JPS63150273A - Charge-transfer complex of benzoquinone derivative and electron donor and production thereof - Google Patents
Charge-transfer complex of benzoquinone derivative and electron donor and production thereofInfo
- Publication number
- JPS63150273A JPS63150273A JP61298371A JP29837186A JPS63150273A JP S63150273 A JPS63150273 A JP S63150273A JP 61298371 A JP61298371 A JP 61298371A JP 29837186 A JP29837186 A JP 29837186A JP S63150273 A JPS63150273 A JP S63150273A
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- JP
- Japan
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- formula
- formulas
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- mathematical
- 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.)
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Links
- 150000004057 1,4-benzoquinones Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 239000012776 electronic material Substances 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract 1
- 150000001733 carboxylic acid esters Chemical group 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- -1 dicyanomethylene groups Chemical group 0.000 description 2
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 150000004059 quinone derivatives Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YMWLPMGFZYFLRP-UHFFFAOYSA-N 2-(4,5-dimethyl-1,3-diselenol-2-ylidene)-4,5-dimethyl-1,3-diselenole Chemical compound [Se]1C(C)=C(C)[Se]C1=C1[Se]C(C)=C(C)[Se]1 YMWLPMGFZYFLRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GRWIABMEEKERFV-UHFFFAOYSA-N methanol;oxolane Chemical compound OC.C1CCOC1 GRWIABMEEKERFV-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 1
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0644—Heterocyclic compounds containing two or more hetero rings
- G03G5/0646—Heterocyclic compounds containing two or more hetero rings in the same ring system
- G03G5/065—Heterocyclic compounds containing two or more hetero rings in the same ring system containing three relevant rings
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0624—Heterocyclic compounds containing one hetero ring
- G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
- G03G5/0631—Heterocyclic compounds containing one hetero ring being five-membered containing two hetero atoms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0644—Heterocyclic compounds containing two or more hetero rings
- G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は有機電子写真材料として有用なベンゾキノン誘
導体と電子供与体との新規な電荷移動錯体およびその製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel charge transfer complex of a benzoquinone derivative and an electron donor useful as an organic electrophotographic material, and a method for producing the same.
有機半導体等の有機電子材料として有用な化合物として
、従来テトラシアノアントラキノジメタン及びその誘導
体が知られている（例えば、特開昭５７−１４９２５９
号、同５８−５５４５０号等）。Tetracyanoanthraquinodimethane and its derivatives have been known as compounds useful as organic electronic materials such as organic semiconductors (for example, JP-A-57-149259).
No. 58-55450, etc.).
このテトラシアノアントラキノジメタン類は次式で示さ
れる基本骨格を有し、種々の置換基で置換されている化
合物である。These tetracyanoanthraquinodimethanes are compounds having a basic skeleton represented by the following formula and substituted with various substituents.
これらのテトラシアノアントラキノジメタン類は対応す
るアンスキキノン類から合成され、有機半導体、有機写
真材料、有機導電体、サーミスター材料等の有機電子材
料として有用な化合物である。These tetracyanoanthraquinodimethanes are synthesized from the corresponding anskiquinones and are useful compounds as organic electronic materials such as organic semiconductors, organic photographic materials, organic conductors, and thermistor materials.
また本発明者等は前記テトラシアノキノジメタン類と電
子供与性化合物とからなる電荷移動錯体を常温で固体の
純品として単離することに成功し、この電荷移動錯体は
単体よりも一層有機電子材料として有用であることを見
出し、更にテトラシアノアントラキノジメタン類の２個
のばンゾ縮金環の少なくとも１方を他の複素縮合環で置
き変え、さらに２個のジシアノメチレン基を種々の基へ
と修飾した化合物も、また同様に有機電子材料として有
用であることを見出した（特願昭６０−１７１１６１号
）。In addition, the present inventors succeeded in isolating a charge transfer complex consisting of the tetracyanoquinodimethane and an electron-donating compound as a pure product that is solid at room temperature, and this charge transfer complex is more organic than the simple substance. They found that it is useful as an electronic material, and furthermore, they replaced at least one of the two banzo-fused metal rings of tetracyanoanthraquinodimethanes with another heterofused ring, and furthermore, they replaced the two dicyanomethylene groups with various It has also been found that compounds modified with the group are also useful as organic electronic materials (Japanese Patent Application No. 171161/1982).
