JPH02268146A - Fluorene derivative - Google Patents
Fluorene derivativeInfo
- Publication number
- JPH02268146A JPH02268146A JP1087860A JP8786089A JPH02268146A JP H02268146 A JPH02268146 A JP H02268146A JP 1087860 A JP1087860 A JP 1087860A JP 8786089 A JP8786089 A JP 8786089A JP H02268146 A JPH02268146 A JP H02268146A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- pyridine
- fluorene
- expressed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 22
- -1 diethyl diphenyl phosphonate Chemical compound 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 17
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 150000008376 fluorenones Chemical class 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000010410 layer Substances 0.000 description 16
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 238000000862 absorption spectrum Methods 0.000 description 12
- 108091008695 photoreceptors Proteins 0.000 description 11
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 9
- 150000002220 fluorenes Chemical class 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- JXPDNDHCMMOJPC-UHFFFAOYSA-N 2-hydroxybutanedinitrile Chemical compound N#CC(O)CC#N JXPDNDHCMMOJPC-UHFFFAOYSA-N 0.000 description 3
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 2
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IMWGBYPLDBMVAA-UHFFFAOYSA-N 1-(chloromethyl)-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(CCl)=CC=C2 IMWGBYPLDBMVAA-UHFFFAOYSA-N 0.000 description 1
- WNRXGAZAUJVHBG-UHFFFAOYSA-N 4-(chloromethyl)-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C=CC=C2CCl WNRXGAZAUJVHBG-UHFFFAOYSA-N 0.000 description 1
- 229930091051 Arenine Natural products 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- MZHJNYFOGXDJOU-UHFFFAOYSA-N butyl 4-formylbenzoate Chemical compound CCCCOC(=O)C1=CC=C(C=O)C=C1 MZHJNYFOGXDJOU-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BJRYGRGGLTYREP-UHFFFAOYSA-N octyl 4-formylbenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C=O)C=C1 BJRYGRGGLTYREP-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、電子写真感光材料と なフルオレン誘導体に関する。[Detailed description of the invention] Industrial applications The present invention relates to an electrophotographic light-sensitive material and fluorene derivatives.
して有用な新規
従来の技術
従来、有機光導電材料を用いた電子写真感光体について
は、可視光を吸収して電荷を発生する１は荷発生材を含
む電荷発生層と、その電荷の輸送を行う電荷輸送材を含
む電荷輸送層とに機能分離された層構成を有する積層型
の感光層を作成することが行われている。そして、電荷
輸送材としては、アミン系化合物、ヒドラゾン化合物、
ピラゾリン化合物、オ午サジアゾール化合物、スチルベ
ン化合物、カルバゾール化合物等、正孔輸送性の種々の
ものが知られている。Conventionally, electrophotographic photoreceptors using organic photoconductive materials have a charge-generating layer containing a charge-generating material and a charge-generating layer that absorbs visible light and generates charges. A laminated photosensitive layer having a functionally separated layer structure including a charge transporting layer containing a charge transporting material that performs the above-described process has been produced. As charge transport materials, amine compounds, hydrazone compounds,
Various compounds having hole-transporting properties are known, such as pyrazoline compounds, odosadiazole compounds, stilbene compounds, and carbazole compounds.
発明が解決しようとする課題
ところで、機能分離型の電子写真感光体においては、機
械的強度の強い電荷輸送層を上層とすることが一般的で
、従来の正孔輸送材料を用いた場合、負帯電型となる。Problems to be Solved by the Invention However, in functionally separated electrophotographic photoreceptors, it is common to have a charge transport layer with strong mechanical strength as an upper layer, and when conventional hole transport materials are used, negative It becomes a charged type.
しかしながら、コロトロンにおけるオゾンの発生防止、
現像剤におけるトナーの帯電制御等の点から、正帯電型
の方が望ましい。電子写真感光体を正帯電型として用い
る場合、電荷輸送層を上層として用いるには電子輸送材
が必要であるが、従来充分有効な電子輸送＋イは知られ
ていない。However, the prevention of ozone generation in the corotron,
From the viewpoint of controlling the charge of toner in the developer, a positively charging type is more desirable. When an electrophotographic photoreceptor is used as a positively charged type, an electron transport material is required to use a charge transport layer as an upper layer, but a sufficiently effective electron transport material has not been known so far.
