JPS6215097B2 - - Google Patents
Info
- Publication number
- JPS6215097B2 JPS6215097B2 JP3574882A JP3574882A JPS6215097B2 JP S6215097 B2 JPS6215097 B2 JP S6215097B2 JP 3574882 A JP3574882 A JP 3574882A JP 3574882 A JP3574882 A JP 3574882A JP S6215097 B2 JPS6215097 B2 JP S6215097B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- photoreceptor
- nitrocarbazole
- bis
- compound
- 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.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 108091008695 photoreceptors Proteins 0.000 description 17
- -1 9-substituted-3,6-bis(p-nitrostyryl)-1-nitrocarbazole Chemical class 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- XRMUUSATUCOGCF-UHFFFAOYSA-N 3,6-dibromo-1-nitro-9h-carbazole Chemical compound N1C2=CC=C(Br)C=C2C2=C1C([N+](=O)[O-])=CC(Br)=C2 XRMUUSATUCOGCF-UHFFFAOYSA-N 0.000 description 2
- 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
- JFGQHAHJWJBOPD-UHFFFAOYSA-N 3-hydroxy-n-phenylnaphthalene-2-carboxamide Chemical compound OC1=CC2=CC=CC=C2C=C1C(=O)NC1=CC=CC=C1 JFGQHAHJWJBOPD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- VYOKOQDVBBWPKO-UHFFFAOYSA-N 1-nitro-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C([N+](=O)[O-])=CC=C2 VYOKOQDVBBWPKO-UHFFFAOYSA-N 0.000 description 1
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YGBCLRRWZQSURU-UHFFFAOYSA-N 4-[(diphenylhydrazinylidene)methyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=NN(C=1C=CC=CC=1)C1=CC=CC=C1 YGBCLRRWZQSURU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ZJAKNSASNSLIOG-UHFFFAOYSA-N methyl 4-bis(4-methoxycarbonylphenyl)phosphanylbenzoate Chemical compound C1=CC(C(=O)OC)=CC=C1P(C=1C=CC(=CC=1)C(=O)OC)C1=CC=C(C(=O)OC)C=C1 ZJAKNSASNSLIOG-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 description 1
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 description 1
- MEYTUZLAONGIPB-UHFFFAOYSA-N tris[2,5-di(propan-2-yl)phenyl]phosphane Chemical compound CC(C)C1=CC=C(C(C)C)C(P(C=2C(=CC=C(C=2)C(C)C)C(C)C)C=2C(=CC=C(C=2)C(C)C)C(C)C)=C1 MEYTUZLAONGIPB-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】
本発明は新規なトリスアゾ化合物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel trisazo compounds.
近年、有機光導電材料を用いた電子写真感光体
が多数提案されている。例えば、ポリ―Ｎ―ビニ
ルカルバゾールと２，４，７―トリニトロフルオ
レン―９―オンを含有する感光層を設けた感光
体、ポリ―Ｎ―ビニルカルバゾールをピリリウム
塩系色素で増感した感光層を設けた感光体、有機
顔料を主成分とする感光層を設けた感光体、電荷
発生層と電荷移送層とを積層した感光層を有する
感光体、染料と樹脂からなる共晶錯体を主成分と
する感光層を設けた感光体などがある。 In recent years, many electrophotographic photoreceptors using organic photoconductive materials have been proposed. For example, a photoreceptor with a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-trinitrofluoren-9-one, a photoreceptor with a photosensitive layer containing poly-N-vinylcarbazole sensitized with a pyrylium salt dye. A photoreceptor with a photoreceptor layer containing organic pigment as the main component, a photoreceptor with a photoreceptor layer consisting of a charge generation layer and a charge transport layer, a photoreceptor with a photoreceptor layer consisting of a charge generation layer and a charge transport layer, a photoreceptor with a eutectic complex consisting of a dye and a resin as the main component. There are photoreceptors that are provided with a photosensitive layer.