本発明者等は、上記化合物の原料であるベンゾキノン誘
導体の類縁化合物について、研究を重ねた結果、ベンゾ
キノン誘導体のある種のものの新規な電荷移動錯体が同
様に有機電子材料として有用であることを見出した。As a result of repeated research on analogues of benzoquinone derivatives, which are raw materials for the above compounds, the present inventors discovered that novel charge transfer complexes of certain benzoquinone derivatives are similarly useful as organic electronic materials. Ta.
従って、本発明の目的はベンゾキノン誘導体と電子供与
体との電荷移動錯体およびその製造方法を提供すること
にある。Therefore, an object of the present invention is to provide a charge transfer complex of a benzoquinone derivative and an electron donor and a method for producing the same.
すなわち、本発明は下記一般式（Ｉ）
示し、一方がこのヘテロ環を表わす場合には、他方は）
Ｒ３でもよいものとし、Ｒ工、Ｒ２及びＲ３は互に独立
したものであって％ Ｈ％アルキル、アリール、アリ
ール置換アルキル、アルコキシ、ハロゲン、ニトロ、シ
アノまたはカルボン酸エステル基を表わす。〕で示され
るベンゾキノン誘導体と電子供与性化合物との電荷移動
錯体、およびその製造方法を提供したものである。That is, the present invention is represented by the following general formula (I), and when one represents this heterocycle, the other is)
R3 may also be used, and R, R2 and R3 are independent of each other and represent an alkyl, aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group. The present invention provides a charge transfer complex of a benzoquinone derivative and an electron-donating compound represented by the following formula, and a method for producing the same.
本発明の電荷移動錯体の原料である前記一般式（Ｉ）で
示されるはンゾキノン誘導体の具体例を下記に構造式で
示す。Specific examples of the quinone derivative represented by the general formula (I), which is a raw material for the charge transfer complex of the present invention, are shown below in the form of structural formulas.
（ＤＴＰＱ） （ＢＤＴ工Ｑ）（ＢＤＴ
Ｑ） （ＢＴＤＴＱ）（ＢＤＴＴＯ）
前記の具体例の化合物のうち、（３）は新規化合物であ
るが、それを含めて製造工程と文献を下記に示（Ｂａｒ
、、 ８８．１７７１ （１９５５） 、 Ｂａｒ、、
９０．４３８ （１９５７） ）（Ａｒｃｈ、 Ｐｈ
ａｒｍ、、 ３０３．２８５ （１９６９） ）（力
（６）（Ｅ、 Ｍ
ｅｒｃｋ ＡＧ、ＤＡＳ １１４９９３４Ｖ、１８，１
２．１９５８ ）ｌＪ
（Ｊ、Ｏｒｇ、 Ｃｈｅｍ、、 ２９．６６０ （１９
６９） ）ＣＡｎｎ、、 ７２６１０３ （１９６９）
）（Ｊ、Ａｍ、Ｃｈｅｍ、Ｓｏｃ、 ７３．３４５９
（１９５１） ）（Ｔｅｔｒａｈａｄｒｏｎ Ｌｅｔ
ｔｅｒＢ１９７７＋ ２２０３ ）（Ｔｅｔｒａｈｅａ
ｒｏｎ Ｌｅｔｔ、、 １９７７、２２０３ ）（Ｃｈ
ｅｍ、 Ａｔ７ｓｔ、 ｓｓ、 ６２３７５６ （１９
７７） ）（Ｔｅｔｒａｈｅａｒｏｎ Ｌｅｔｔｅｒｓ
１９７７＋ ２２０３ ）次に本発明の電荷移動錯体
のもう一方の原料である電子供与体としては、例えばば
ンゼン、ナフタレン、アントラセン、ピレン、ペリレン
等の芳香族化合物、ｐ−フェニレンジアミンおよび類似
の縮合環型の芳香族化合物、テトラチアフルバレン（Ｔ
ＴＦ）、テトラチアテトラセン（ＴＴＴ）およびテトラ
メチルチアフルバレン（ＴＭＴＳＦ）のような含硫黄電
子供与性化合物等が挙げられる。(DTPQ) (BDT engineering Q) (BDT
Q) (BTDTQ) (BDTTO) Among the compounds in the above specific examples, (3) is a new compound, but the manufacturing process and literature including it are shown below (Bar
,, 88.1771 (1955), Bar.