本発明は、この様な事情に鑑みてなされたもので、正帯
電用の積層型電子写真感光体におけるＴｌ！子輸子材送
材て有用な有機光導電性材料を提１！（することを目的
とする。The present invention has been made in view of these circumstances, and is aimed at reducing Tl! in a positively charging laminated electrophotographic photoreceptor. We present an organic photoconductive material that is useful for transporting electron transport materials! (The purpose is to
本発明者等は、種々の化合物を合成し、その゛電子写真
特性について検討した結果、ある−群のフルオレン誘導
体が、電子輸送材として優れたものであることを見出だ
し、本発明を完成するに至った。As a result of synthesizing various compounds and studying their electrophotographic properties, the present inventors discovered that a certain group of fluorene derivatives are excellent as electron transport materials, and completed the present invention. reached.
課題を解決するための手段
本発明のフルオレン誘導体は、Ｆ記一般式（１）％式％
（式中、Ｒ１は水素原子又はフェニル基を表わし、Ｒ２
は水素原子、ニトロ基又はアルコキシカルボニル基を表
わし、Ｒ３及びＲ４は、それぞれ水素原子又はアルキル
基を表わす）
上記一般式（１）で示されるフルオレン誘導体がフルオ
レン核の２位又は４位に存在するものである。又、Ｒ２
がアルコキシカルボニル基を示す場合には、炭素数２〜
９個の基であることが好ましい。Means for Solving the Problems The fluorene derivative of the present invention has the general formula (1) F (wherein R1 represents a hydrogen atom or a phenyl group, and R2
represents a hydrogen atom, a nitro group, or an alkoxycarbonyl group, and R3 and R4 each represent a hydrogen atom or an alkyl group) The fluorene derivative represented by the above general formula (1) is present at the 2- or 4-position of the fluorene nucleus. It is something. Also, R2
When represents an alkoxycarbonyl group, the number of carbon atoms is 2 to
Preferably there are nine groups.
本発明の上記フルオレン誘導体は、下記反応式で示すよ
うに、一般式（ｎ）で示されるフルオレン誘導体をピリ
ジン等の溶剤中で酸化して、一般式（ｍ）で示されるフ
ルオレノン誘導体を合成し、次いで、ピリジン等の溶剤
中でマロンニトリルと加熱還流することによって製造す
ることができる。The fluorenone derivative of the present invention can be obtained by oxidizing a fluorenone derivative represented by general formula (n) in a solvent such as pyridine to synthesize a fluorenone derivative represented by general formula (m), as shown in the reaction formula below. , and then heated under reflux with malonitrile in a solvent such as pyridine.
（ＩＩ） （ＩＩＩ）（式中、Ｒ１
ないしＲ４は上記の定義と同一である）
なお、一般式Ｃ■）で示されるフルオレン誘導体は、ホ
ルミルフルオレンを、例えばジエチルジフェニルホスホ
ナートと反応させるか、或いは、クロロメチルフルオレ
ンをトリフェニルホスフィンと反応させ、次いで、相当
するベンズアルデヒドと縮合して合成することができる
。(II) (III) (wherein, R1
to R4 are the same as defined above) The fluorene derivative represented by the general formula C■) can be obtained by reacting formylfluorene with, for example, diethyldiphenylphosphonate, or reacting chloromethylfluorene with triphenylphosphine. and then condensation with the corresponding benzaldehyde.
本発明の上記一般式（１）で示されるフルオレン誘導体
は、優れた電子輸送性を示し、電子写真感光体の電子輸
送材として使用した場合、優れた電子写真特性を示す正
帯電用電子写真感光体を製造することができる。The fluorene derivative represented by the above general formula (1) of the present invention exhibits excellent electron transport properties, and when used as an electron transport material for an electrophotographic photoreceptor, it exhibits excellent electrophotographic properties. body can be manufactured.