前記の感光体はいくつかの勝れた特性を有する
ものであるが、セレンに代表される無機感光体に
比べて概して光感度の低いことが電子写真感光体
としての大きい短所の一つとなつている。 Although the above photoreceptors have some excellent properties, one of their major drawbacks as electrophotographic photoreceptors is that they generally have lower photosensitivity than inorganic photoreceptors such as selenium. There is.
本発明の目的は、上記の欠点を解消し、光導電
材料として勝れた特性を有する新規なトリスアゾ
化合物を提供することにある。 An object of the present invention is to eliminate the above-mentioned drawbacks and to provide a novel trisazo compound having excellent properties as a photoconductive material.
即ち、本発明は、一般式〔Ｉ〕 （但し、Ｒはアルキル基。） で示される新規なトリスアゾ化合物である。 That is, the present invention provides general formula [I] (However, R is an alkyl group.) This is a novel trisazo compound represented by:
上記の本発明のトリスアゾ化合物〔Ｉ〕は下記
の方法によつて製造することができる。即ち、一
般式〔〕
（但し、Ｘはアニオン官能基で、R2はアルキル
基、シクロアルキル基又はアラルキル基。）
で示されるヘキサゾニウム塩と、一般式〔〕
（但し、R1はアルキル基、アルコキシ基、ニトロ
基、ジアルキルアミノ基又はハロゲン、ｎは０、
１、２又は３の整数であつて、ｎが２又は３の整
数である場合には同一又は異なつた基のいずれで
もよい。）
で示される化合物とを反応させる。 The above trisazo compound [I] of the present invention can be produced by the following method. That is, the general formula [] (However, X is an anionic functional group, and R 2 is an alkyl group, cycloalkyl group, or aralkyl group.) A hexazonium salt represented by the general formula [] (However, R 1 is an alkyl group, alkoxy group, nitro group, dialkylamino group, or halogen, n is 0,
They are an integer of 1, 2 or 3, and when n is an integer of 2 or 3, they may be the same or different groups. ) is reacted with the compound shown in
前記ヘキサゾニウム塩は、一般式〔〕
（但し、Ｙは臭素又は沃素、R2はアルキル基、シ
クロアルキル基又はアラルキル基を表わす。）で
示される、例えば、９―置換―３，６―ジハロ―
１―ニトロカルバゾールとｐ―ニトロスチレンを
反応させて製造される、一般式〔〕
で示される新規化合物の９―置換―３，６―ビス
（ｐ―ニトロスチリル）―１―ニトロカルバゾー
ルを還元して、一般式〔〕
で示される９―置換―３，６―ビス（ｐ―アミノ
スチリル）―１―アミノカルバゾールとし、次い
でジアゾ化することにより得ることができる。 The hexazonium salt has the general formula [] (However, Y represents bromine or iodine, and R 2 represents an alkyl group, cycloalkyl group, or aralkyl group.) For example, 9-substituted-3,6-dihalo-
General formula [] produced by reacting 1-nitrocarbazole and p-nitrostyrene By reducing the 9-substituted-3,6-bis(p-nitrostyryl)-1-nitrocarbazole of the new compound represented by the general formula [] It can be obtained by preparing a 9-substituted-3,6-bis(p-aminostyryl)-1-aminocarbazole represented by the formula and then diazotizing it.
９―置換―３，６―ジハロ―１―ニトロカルバ
ゾールとｐ―ニトロスチレンの反応には通常、触
媒とハロゲン化水素捕促剤とが必要とされる。触
媒としては酢酸パラジウム等の貴金属化合物とト
リアリールホスフインなどのリン化合物との組み
合せが適当である。 The reaction of 9-substituted-3,6-dihalo-1-nitrocarbazole with p-nitrostyrene typically requires a catalyst and a hydrogen halide scavenger. A suitable catalyst is a combination of a noble metal compound such as palladium acetate and a phosphorus compound such as triarylphosphine.