90.438 (1957)) (Arch, Ph.
arm,, 303.285 (1969)) (force
(6) (E, M
erck AG, DAS 1149934V, 18,1
2.1958 ) lJ (J, Org, Chem,, 29.660 (19
69) ) CA Ann, 726103 (1969)
) (J, Am, Chem, Soc, 73.3459
(1951) ) (Tetrahadron Let
terB1977+ 2203) (Tetrahea
ron Lett, 1977, 2203) (Ch.
em, At7st, ss, 623756 (19
77) ) (Tetrahearon Letters
1977+2203) Next, as the electron donor which is the other raw material for the charge transfer complex of the present invention, aromatic compounds such as banzene, naphthalene, anthracene, pyrene, perylene, p-phenylenediamine and similar condensed rings can be used. A type of aromatic compound, tetrathiafulvalene (T
TF), sulfur-containing electron-donating compounds such as tetrathiatetracene (TTT) and tetramethylthiafulvalene (TMTSF).
また、ポリビニルカルバゾール（ＰＶＫ）などのポリマ
ーを用いることもできる。Additionally, polymers such as polyvinylcarbazole (PVK) can also be used.
これらの電子供与体および他の例を下記に構造式で示す
。These electron donors and other examples are shown in the structural formulas below.
（Ｋ）（ンＮ４Σｉ （ＴＭＢ）。(K) (N4Σi (TMB).
（Ｌ） （ＨｚＮ（■（３，３Ｓ５，５’−ＴＭＢ）。(L) (HzN(■(3,3S5,5'-TMB).
晶３
このような本発明の電荷移動錯体は以下のような本発明
の方法によって製造することができる。Crystal 3 Such a charge transfer complex of the present invention can be produced by the method of the present invention as described below.
（１）一般式（Ｉ）で示される化合物と電子供与性化合
物とを、これら両者が可溶性で、生成錯体が不溶性また
は難溶性の溶媒中で反応させ生成物を沈澱させる方法。(1) A method in which a compound represented by general formula (I) and an electron-donating compound are reacted in a solvent in which both are soluble and the resulting complex is insoluble or sparingly soluble to precipitate the product.
（２）一般式（Ｉ）で示される化合物と電子供与性化合
物の両原料および生成物が可溶性の溶媒中で反応させた
後、生成物の貧溶媒を加えて生成物を沈澱させる方法。(2) A method in which the compound represented by general formula (I) and the electron-donating compound are reacted in a solvent in which both raw materials and the product are soluble, and then a poor solvent for the product is added to precipitate the product.
（３）同じく両原料および生成物が可溶性の溶媒中で反
応させ、生成物の貧溶媒を加えるか、または加えないで
反応溶媒を留去して生成物を沈澱させる方法。(3) Similarly, a method in which both raw materials and the product are reacted in a soluble solvent, and the reaction solvent is distilled off to precipitate the product, with or without adding a poor solvent for the product.
一般式（Ｉ）で示されるはンゾキノン誘導体と電子供与
体との電荷移動錯体は有機電子材料として有用であり、
有機電子写真材料、コンデンサ材料、低抵抗感熱素子、
センサー材料などに利用可能である。例えば電子写真感
光体の電荷輸送材とじて用いる場合にはポリカーボネー
ト、ポリエステル等の結着樹脂と共に用いて電荷輸送層
としたり、電荷発生層中に電荷発生材と共に含有させて
用いることができる。A charge transfer complex of a quinone derivative and an electron donor represented by the general formula (I) is useful as an organic electronic material,
Organic electrophotographic materials, capacitor materials, low resistance heat-sensitive elements,
It can be used for sensor materials, etc. For example, when used as a charge transport material for an electrophotographic photoreceptor, it can be used together with a binder resin such as polycarbonate or polyester to form a charge transport layer, or it can be contained in a charge generation layer together with a charge generation material.