実施例
実施例１
２−ホルミルフルオレンとジエチルジフェニルホスホナ
ートとをｎ−ブチルリチウムの存在下、テトラヒドロフ
ラン中で還流して反応させることによって得られた下記
構造式
で示されるフルオレン化合物（ａ＋、ｐ、 １３６．５
〜１３８”Ｃ） ８．５．及びピリジン１００ ｍｌ）
を、１５０ ｒａｎの三つロフラスコに入れ、水冷し、
ベンジルトリメチルアンモニウム・ヒドロキシドの４０
％メタノール溶液０．５−を加え、酸素気流中で１時間
撹拌した。反応終了後、内容物を水１００ ｍＯ中に注
入し、生成した黄色沈澱を濾別し、希塩酸、次いで水で
洗浄した。次いで、塩化メチレンに溶解し、Ｎａ２ＳＯ
４で乾燥した後、シリカゲルショートカラム（塩化メチ
レン／ヘキサン−１／１）で精製し、溶媒を減圧留去し
た後、残渣を酢酸エチル−エタノール混液から再結晶し
て、下記ｌＲ構造式示されるフルオレノン化合物８．５
ｇ ＜収率９４％）を橙黄色針状結晶としてｉｌ）た
。 融点＝１７２〜１７３．５ ℃。Examples Example 1 A fluorene compound represented by the following structural formula (a+, p, 136.5
~138"C) 8.5. and 100 ml of pyridine)
was placed in a 150 ran three-necked flask, cooled with water,
Benzyltrimethylammonium hydroxide 40
% methanol solution was added, and the mixture was stirred for 1 hour in an oxygen stream. After the reaction was completed, the contents were poured into 100 mO of water, and the resulting yellow precipitate was filtered off and washed with dilute hydrochloric acid and then with water. Then dissolved in methylene chloride and NaSO
4, purified with a silica gel short column (methylene chloride/hexane - 1/1), the solvent was distilled off under reduced pressure, and the residue was recrystallized from an ethyl acetate-ethanol mixture to give the following 1R structural formula: Fluorenone compound 8.5
g <94% yield) as orange-yellow needle crystals. Melting point = 172-173.5°C.
このフルオレノン誘導体５．０ｇをピリジン９０１Ｊ２
と共に２５０−三つロフラスコに入れ、窒素気流中１０
０℃に加熱して溶解した後、マロンニトリル１．８ ｇ
をピリジン１０ ｒｎ（！に溶解した溶液を、約ｌ口分
間で滴下し、滴下終了後、混合物を１時間還流した。次
いで室温まで冷却した後、反応混合物を水１００ＩｌΩ
中に注入し、生成した沈澱を濾別し、ピリジン、希塩酸
、水、メタノールの順に洗浄して、下記構造式
で示されるフルオレン化合物（化合物１）５．５ ｇ（
収率９７％）を茶褐色粉末として得た。融点＝２９３〜
２９５．５ ℃
元素分析：
ＣＨＮ
計算値 ８Ｂ、６５ ４．４６ ６．８
９実測値 ８８．７５ ４．２９ ６．
７８質量分析：Ｍ”４０Ｂ
ＵＶ吸収スペクトルλｆｆ１ａＸ ： ５２５ｎＩＢ
、３２３ｎｍＣ１１２Ｃ１２ｒｌｉ
赤外吸収スペクトル： ２２２０ｃｍ −’ （Ｋ１３
ｒ）実施例２
２．７−ジー【−ブチル−４−クロルメチルフルオレン
をトリフェニルホスフィンと反応させ、次いで、４−ニ
トロベンズアルデヒドと縮合して得られた下で示される
フルオレン化合物（融点２０５．５〜２０７．５℃）
５．０ｇを、水酸化カリウム０．３ｇ及びピリジン１
００−と共に、２００ａ＋ｆの丸底フラスコに入れ、空
気雰囲気下で室温において２０時間撹拌した。・反応終
了後、２００ｍｇの水を加え、塩化メチレンで抽出した
後、有機層をＮ ａ ２ Ｓ ０４で乾燥した。溶媒を
減圧留去した後、残渣をシリカゲルショートカラム（塩
化メチレン／ヘキサン−２／ｌ）で精製した。溶媒を減
圧留去した後、残渣を酢酸エチル−エタノール混液から
再結晶して、下記溝で示されるフルオレノン化合物１．
７ ｔｒ （収率３３％）を黄色粉末として得た。融点
：２２３〜２２４℃。5.0g of this fluorenone derivative was added to pyridine 901J2.
Place in a 250-3-necked flask with
After heating to 0℃ and dissolving, 1.8 g of malonitrile
was dissolved in 10 rms of pyridine (!) was added dropwise over a period of about 1 inlet, and after the addition, the mixture was refluxed for 1 hour. After cooling to room temperature, the reaction mixture was poured into 100 IlΩ of water.