トリアリールホスフインとしては、トリフエニ
ルホスフイン、トリ―ｏ―トリルホスフイン、ト
リス（２，５―ジイソ―プロピルフエニル）ホス
フイン、トリ―α―ナフチルホスフイン、トリス
（２，３，４，５―テトラメチル）フエニルホス
フイン、トリス（２−メチル―５―ｔ―ブチルフ
エニル）ホスフイン、トリス（ｐ―カルボメトキ
シフエニル）ホスフインなどのホスフインを挙げ
ることができるが、特にトリ―ｏ―トリルホスフ
イン、トリス（２―メチル―５―ｔ―ブチルフエ
ニル）ホスフインの使用が好ましい。本発明に使
用するトリアリールホスフインは酢酸パラジウム
１モルに対して0.5〜10モルが適当である。ま
た、酢酸パラジウムの使用量はスチレン誘導体使
用量の0.25〜２モル％が適当である。 Triarylphosphines include triphenylphosphine, tri-o-tolylphosphine, tris(2,5-diiso-propylphenyl)phosphine, tri-α-naphthylphosphine, tris(2,3,4, Mention may be made of phosphine such as 5-tetramethyl)phenylphosphine, tris(2-methyl-5-t-butylphenyl)phosphine, tris(p-carbomethoxyphenyl)phosphine, but especially tri-o-tolyl Preference is given to using phosphine, tris(2-methyl-5-t-butylphenyl)phosphine. The triarylphosphine used in the present invention is suitably used in an amount of 0.5 to 10 mol per mol of palladium acetate. Further, the appropriate amount of palladium acetate to be used is 0.25 to 2 mol% of the amount of styrene derivative used.
ハロゲン化水素捕促剤としては、２級アミン、
３級アミン類や炭酸水素ナトリウム、炭酸ナトリ
ウムなどの塩基性の塩などが適当である。このよ
うな２級アミン、３級アミンとしては、ジエチル
アミン、ジ―ｎ―ブチルアミン、ピペリジン、モ
ルホリン、トリエチルアミン、トリ―ｎ―ブチル
アミン、トリアミルアミン、テトラメチルエチレ
ンジアミン等のごくありふれたアミンでよく、そ
の使用量は発生するハロゲン化水素に当モルより
少し過剰に使用する。反応溶媒としては一般的な
もの、例えば、Ｎ，Ｎ―ジメチルホルムアミド、
ジメチルアセトアミド、トルエン、キシレン、ク
ロルベンゼン、ｏ―ジクロルベンゼン、トリクロ
ルベンゼン、Ｎ―メチル―２―ピロリドン、ジメ
チルスルホキシドが用いられる。反応は75〜150
℃の温度範囲で行われる。 As hydrogen halide scavengers, secondary amines,
Tertiary amines and basic salts such as sodium bicarbonate and sodium carbonate are suitable. Such secondary amines and tertiary amines may be common amines such as diethylamine, di-n-butylamine, piperidine, morpholine, triethylamine, tri-n-butylamine, triamylamine, and tetramethylethylenediamine. The amount used is slightly in excess of the molar equivalent of hydrogen halide generated. Common reaction solvents such as N,N-dimethylformamide,
Dimethylacetamide, toluene, xylene, chlorobenzene, o-dichlorobenzene, trichlorobenzene, N-methyl-2-pyrrolidone, and dimethyl sulfoxide are used. Reaction is 75-150
It is carried out in a temperature range of ℃.
このようにして得られる新規化合物の９―置換
―３，６―ビス（ｐ―ニトロスチリル）―１―ニ
トロカルバゾール〔〕は還元して９―置換―
３，６―ビス（ｐ―アミノスチリル）―１―アミ
ノカルバゾールとし、ジアゾ化してヘキサゾニウ
ム塩とするが、ジアゾ化は９―置換―３，６―ビ
ス（ｐ―アミノスチリル）―１―アミノカルバゾ
ールを希塩酸、希硫酸のような希薄無機酸中に加
え、さらに、これに亜硝酸ナトリウム水溶液を−
10〜10℃の温度に保ちつゝ添加することにより行
われる。このジアゾ化は30分〜２時間で完結す
る。この場合、反応混合物は、例えば硼弗化水素
酸などを加えてヘキサゾニウム塩として沈澱さ
せ、取して結晶を得ることが望ましい。 The thus obtained new compound 9-substituted-3,6-bis(p-nitrostyryl)-1-nitrocarbazole [] is reduced to 9-substituted-
3,6-bis(p-aminostyryl)-1-aminocarbazole is diazotized to form a hexazonium salt, but diazotization is 9-substituted-3,6-bis(p-aminostyryl)-1-aminocarbazole. is added to a dilute inorganic acid such as dilute hydrochloric acid or dilute sulfuric acid, and then a sodium nitrite aqueous solution is added to this.