参考例Ｉ
で示されるベンゾキノン誘導体の合成
りロラ＝ル（１１２，３９（５０ｍｏＺ）を１８０ｄの
ＤＭＦに懸濁させ、水浴中で１０℃に冷却しておく。マ
ロンニトリルＣＨ２（ＯＮ）２、二硫化炭素および水酸
化ナトリウムから調製した（ＣＮ）２Ｃ２Ｓ２Ｎｃ２（
Ｊ、 Ｏｒｇ。Synthesis of benzoquinone derivative shown in Reference Example I Loral (112,39 (50moZ)) was suspended in 180d of DMF and cooled to 10°C in a water bath. (CN)2C2S2Nc2 (prepared from carbon sulfide and sodium hydroxide)
J, Org.
Ｃｈｅｍ、、 ２９．６６０ （１９６９）参照〕１８
．４９ （９９湿Ｚ）を５０ｄの水に溶解した溶液を先
のＤＭＦ’溶液に３０分間かけて滴下し、次いで室温で
５時間攪拌した後、水５０ｄを加えて氷冷する。沈澱を
炉別し、１００コの水で洗浄後、ＴＨＦ−メタノールか
ら再結晶して次式
で示されるヒドロキノン誘導体を１０．０’ｌ（収率５
２チ）、黄緑色針状晶（融点〉３８４℃）として得る。See Chem, 29.660 (1969)] 18
．． A solution prepared by dissolving 49 (99 wet Z) in 50 d of water was added dropwise to the above DMF' solution over 30 minutes, and after stirring at room temperature for 5 hours, 50 d of water was added and cooled on ice. The precipitate was separated in a furnace, washed with 100 g of water, and then recrystallized from THF-methanol to obtain 10.0'l of a hydroquinone derivative represented by the following formula (yield 5.
2), obtained as yellow-green needles (melting point>384°C).
このヒドロキノン誘導体２．Ｏｆ （５，１８閣ｔ）を
１５０ゴの無水ＴＨＥ”に懸濁させ、ジシアノジクロロ
−ｐ−ベンゾキノｙ １．４１ ’ｊ （６，２２ｍｍ
ｏｌ 、 ＬＺ ａ量）を２０−の乾燥ＴＨＥ’に溶か
した溶液を２０分間で滴下する。This hydroquinone derivative 2. Of (5,18 mm) was suspended in 150 g of anhydrous THE'' and dicyanodichloro-p-benzoquinoy 1.41'j (6,22 mm
A solution of 20-ml of dry THE' was added dropwise over 20 minutes.
４時間室温で攪拌し、紫色結晶を炉別する。収量１５２
１１） （７６％）。Stir for 4 hours at room temperature and filter out the purple crystals. Yield 152
11) (76%).
融点：３９７℃以上（分解）；
工Ｒ： Ｌ）％’：、” ＝ ２２０３ ｃｍ−” ；
Ｍｌ！ＬＦ３８ ： ｍ７ｇ ３８４ （Ｍ”、１００
％） ；元素分析：０□４’４Ｓ４０２として
計算値：Ｃ４３，７４Ｎ １４．５７ ８３３．７６実
測値： Ｃ４３，７４Ｎ １４．６８ Ｓ ３３．２
４゜実施例Ｉ
ＢＤＴＩＱ−ＤＢＴＴＦ’（１： １ ）錯体（２１（
Ａ）
３５ＭＩ！ノ無水ＣＨ２ＣＡ２Ｋ（２）を３８Ｗ （０
，１ミリ溶かした沸騰溶液へ、１０ｍの無水ＣＨ２Ｃｌ
２に（＾を３０ＦＱ（Ｑ、 ｌ ｍｒｎｏｌ）溶かした
沸騰溶液を加え、５分間加熱攪拌した。放冷後析出した
結晶を炉別し、１：１の錯体６７■を得る。Melting point: 397°C or higher (decomposition); Engineering R: L)%': ," = 2203 cm-";
Ml! LF38: m7g 384 (M”, 100
%); Elemental analysis: Calculated value as 0□4'4S402: C43,74N 14.57 833.76 Actual value: C43,74N 14.68 S 33.2
4゜Example I BDTIQ-DBTTF' (1:1) complex (21(
A) 35MI! Anhydrous CH2CA2K (2) at 38W (0
, 10 m of anhydrous CH2Cl to the boiling solution dissolved 1 m
A boiling solution containing 30 FQ (Q, l mrnol) of (^) was added to the mixture and stirred under heating for 5 minutes. After cooling, the precipitated crystals were separated in a furnace to obtain a 1:1 complex 67.