The precipitate formed was filtered and washed with pyridine, diluted hydrochloric acid, water, and methanol in this order to obtain 5.5 g of a fluorene compound (compound 1) represented by the following structural formula (
(Yield: 97%) was obtained as a brown powder. Melting point = 293~
295.5 °C Elemental analysis: CHN Calculated value 8B, 65 4.46 6.8
9 Actual value 88.75 4.29 6.
78 Mass spectrometry: M”40B UV absorption spectrum λff1aX: 525nIB
, 323nm C112C12rli Infrared absorption spectrum: 2220cm -' (K13
r) Example 2 The fluorene compound shown below (melting point 205. 5-207.5℃)
5.0g, potassium hydroxide 0.3g and pyridine 1
00- in a 200a+f round bottom flask and stirred for 20 hours at room temperature under an air atmosphere. - After the reaction was completed, 200 mg of water was added, and after extraction with methylene chloride, the organic layer was dried with Na 2 S 04. After evaporating the solvent under reduced pressure, the residue was purified with a silica gel short column (methylene chloride/hexane-2/l). After evaporating the solvent under reduced pressure, the residue was recrystallized from an ethyl acetate-ethanol mixture to obtain the fluorenone compound 1. shown in the groove below.
7 tr (yield 33%) was obtained as a yellow powder. Melting point: 223-224°C.
このフルオレノン誘導体１１０ ｍｇ、マロンニトリル
０．３３ｉ、及びピリジン５０ ｔａｐを、１００−枝
付きフラスコに入れ、混合物を窒素気流中１時間還流し
た後、ピリジンを減圧留去した。残渣を塩化メチレンに
溶かし、シリカゲルショートカラム（塩化メチレンで溶
出）で精製した。塩化メチレンを減圧留去した後、残渣
をメタノールで洗浄し、酢酸エチルから再結晶して、下
記構造式
で示されるフルオレン化合物（化合物２）０．８４ｇ（
収率６９％）を赤茶色針状結晶として得た。融点：２１
１９〜２９０℃
元素分析：
ＣＨＮ
計算値 ７８．８３ ５．９９ ８．８
２実測値 ７ｇ、９４ ５．８２ ８．
５８質量分析： Ｍ＋ ４８７
ＵＶ吸収スペクトルλｗａｘ ： ３１３Ｂｒｖ 、
２５９ｎｉＣ１１２ＣＩ２中
赤外吸収スペクトル： ２２２４．１５９４．１５２８
．１３４４（至）−’（ＫＢｒ）
実施例３
４−クロルメチルフルオレンをトリフェニルホスフィン
と反応させ、次いで、４−ホルミル安息香酸ブチルを反
応させることによって合成された下記構造式
で示されるフルオレン化合物（融点＝７６〜７７℃）を
、実施例２におけると同様にして処理して、シリカゲル
カラム（塩化メチレン／ヘキサン−１／２〜１１Ｏ）で
精製し、下記構造式
％式％
で示されるフルオレノン化合物［シス体、融点：９Ｂ、
５〜９７．５℃（収率７．７％）、トランス体、融点：
１１８−１１７．５℃（収率８１，８％）］を得た。110 mg of this fluorenone derivative, 0.33 i of malonitrile, and 50 taps of pyridine were placed in a 100-branched flask, and the mixture was refluxed in a nitrogen stream for 1 hour, and then pyridine was distilled off under reduced pressure. The residue was dissolved in methylene chloride and purified on a short silica gel column (eluted with methylene chloride). After distilling off methylene chloride under reduced pressure, the residue was washed with methanol and recrystallized from ethyl acetate to obtain 0.84 g of a fluorene compound (compound 2) represented by the following structural formula (
(Yield: 69%) was obtained as reddish brown needle crystals. Melting point: 21
19-290℃ Elemental analysis: CHN Calculated value 78.83 5.99 8.8
2 Actual value 7g, 94 5.82 8.
58 Mass spectrometry: M+ 487 UV absorption spectrum λwax: 313Brv,
259niC112CI2 mid-infrared absorption spectrum: 2224.1594.1528
．． 1344(to)-'(KBr) Example 3 A fluorene compound represented by the following structural formula synthesized by reacting 4-chloromethylfluorene with triphenylphosphine and then reacting with butyl 4-formylbenzoate ( (melting point = 76-77°C) was treated in the same manner as in Example 2 and purified with a silica gel column (methylene chloride/hexane-1/2-11O) to obtain a fluorenone compound represented by the following structural formula % Formula % [cis form, melting point: 9B,
5-97.5°C (yield 7.7%), trans form, melting point:
118-117.5°C (yield 81.8%)].