This is done by adding while maintaining the temperature at 10 to 10°C. This diazotization is completed in 30 minutes to 2 hours. In this case, it is desirable that the reaction mixture is precipitated as a hexazonium salt by adding, for example, borofluoric acid, and then collected to obtain crystals.
次いで前記ヘキサゾニウム塩〔〕に前記化合
物〔〕をヘキサゾニウム基に対して１〜10倍モ
ル、好ましくは２〜５倍モル量を添加して、カツ
プリング反応を起こさせる。実際には、この反応
はＮ，Ｎ―ジメチルホルムアミドやジメチルスル
ホキシドなどの有機溶媒にヘキサゾニウム塩及び
カツプリング成分を溶解しておき、−10〜10℃の
温度に保持しつゝ、酢酸ナトリウム水溶液などの
アルカリ水溶液を滴下することにより行なわれ
る。 Next, the compound [] is added to the hexazonium salt [] in an amount of 1 to 10 times the molar amount, preferably 2 to 5 times the molar amount based on the hexazonium group, to cause a coupling reaction. In reality, this reaction is carried out by dissolving the hexazonium salt and the coupling component in an organic solvent such as N,N-dimethylformamide or dimethyl sulfoxide, and then maintaining it at a temperature of -10 to 10°C while using an aqueous solution such as sodium acetate. This is done by dropping an aqueous alkaline solution.
かくして得られる本発明の新規なトリスアゾ化
合物は、電子写真用感光体の光導電素材として特
に有用である。従つて、例えば
(1) トリスアゾ化合物からなる感光層
(2) トリスアゾ化合物をバインダー中に分散させ
た感光層
(3) トリスアゾ化合物を周知の電荷移動媒体中に
分散させた感光層
(4) 前記(1)〜(3)の感光層を電荷発生層とし、これ
に周知の電荷移動媒体を含む電荷移動層を積層
した感光層
などが新規トリスアゾ化合物の用途例として挙げ
ることができる。 The novel trisazo compound of the present invention thus obtained is particularly useful as a photoconductive material for electrophotographic photoreceptors. Therefore, for example, (1) a photosensitive layer made of a trisazo compound (2) a photosensitive layer containing a trisazo compound dispersed in a binder (3) a photosensitive layer containing a trisazo compound dispersed in a known charge transfer medium (4) the above ( Examples of uses of the novel trisazo compound include a photosensitive layer in which the photosensitive layers 1) to (3) are used as a charge generation layer, and a charge transfer layer containing a well-known charge transfer medium is laminated thereon.
以下に、本発明を実施例により具体的に説明す
るが、本発明はこれら実施例のみに限定されるも
のではない。 EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.
実施例
の合成
３，６―ジブロモカルバゾール6.5部（重量
部、以下同じ）を酢酸80部に溶解し、撹拌しなが
ら酢酸10部に溶解させた発煙硝酸（ｄ＝1.52）
1.33部を室温にて滴下し、滴下終了後、70℃に加
熱し２時間反応させた。冷却して析出してくる析
出物を取し、クロロベンゼンより再結晶するこ
とにより、３，６―ジブロモ―１―ニトロカルバ
ゾール5.17部（収率70％）を黄色結晶として得
た。融点267.8℃。Example Synthesis of fuming nitric acid (d=1.52) in which 6.5 parts of 3,6-dibromocarbazole (parts by weight, same hereinafter) was dissolved in 80 parts of acetic acid, and dissolved in 10 parts of acetic acid with stirring.