紺色結晶、融点２５５〜２５８℃（分解）。Dark blue crystals, melting point 255-258°C (decomposed).
υ％Ｘ ： 〜２２０３ ｃｍ−” ；元素分析：Ｃ２
８Ｈ８Ｎ４Ｓ８０２として計算値（に）： ０４８．８
２ １１．１７ Ｎ ８．１３実測値（％） ： Ｃ
４８，３６ＨＯ，９６Ｎ ７．９８実施例２
ＢＤＴＩＱ −ＴＴＭＴＴＦ （１： １ ）錯体（２
１（Ｂ）
した沸騰溶液へ（至）を２５ Ｗ （０，０７ｍｙｎｏ
ｌ、 ）を加え、黒色の沈澱が析出しはじめるまで加熱
攪拌した。放冷後沖別して１：１錯体４９■を得る。黒
色沈澱。υ%X: ~2203 cm-”; Elemental analysis: C2
Calculated value as 8H8N4S802: 048.8
2 11.17 N 8.13 Actual value (%): C
48,36HO,96N 7.98 Example 2 BDTIQ-TTMTTF (1:1) complex (2
1(B) to a boiling solution of 25 W (0.07 myno
1, ) was added, and the mixture was heated and stirred until a black precipitate began to precipitate. After cooling, the mixture was separated to obtain 1:1 complex 49■. Black precipitate.
融点 １８４〜１８６℃（分解）。Melting point: 184-186°C (decomposed).
４’ ： ２２０７ ｃｒｒｃ−”。4’: 2207 crrc-”.
元素分析” Ｃ２４Ｈ１□Ｎ４ Ｓ１２としてＨＮ
計算値（＠ ３７．２８ １．５６ ７．２５
実測値（４３７，１３１，２５＆０７
０７実施
ＢＤＴＱ−ＴＭＴＳＦ （１： １ ）錯体（３）
（Ｇ）
３０１Ｌｌノ無水ＣＨ２Ｃｌ２Ｋ（３）を２９ ”Ｓ’
（０，０８ｍｍｏｌ ） 溶かした沸騰溶液へ、２
５ｔ／の無水ＣＨ２Ｃｌ２ に（Ｇ）を３４７ｖ（０，
０８ｍｍｏｌ ）溶かした沸騰溶液を加え、５分間加熱
攪拌後、冷却して黒色沈澱として１：１の錯体６１Ｔｎ
ｇを得る。Elemental analysis” C24H1□N4 HN as S12 Calculated value (@ 37.28 1.56 7.25
Actual value (437,131,25&0707 implementation BDTQ-TMTSF (1:1) complex (3)
(G) 301 Ll anhydrous CH2Cl2K (3) to 29 "S'
(0,08 mmol) into the dissolved boiling solution, 2
(G) in 5t/anhydrous CH2Cl2 at 347v (0,
08 mmol) Add the dissolved boiling solution, heat and stir for 5 minutes, cool and form a 1:1 complex 61Tn as a black precipitate.
get g.
融点２２０〜２３０℃（分解）。Melting point 220-230°C (decomposition).
１／ＫＢｒ： ２２０２ｍ−” ；
元素分析二０２４Ｈ１２Ｎ４Ｓ４８８４０２としてＣＨ
Ｎ
計算値 ３４．６３ １．４５ ６．７３実測値
３５．１ＯＬ３０ ７．０７実施例４
ＢＴＤＴＱ −ＴＭＴＴＦ’ （１： １ ）錯体（４
）（Ｄ）
１５１１ＬｌのＣＨ２（Ｊ ２に（４）を３２ｍｇ（ｏ
、ｔ ｍｍｏｌ ）溶かした沸騰溶液へ５ｄのＣＨ２Ｃ
ｌ２に（ト）を２６”９ （０，１ｍｍｏＬ ）溶かし
た沸騰溶液を加えた。放冷後、緑灰色沈澱として１：１
錯体を５５■得る。融点２５８℃以上（分解）。1/KBr: 2202m-”; CH as elemental analysis 2024H12N4S488402
N Calculated value 34.63 1.45 6.73 Actual value 35.1 OL30 7.07 Example 4 BTDTQ-TMTTF' (1:1) complex (4
) (D) Add 32 mg (o) of (4) to 1511 Ll of CH2 (J
, t mmol) 5d of CH2C into the dissolved boiling solution
A boiling solution of 26"9 (0.1 mmol) of (g) dissolved in l2 was added. After cooling, a green-gray precipitate was formed at a ratio of 1:1.