上記のトランス体を用い、実施例２におけると同様に処
理して、下記構造式
％式％
で示されるフルオレン化合物（化合物３）を赤橙色針状
結晶として得た。融点： １７１−１７２℃（収率７７
．６％）
元素分析：
ＣＨＮ
計算値 ８０．９１ ５．１５ ６．５
１実測値 ８０．９３ ５．２９ ８．
４９質量分析： Ｍ＋ ４３０
ＵＶ吸収スペクトルλｉａｘ ： ３４５ｒ＋ａ＋ 、
３１６ｎｍ、８７ｎｍ
赤外吸収スペクトル： ２２２０．１７３０．１７０８
ｃｍ（ＫＢｒ） 、２２２４．１７１２ｃｍ−’ （
ＣＩＩＣＩ３ ）実施例４
実施例３において得られた構造式（１）で示されるフル
オレノン化合物のシス体を用い、実施例２におけると同
様に処理して、
下記構造式
で示されるフルオレン化合物（化合物４）を橙色粉末と
して得た。融点：１６３〜１８５℃（収率８１．２％）
元素分析：
計算値 ８０．９１
実測値 ８０．８９
質量分析： Ｍ” ４３０
ＵＶ吸収スペクトルλｌ１ａｘ
２８８ｎｔｓ ｓ ２７０ｎｔｓ
赤外吸収スペクトル： ２２２４、
実施例５
下記構造式
％式％
（式中、ｐｈはフェニル基を表わす）
テ示されるフルオレン化合物と４−ホルミル安息香酸オ
クチルを反応させることによって合成された下記構造式
で示されるフルオレン化合物（融点＝６７〜７３℃）を
、実施例２におけると同様にして処理して、シリカゲル
カラム（塩化メチレン／ヘキサン−１７２〜１１Ｏ）で
精製し、下記構造式
％式％
で示されるフルオレノン化合物［シス体、融点＝８１〜
８３℃（収率８．９Ｘ） 、トラ：／ス体、融点＝１１
３．５〜ｌ１４．５℃（収率８０．２％）］を得た。The above trans isomer was used and treated in the same manner as in Example 2 to obtain a fluorene compound (compound 3) represented by the following structural formula % as red-orange needle crystals. Melting point: 171-172°C (yield 77
．． 6%) Elemental analysis: CHN Calculated value 80.91 5.15 6.5
1 Actual value 80.93 5.29 8.
49 Mass spectrometry: M+ 430 UV absorption spectrum λiax: 345r+a+,
316nm, 87nm infrared absorption spectrum: 2220.1730.1708
cm (KBr), 2224.1712 cm-' (
CIICI3) Example 4 The cis form of the fluorenone compound represented by the structural formula (1) obtained in Example 3 was treated in the same manner as in Example 2 to obtain a fluorenone compound (compound 4) represented by the following structural formula. ) was obtained as an orange powder. Melting point: 163-185°C (yield 81.2%)
Elemental analysis: Calculated value 80.91 Actual value 80.89 Mass spectrometry: M" 430 UV absorption spectrum λl1ax 288 nts s 270 nts Infrared absorption spectrum: 2224, Example 5 The following structural formula % formula % (wherein, ph is a phenyl group A fluorene compound represented by the following structural formula (melting point = 67 to 73°C) synthesized by reacting the fluorene compound represented by Te and octyl 4-formylbenzoate was treated in the same manner as in Example 2. and purified with a silica gel column (methylene chloride/hexane-172~11O) to obtain a fluorenone compound [cis form, melting point = 81~
83°C (yield 8.9X), tra:/s body, melting point = 11
3.5-114.5°C (yield 80.2%)] was obtained.
上記のトランス体を用い、実施例２におけると同様に処
理して、下記構造式
００２ＣＩＩＨＩフ
で示されるフルオレン化合物（化合物３）を赤橙色針状
結晶として得た。融点：１４２〜１４４℃（収率８２．
０％）
元素分析：
ＣＨＮ
計算値 ８１．４５ Ｂ、２１ ５．
７６実測値 ８１．４８ Ｂ、２６
５．８３質量分析： Ｍ” ４８６
ＵＶ吸収スペクトルλＩｌｌａｗ ： ３４５ｎｍ 、
３１５ｎｉ 。The above trans isomer was used and treated in the same manner as in Example 2 to obtain a fluorene compound (compound 3) represented by the following structural formula 002CIIHI as red-orange needle-like crystals. Melting point: 142-144°C (yield 82.