1.33 parts were added dropwise at room temperature, and after the addition was completed, the mixture was heated to 70°C and reacted for 2 hours. The precipitate deposited after cooling was collected and recrystallized from chlorobenzene to obtain 5.17 parts (yield 70%) of 3,6-dibromo-1-nitrocarbazole as yellow crystals. Melting point: 267.8℃.
３，６―ジブロモ―１―ニトロカルバゾール
5.0部をジメチルホルムアミド（以下、DMFと略
す）45部中に分散させた後、粉末のKOH0.8部を
加えた。DMF5部に溶解させたイソアミルブロマ
イド2.15部を室温にて滴下し、滴下終了後、70℃
にて５時間、90℃にて３時間反応させた。冷却
後、反応物を300部の水中に注加し、析出してく
る析出物を取し、十分水洗後、エタノールより
再結晶することにより、９―イソアミル―３，６
―ジブロモ―１―ニトロカルバゾール4.00部（収
率67％）を黄色結晶として得た。 3,6-dibromo-1-nitrocarbazole
After dispersing 5.0 parts in 45 parts of dimethylformamide (hereinafter abbreviated as DMF), 0.8 parts of powdered KOH was added. 2.15 parts of isoamyl bromide dissolved in 5 parts of DMF was added dropwise at room temperature.
The reaction was carried out for 5 hours at 90°C and for 3 hours at 90°C. After cooling, the reaction product was poured into 300 parts of water, the precipitate was collected, washed thoroughly with water, and recrystallized from ethanol to obtain 9-isoamyl-3,6.
4.00 parts of -dibromo-1-nitrocarbazole (yield 67%) was obtained as yellow crystals.
９―イソアミル―３，６―ジブロモ―１―ニト
ロカルバゾール4.00部、ｐ―ニトロスチレン3.12
部、トリ―ｎ―ブチルアミン3.88部、トリ―ｏ―
トリルホスフイン0.111部、酢酸パラジウム0.041
部、Ｎ―メチル―２―ピロリドン（以下、NMP
と略す）15部からなる混合物を窒素雰囲気下で撹
拌しながら100℃で10時間反応させた。反応物を
大量のメタノール中に注加することにより、析出
してくる析出物を取した。十分メタノールで洗
滌後、NMPより再結晶することにより、９―イ
ソアミル―３，６―ビス（ｐ―ニトロスチリル）
―１―ニトロカルバゾール3.87部（収率74％）を
橙色結晶として得た。 9-isoamyl-3,6-dibromo-1-nitrocarbazole 4.00 parts, p-nitrostyrene 3.12
parts, tri-n-butylamine 3.88 parts, tri-o-
Tolylphosphine 0.111 parts, palladium acetate 0.041 parts
N-methyl-2-pyrrolidone (hereinafter referred to as NMP)
A mixture consisting of 15 parts of the mixture was reacted at 100° C. for 10 hours with stirring under a nitrogen atmosphere. By pouring the reactant into a large amount of methanol, the deposited precipitate was collected. After thorough washing with methanol, recrystallization from NMP yields 9-isoamyl-3,6-bis(p-nitrostyryl).
3.87 parts of -1-nitrocarbazole (yield 74%) was obtained as orange crystals.
９―イソアミル―３，６―ビス（ｐ―ニトロス
チリル）―１―ニトロカルバゾール3.87部、鉄粉
7.38部、濃塩酸2.58（容積）部、水12.3部、
NMP150部よりなる混合物を撹拌しながら90℃で
13時間反応させた。反応混合物に20％炭酸ナトリ
ウム水溶液を加え、PH８に調整した。反応混合物
を熱時過した後、液を大量の水に注加し、析
出してくる析出物を取し、十分水洗後、乾燥す
ることにより、９―イソアミル―３，６―ビス
（ｐ−アミノスチリル）―１―アミノカルバゾー
ル3.13部（収率96％）を黄色固体として得た。 3.87 parts of 9-isoamyl-3,6-bis(p-nitrostyryl)-1-nitrocarbazole, iron powder
7.38 parts, concentrated hydrochloric acid 2.58 parts (volume), water 12.3 parts,
A mixture consisting of 150 parts of NMP was heated at 90°C with stirring.