55 μ of the complex are obtained. Melting point: 258°C or higher (decomposition).
元素分析：Ｃ□８Ｈ□２０□Ｓ１ｏとしてＣＨ
計算値 ３７．２２ ２．０８
実測値 ３７．０４ ２．０９゜実施例５
ＢＴＤＴＱ −ＴＴＴ （１： １ ）錯体（４）＠
４０ｄのＣＨ２Ｃｌ２に（４）を３２Ｗ （０，ｔ ｒ
ｎｍｏｔ、 ）溶かし、ソックスレイ抽出器を用いてＨ
３５■（０，１ｍｒｎｏｌ ）を先の溶液で２４時間抽
出する。放冷後黒色沈澱として＠４０■を得る。融点
４００’Ｃ以上（分解）。Elemental analysis: CH as C□8H□20□S1o Calculated value 37.22 2.08 Actual value 37.04 2.09゜Example 5 BTDTQ-TTT (1:1) Complex (4) @ 40d of CH2Cl2 ( 4) at 32W (0, t r
nmot, ) and H using a Soxhlet extractor.
35 ml (0.1 mrnol) was extracted with the above solution for 24 hours. After cooling, @40■ was obtained as a black precipitate. melting point
400'C or higher (decomposition).
元素分析：Ｃ２６Ｈ８０２Ｓ１ｏとしてＣ”Ｈ
計算値 ４６，４０ １．２０
実測値 ４７．５２ １．４６
実施例６
ＤＴＰＱ−ＴＴＴ（１： １ ）錯体
（１） に）
２５０−のＣＨ２Ｃｌ２に（１）を３２”ｌＦ （０，
１ｒｎｍｏｌ）懸濁し、ソックスレイ抽出器を用いて（
ロ）３５■（Ｑ、 ｌ ｒ７１７７Ｌｏりを先の懸濁液
で２４時間抽出する。５ｏ１ｒＬｌ！まで濃縮し、茶色
の沈澱として１：１錯体５０■を得る。融点４００℃以
上。Elemental analysis: C''H as C26H802S1o Calculated value 46,40 1.20 Actual value 47.52 1.46 Example 6 DTPQ-TTT (1:1) complex (1)) 250- CH2Cl2 (1) 32”lF (0,
1rnmol) and using a Soxhlet extractor (
b) 35■ (Q, l Extract 7177Lo with the above suspension for 24 hours. Concentrate to 5o1rLl! to obtain 1:1 complex 50■ as a brown precipitate. Melting point: 400°C or higher.
参考例２
電荷移動錯体の電導性
下記の表１に示すドナー（電子供与体）とアクセプター
（電子受容体）との組合せからなる電荷移動錯体につい
て、ベレットとして二端子法または四端子法により比抵
抗値（ρ１０ｍ）を求めた結果を示す。Reference Example 2 Electrical conductivity of charge transfer complexes Regarding charge transfer complexes consisting of the combinations of donors (electron donors) and acceptors (electron acceptors) shown in Table 1 below, the specific resistance was determined by the two-terminal method or the four-terminal method as a pellet. The results of determining the value (ρ10m) are shown.