0%) Elemental analysis: CHN calculated value 81.45 B, 21 5.
76 Actual value 81.48 B, 26
5.83 Mass spectrometry: M” 486 UV absorption spectrum λIllaw: 345 nm,
315ni.
６５ｎｓ
赤外吸収スペクトル： ２２２０．１７２８．１７１０
ａｍ（ＫＢｒ）
実施例６
実施例５において得られた構造式（２）で示されるフル
オレノン化合物のシス体を用い、実施例２におけると同
様に処理して、
下記構造式
で示されるフルオレン化合物（化合物６）を橙色綿状結
晶として得た。融点＝１２０〜１２１．５℃（収率６０
．４％）
元素分析：
ＣＨＮ
計算値 ８１．４５ Ｂ、２１ ５．
７６実測値 ８１．５５ Ｂ、０５
５．８７質量分析： Ｍ” ４８６
ＵＶ吸収スペクトルλｍａｘ ： ３５５ｎＩｌ、 ２
９７ｎｍ ｓ２８５ｎｍ 、２７０ｎａ＋
赤外吸収スペクトル： ２２２４．１７０８ｃｍ −’
（Ｋｌ）ｒ）応用例１
導電性基板上に、三方晶系セレン／ポリビニルカルバゾ
ール（三方晶系セレンニア容量％）からなる電荷発生層
（２，５Ｉｍ）を設け、その上に、化合物３．４．５又
は８０．５ｇ及びポリカーボネート０．７５ｇを塩化メ
チレン７ｇに溶解した溶液を、湿潤時のギャップ５ミル
で塗布し乾燥して、電子写真感光体を作成した。これら
の電子写真感光体について、静電複写紙試験装置Ｃ３Ｐ
４２Ｂ 、川口電機製作所■製）を用いて＋８００ｖ及
び−８００Ｖに帯電し、５ルツクスの白色光を露光し、
感度（ｄＶ／ｄＴ）を測定した。結果を第１表に示す。65ns Infrared absorption spectrum: 2220.1728.1710
am(KBr) Example 6 Using the cis form of the fluorenone compound represented by the structural formula (2) obtained in Example 5, the same treatment as in Example 2 was carried out to obtain a fluorenone compound represented by the following structural formula ( Compound 6) was obtained as orange flocculent crystals. Melting point = 120-121.5°C (yield 60
．． 4%) Elemental analysis: CHN calculated value 81.45 B, 21 5.
76 Actual value 81.55 B, 05
5.87 Mass spectrometry: M” 486 UV absorption spectrum λmax: 355nIl, 2
97nm s285nm, 270na+ Infrared absorption spectrum: 2224.1708cm -'
(Kl)r) Application example 1 A charge generation layer (2.5Im) made of trigonal selenium/polyvinylcarbazole (trigonal selenium capacity %) is provided on a conductive substrate, and a charge generation layer (2.5Im) made of trigonal selenium/polyvinylcarbazole (trigonal selenium capacity %) is provided on the conductive substrate, and a charge generation layer (2.5Im) is formed on the conductive substrate. A solution prepared by dissolving 0.5 or 80.5 g of polycarbonate and 0.75 g of polycarbonate in 7 g of methylene chloride was coated with a wet gap of 5 mil and dried to prepare an electrophotographic photoreceptor. For these electrophotographic photoreceptors, electrostatic copying paper tester C3P
42B, manufactured by Kawaguchi Electric Seisakusho ■) to +800 V and -800 V, and exposed to 5 Lux white light.
Sensitivity (dV/dT) was measured. The results are shown in Table 1.
参考例
化合物３の代わりに２．４．７−ドリニトロフルオレノ
ン（ＴＮＰ）を用いた以外は、応用例１におけると同様
にして電子写真感光体を作成し、同様にして感度を測定
した。結果を第１表に示す。Reference Example An electrophotographic photoreceptor was prepared in the same manner as in Application Example 1, except that 2.4.7-dolinitrofluorenone (TNP) was used in place of Compound 3, and the sensitivity was measured in the same manner. The results are shown in Table 1.