The reaction was allowed to proceed for 13 hours. A 20% aqueous sodium carbonate solution was added to the reaction mixture to adjust the pH to 8. After heating the reaction mixture, the solution was poured into a large amount of water, the precipitate was collected, thoroughly washed with water, and dried to obtain 9-isoamyl-3,6-bis(p- 3.13 parts (yield 96%) of (aminostyryl)-1-aminocarbazole was obtained as a yellow solid.
９―イソアミル―３，６―ビス（ｐ―アミノス
チリル）―１―アミノカルバゾール1.50部を濃塩
酸7.7部、水7.7部よりなる希塩酸に加え、60℃で
30分間撹拌した。次いで混合物を０℃に冷却し、
これに亜硝酸ナトリウム0.65部を水2.6部に溶解
した溶液を滴下した。滴下後、同温度で30分間撹
拌し、不溶物を別し、液に42％硼弗化水素酸
水溶液8.2部を加え、析出してくる結晶を取
し、水洗後乾燥して、ヘキサゾニウムトリフルオ
ロボレートを濃茶色結晶として得た。 1.50 parts of 9-isoamyl-3,6-bis(p-aminostyryl)-1-aminocarbazole was added to dilute hydrochloric acid consisting of 7.7 parts of concentrated hydrochloric acid and 7.7 parts of water, and the mixture was heated at 60°C.
Stir for 30 minutes. The mixture was then cooled to 0°C,
A solution of 0.65 parts of sodium nitrite dissolved in 2.6 parts of water was added dropwise to this. After dropping, stir at the same temperature for 30 minutes, separate insoluble matter, add 8.2 parts of 42% borohydrofluoric acid aqueous solution, collect precipitated crystals, wash with water, dry, and remove hexazonium. Trifluoroborate was obtained as dark brown crystals.
このようにして得たヘキサゾニウム塩とカツプ
リング成分として２―ヒドロキシ―３―ナフトエ
酸アニリド（ナフトールAS）2.68部とを冷却し
たDMF200部に溶解し、これに酢酸ナトリウム
7.59部および水50部からなる水溶液４〜８℃の温
度下にて約１時間で滴下し、滴下後、室温にて３
時間撹拌した。生成した沈澱を取し、水200部
で３回洗浄した後、DMF300部で３回洗浄し、さ
らにアセトンで１回洗浄した。これを乾燥して表
記のトリスアゾ化合物1.56部（収率39％）を得
た。 The hexazonium salt thus obtained and 2.68 parts of 2-hydroxy-3-naphthoic acid anilide (naphthol AS) as a coupling component were dissolved in 200 parts of cooled DMF, and sodium acetate was added to the solution.
An aqueous solution consisting of 7.59 parts and 50 parts of water was added dropwise at a temperature of 4 to 8°C for about 1 hour.
Stir for hours. The generated precipitate was collected and washed three times with 200 parts of water, three times with 300 parts of DMF, and once with acetone. This was dried to obtain 1.56 parts (yield: 39%) of the indicated trisazo compound.
トリスアゾ化合物の赤外吸収スペクトルを第１
図に示した。 The first infrared absorption spectrum of trisazo compound
Shown in the figure.
構造式
元素分析値
Ｃ Ｈ Ｎ
実測値（％） 76.78 5.01 10.84
計算値（％） 77.05 4.93 10.70
応用例
実施例で合成したトリスアゾ顔料とポリエステ
ル樹脂（東洋紡績製：バイロン200）を１：２の
重量比で混合し、これをｎ―ブチルアミンとエチ
レンジアミンの１：１（容積比）混合溶剤に溶解
させ8.4重量％の溶液とした。Structural formula Elemental analysis value C H N Actual value (%) 76.78 5.01 10.84 Calculated value (%) 77.05 4.93 10.70 Application example Trisazo pigment synthesized in the example and polyester resin (Toyobo Co., Ltd.: Vylon 200) were mixed at a weight ratio of 1:2. This was mixed and dissolved in a 1:1 (volume ratio) mixed solvent of n-butylamine and ethylenediamine to form an 8.4% by weight solution.
