熱し、重量変化を測定した（図４）。その結果、3,6-bis(trimethylsilyl)calbazoleはcalbazoleと比べて熱安定性が向上していることがわかった。
1.6. Measurement of thermogravimetric decrease of 3,6-bis (trimethylsilyl) calbazole Further, 3,6-bis (trimethylsilyl) calbazole and calbazole were heated in a nitrogen atmosphere, respectively, and the weight change was measured (FIG. 4). As a result, 3,6-bis (trimethylsilyl) calbazole was found to have improved thermal stability compared to calbazole.
2. 2,7-bis(trimethylsilyl)calbazoleの合成
2.1. 4,4'-dibromo-2-nitrobiphenyl の合成
2.1. Synthesis of 4,4'-dibromo-2-nitrobiphenyl
2.2. 2,7-dibromocalbazole の合成
2.3. 2,7-bis(trimethylsilyl)calbazole の合成
mL） を滴下し、2 時間撹拌した。Me3SiCl (502.0 mg) を滴下後、−78°Cのまま 30 分撹拌し、徐々に室温に戻し、終夜で撹拌した。再び氷浴にし、5% 塩酸水溶液を 5 mL 入れた。飽和塩化アンモニウム水溶液と Et2O で洗浄、分液し、有機相を無水硫酸マグネシウムで乾燥した。硫酸マグネシウムを除去後、溶媒を減圧下で除去した。ポリマー分を除去し、リサイクル型高速液体クロマトグラフィーにて分取することで目的化合物である 2,7-bis(trimethylsilyl)-calbazole を白色固体として、収量 130 mg、収率 67% で得た。
MS（質量分析） (EI, 70 eV) m/z (%) 311 (M+, 82), 296 (100), 73 (8)
IR（赤外吸収スペクトル） (KBr) cm-1 3408, 3049, 3028, 2955, 2895, 1447, 1442, 1333, 1323, 1246, 1211, 1086, 914, 835, 806, 754, 679, 621
1H NMR （核磁気共鳴スペクトル）(500 MHz, CDCl3) δ 0.32 (s, 18H), 7.35 (d, 2H),
7.58 (s 2H), 7.98 (s, 1H), 8.04 (d, 2H) ppm
13C NMR (126 MHz, CDCl3) δ -0.81, 115.44, 119.79, 123.77, 124.00, 138.03, 139.31 ppm
29Si NMR (99 MHz, CDCl3) δ -3.3 ppm
2.3. Synthesis of 2,7-bis (trimethylsilyl) calbazole
mL) was added dropwise and stirred for 2 hours. After dropwise addition of Me 3 SiCl (502.0 mg), the mixture was stirred at −78 ° C. for 30 minutes, gradually returned to room temperature, and stirred overnight. It was made into an ice bath again, and 5 mL of 5% hydrochloric acid aqueous solution was put. The organic phase was washed with a saturated aqueous ammonium chloride solution and Et 2 O and separated, and dried over anhydrous magnesium sulfate. After removing the magnesium sulfate, the solvent was removed under reduced pressure. The polymer content was removed and fractionated by recycle high performance liquid chromatography to obtain the target compound 2,7-bis (trimethylsilyl) -calbazole as a white solid in a yield of 130 mg and a yield of 67%.
MS (mass spectrometry) (EI, 70 eV) m / z (%) 311 (M + , 82), 296 (100), 73 (8)
IR (infrared absorption spectrum) (KBr) cm -1 3408, 3049, 3028, 2955, 2895, 1447, 1442, 1333, 1323, 1246, 1211, 1086, 914, 835, 806, 754, 679, 621
1 H NMR (nuclear magnetic resonance spectrum) (500 MHz, CDCl 3 ) δ 0.32 (s, 18H), 7.35 (d, 2H),
7.58 (s 2H), 7.98 (s, 1H), 8.04 (d, 2H) ppm
13 C NMR (126 MHz, CDCl 3 ) δ -0.81, 115.44, 119.79, 123.77, 124.00, 138.03, 139.31 ppm
29 Si NMR (99 MHz, CDCl 3 ) δ -3.3 ppm
2.4. 2,7-bis(trimethylsilyl)calbazoleの紫外吸収スペクトル
2,7-bis(trimethylsilyl)calbazoleおよびcalbazoleの紫外吸収スペクトルを ジクロロメタン中、室温で測定した結果を図５に示す。いずれのピークに関しても、シリル基の導入により長波長シフトしていることがわかる。
2.4. UV absorption spectrum of 2,7-bis (trimethylsilyl) calbazole
The ultraviolet absorption spectra of 2,7-bis (trimethylsilyl) calbazole and calbazole measured in dichloromethane at room temperature are shown in FIG. It can be seen that any of the peaks is shifted by a long wavelength due to the introduction of the silyl group.
2.5. 2,7-bis(trimethylsilyl)calbazoleの蛍光発光スペクトル
2,7-bis(trimethylsilyl)calbazoleおよびcalbazoleの蛍光スペクトルを2-メチル ＴＨＦ中、室温、励起波長 300 nm で測定した結果を図６に示す。蛍光極大は 359 nm、 375 nm であり、calbazoleの対応する蛍光極大よりも長波長シフトしていることがわかる。
2.5. Fluorescence emission spectrum of 2,7-bis (trimethylsilyl) calbazole
The fluorescence spectra of 2,7-bis (trimethylsilyl) calbazole and calbazole were measured in 2-methyl THF at room temperature at an excitation wavelength of 300 nm. The fluorescence maximums are 359 nm and 375 nm, indicating that the wavelength shifts longer than the corresponding fluorescence maximum of calbazole.
2.6. 2,7-bis(trimethylsilyl)calbazoleの熱重量減少の測定
さらに、2,7-bis(trimethylsilyl)calbazoleおよびcalbazoleをそれぞれ窒素雰囲気下で加熱し、重量変化を測定した（図７）。その結果、2,7-bis(trimethylsilyl)calbazoleはcalbazoleと比べて熱安定性が向上していることがわかった。
2.6. Measurement of thermogravimetric decrease of 2,7-bis (trimethylsilyl) calbazole Further, 2,7-bis (trimethylsilyl) calbazole and calbazole were heated in a nitrogen atmosphere, respectively, and the weight change was measured (FIG. 7). As a result, it was found that 2,7-bis (trimethylsilyl) calbazole had improved thermal stability compared with calbazole.
Claims (5)
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| CN102875447A (en) * | 2012-03-06 | 2013-01-16 | 河南省科学院化学研究所有限公司 | Method for preparing 2,7-dibromocarbazole |
| JP2013227268A (en) * | 2011-09-15 | 2013-11-07 | Jnc Corp | Carbazole compound with substituent group containing electron-accepting nitrogen containing heteroaryl and organic electroluminescent device |
| JP2014196464A (en) * | 2013-03-08 | 2014-10-16 | 住友化学株式会社 | Production method for amine compound |
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| JP2014196464A (en) * | 2013-03-08 | 2014-10-16 | 住友化学株式会社 | Production method for amine compound |
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