応用例２
導電性基板上に、無金属フタロシアニンを蒸着して、厚
さｏ、ｔ ｇの電荷発生層を形成した。一方、化合物ｌ
または２０．５ｇ及びビスフェノールＡポリカーボネー
ト０．７５ｇを１．２ジクロルエタンに分散させ、ボー
ルミルで処理した後、得られた分散物を、上記電荷発生
層上に、湿潤時のギャップ７ミルで塗布し乾燥して、電
子写真感光体を作成した。これらの電子写真感光体につ
いて、応用例１におけると同様にして感度を１ｌｌｌ＋
定した。ただし、表面電位＋５００ｖ及び−５００ｖに
帯電した。結果を第１表に示す。Application Example 2 Metal-free phthalocyanine was deposited on a conductive substrate to form a charge generation layer having a thickness of o and tg. On the other hand, compound l
Alternatively, 20.5 g of bisphenol A polycarbonate and 0.75 g of bisphenol A polycarbonate are dispersed in 1.2 dichloroethane, treated with a ball mill, and the resulting dispersion is applied onto the charge generating layer with a wet gap of 7 mil and dried. An electrophotographic photoreceptor was prepared. Regarding these electrophotographic photoreceptors, the sensitivity was increased to 1llll+ in the same manner as in Application Example 1.
Established. However, the surface potentials were charged to +500v and -500v. The results are shown in Table 1.
第１表
発明の効果
本発明の上記一般式（Ｉ）で示されるフルオレン誘導体
は、従来比較的優れたものとして知られているＴＮＦよ
りも優れた電子輸送性を示し、電子写真感光体の電子輸
送材として有用である。例えば、導電性支持体上に電荷
発生層を設けた後、上記フルオレン誘導体を成膜性の樹
脂と共に塗布して電荷輸送層を形成させると、優れた電
子写真特性を有する正帯電用電子写真感光体を製造する
ことができる。Table 1 Effects of the Invention The fluorene derivative of the present invention represented by the above general formula (I) exhibits better electron transport properties than TNF, which is conventionally known to be relatively excellent, and is capable of transporting electrons in electrophotographic photoreceptors. Useful as a transportation material. For example, after a charge generation layer is provided on a conductive support, the above-mentioned fluorene derivative is coated with a film-forming resin to form a charge transport layer. body can be manufactured.
特許出願人 富士ゼロックス株式会社代理人
弁理士 渡部 剛Patent applicant Fuji Xerox Co., Ltd. Agent
Patent Attorney Tsuyoshi Watanabe
Claims (1)
＿２は水素原子、ニトロ基又はアルコキシカルボニル基
を表わし、Ｒ＿３及びＲ＿４は、それぞれ水素原子又は
アルキル基を表わす）(1) A fluorene derivative represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a phenyl group, and R
_2 represents a hydrogen atom, a nitro group or an alkoxycarbonyl group, and R_3 and R_4 each represent a hydrogen atom or an alkyl group)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087860A JPH0657689B2 (en) | 1989-04-10 | 1989-04-10 | Fluorene derivative |
| US07/506,602 US5075487A (en) | 1988-11-16 | 1990-04-10 | Fluorene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1087860A JPH0657689B2 (en) | 1989-04-10 | 1989-04-10 | Fluorene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02268146A true JPH02268146A (en) | 1990-11-01 |
| JPH0657689B2 JPH0657689B2 (en) | 1994-08-03 |
Family
ID=13926640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1087860A Expired - Fee Related JPH0657689B2 (en) | 1988-11-16 | 1989-04-10 | Fluorene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0657689B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100450188B1 (en) * | 1996-12-04 | 2004-12-03 | 삼성에스디아이 주식회사 | Electron receptor for color display panel light conducting layer, especially including fluorenone derivative |
| JP2013100288A (en) * | 2007-07-18 | 2013-05-23 | Idemitsu Kosan Co Ltd | Organic electroluminescent device material and organic electroluminescent device |
-
1989
- 1989-04-10 JP JP1087860A patent/JPH0657689B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100450188B1 (en) * | 1996-12-04 | 2004-12-03 | 삼성에스디아이 주식회사 | Electron receptor for color display panel light conducting layer, especially including fluorenone derivative |
| JP2013100288A (en) * | 2007-07-18 | 2013-05-23 | Idemitsu Kosan Co Ltd | Organic electroluminescent device material and organic electroluminescent device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0657689B2 (en) | 1994-08-03 |
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