この溶液を、アルミニウム基板上にアプリケー
ターで塗布し、乾燥して厚さ約１μの電荷発生層
を形成せしめた。この上に、ｐ―ジエチルアミノ
ベンズアルデヒド―Ｎ，Ｎ―ジフエニルヒドラゾ
ンおよびポリカーボネート樹脂（テイジン製：パ
ンライトＬ）を１：１の重量比で配合し、テトラ
ヒドロフランに溶解して18重量％の溶液を作り、
乾燥後の膜厚が約10μになるようにアプリケータ
ーで塗布し、乾燥して電荷移動層を形成させ、２
層からなる感光層を有する電子写真用感光体を得
た。 This solution was applied onto an aluminum substrate using an applicator and dried to form a charge generation layer with a thickness of about 1 μm. On top of this, p-diethylaminobenzaldehyde-N,N-diphenylhydrazone and polycarbonate resin (manufactured by Teijin: Panlite L) were blended at a weight ratio of 1:1, and dissolved in tetrahydrofuran to make a 18% by weight solution. ,
Apply with an applicator so that the film thickness after drying is approximately 10μ, dry to form a charge transfer layer, and
An electrophotographic photoreceptor having a photosensitive layer consisting of layers was obtained.
この感光体について、静電複写紙試験装置（川
口電機製作所製：SP―428型）を用いて、−6KV
のコロナ放電を15秒間行つて負に帯電せしめた
後、20秒間暗所に放置し、その時の表面電位V0
（Ｖ）を測定し、次いでタングステンランプによ
つてその表面が照度20ルツクスになるように光照
射し、その表面電位がV0の1/2になるまでの時間
（秒）を測定し、半減露光量Ｅ1/2（ルツクス・
秒）を求めた。 This photoreceptor was tested at -6KV using an electrostatic copying paper tester (Kawaguchi Electric Manufacturing Co., Ltd.: Model SP-428).
After performing corona discharge for 15 seconds to make it negatively charged, it was left in a dark place for 20 seconds, and the surface potential at that time V 0
(V), then irradiate the surface with light using a tungsten lamp at an illuminance of 20 lux, measure the time (seconds) until the surface potential becomes 1/2 of V0 , and reduce by half. Exposure amount E1/2 (Lux/
seconds) was calculated.
その結果はV0＝−740V、Ｅ1/2＝42ルツクス・
秒であり、暗所における電荷の保持性、光感度が
ともに大であつた。 The result is V 0 = -740V, E1/2 = 42 Lux.
seconds, and both charge retention in the dark and photosensitivity were high.
第１図は実施例により製造された本発明トリス
アゾ化合物の赤外線吸収スペクトルを示す。
FIG. 1 shows the infrared absorption spectrum of the trisazo compound of the present invention produced in the example.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3574882A JPS58154560A (en) | 1982-03-09 | 1982-03-09 | Novel trisazo compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3574882A JPS58154560A (en) | 1982-03-09 | 1982-03-09 | Novel trisazo compound and its preparation |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16808786A Division JPS6211772A (en) | 1986-07-18 | 1986-07-18 | Preparation of novel trisazo compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58154560A JPS58154560A (en) | 1983-09-14 |
| JPS6215097B2 true JPS6215097B2 (en) | 1987-04-06 |
Family
ID=12450436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3574882A Granted JPS58154560A (en) | 1982-03-09 | 1982-03-09 | Novel trisazo compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58154560A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6289770A (en) * | 1986-07-18 | 1987-04-24 | Asahi Glass Co Ltd | Preparation of novel trisazo compound |
| JP5239130B2 (en) * | 2006-06-16 | 2013-07-17 | 三菱化学株式会社 | Electrophotographic photoreceptor, image forming method, image forming apparatus, and amine compound |
-
1982
- 1982-03-09 JP JP3574882A patent/JPS58154560A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58154560A (en) | 1983-09-14 |
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