Claims (1)
、化学式、表等があります▼のいずれか一方は、▲数式
、化学式、表等があります▼、▲数式、化学式、表等が
あります▼、▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼で示されるヘテロ環を示し、一方がこ
のヘテロ環を表わす場合には、他方は▲数式、化学式、
表等があります▼でもよいものとし、Ｒ＿１、Ｒ＿２及
びＲ＿３は互に独立したものであつて、Ｈ、アルキル、
アリール、アリール置換アルキル、アルコキシ、ハロゲ
ン、ニトロ、シアノまたはカルボン酸エステル基を表わ
す。〕で示されるベンゾキノン誘導体と電子供与性化合
物との電荷移動錯体。 ２）下記一般式（ I ） ▲数式、化学式、表等があります▼（ I ） 〔式中、▲数式、化学式、表等があります▼及び▲数式
、化学式、表等があります▼のいずれか一方は、▲数式
、化学式、表等があります▼、▲数式、化学式、表等が
あります▼、▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼で示されるヘテロ環を示し、一方がこ
のヘテロ環を表わす場合には、他方は▲数式、化学式、
表等があります▼でもよいものとし、Ｒ＿１、Ｒ＿２及
びＲ＿３は互に独立したものであつて、Ｈ、アルキル、
アリール、アリール置換アルキル、アルコキシ、ハロゲ
ン、ニトロ、シアノまたはカルボン酸エステル基を表わ
す。〕で示されるベンゾキノン誘導体と電子供与性化合
物との電荷移動錯体の製造方法において、 ｉ）原料が可溶性で、生成錯体が不溶性または難溶性の
溶媒中で反応させ生成物を沈澱させるか、 ｉｉ）原料および生成物が可溶性の溶媒中で反応させた
後、生成物の貧溶媒を加えて生成物を沈澱させるか、ま
たは ｉｉｉ）原料および生成物が可溶性の溶媒中で反応させ
、生成物の貧溶媒を加えるかまたは加えないで反応溶媒
を留去して生成物を沈澱させるかすることを特徴とする
製造方法。[Claims] 1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) Either one of ▼ has mathematical formulas, chemical formulas, tables, etc. ▼, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼, ▲ has mathematical formulas, chemical formulas, tables, etc. ▼、▲Mathematical formula, chemical formula,
There are tables etc. showing the heterocycle shown by ▼, and when one side represents this heterocycle, the other one is ▲ mathematical formula, chemical formula,
There is a table etc. ▼ is also acceptable, and R_1, R_2 and R_3 are mutually independent, H, alkyl,
Represents aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group. ] A charge transfer complex of a benzoquinone derivative and an electron-donating compound. 2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas ,
There are tables etc. showing the heterocycle shown by ▼, and when one side represents this heterocycle, the other one is ▲ mathematical formula, chemical formula,
There is a table etc. ▼ is also acceptable, and R_1, R_2 and R_3 are mutually independent, H, alkyl,
Represents aryl, aryl-substituted alkyl, alkoxy, halogen, nitro, cyano or carboxylic acid ester group. ] In the method for producing a charge transfer complex of a benzoquinone derivative and an electron-donating compound, the raw material is soluble, and the resulting complex is reacted in a solvent in which it is insoluble or poorly soluble, or ii) the product is precipitated. Either the raw materials and products are reacted in a solvent in which they are soluble and then a product poor solvent is added to precipitate the product, or iii) the raw materials and products are reacted in a solvent in which they are soluble and the product is precipitated. A production method characterized in that the reaction solvent is distilled off and the product is precipitated with or without addition of a solvent.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61298371A JPH06773B2 (en) | 1986-12-15 | 1986-12-15 | Method for producing charge transfer complex of benzoquinone derivative and electron donor |
| US07/131,665 US4960886A (en) | 1986-12-15 | 1987-12-11 | Charge transfer complex formed between benzoquinone derivative and electron donor and process for producing the same |
| US07/541,517 US5151528A (en) | 1986-12-15 | 1990-06-21 | Charge transfer complex formed between benzoquinone derivative and electron donor and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61298371A JPH06773B2 (en) | 1986-12-15 | 1986-12-15 | Method for producing charge transfer complex of benzoquinone derivative and electron donor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63150273A true JPS63150273A (en) | 1988-06-22 |
| JPH06773B2 JPH06773B2 (en) | 1994-01-05 |
Family
ID=17858822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61298371A Expired - Lifetime JPH06773B2 (en) | 1986-12-15 | 1986-12-15 | Method for producing charge transfer complex of benzoquinone derivative and electron donor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06773B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247576A (en) * | 2000-03-09 | 2001-09-11 | Tdk Corp | Thiophene derivative and its polymer |
| WO2009022736A1 (en) | 2007-08-16 | 2009-02-19 | Fujifilm Corporation | Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent |
| JP2018501225A (en) * | 2014-12-09 | 2018-01-18 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Device for controlling the passage of energy |
-
1986
- 1986-12-15 JP JP61298371A patent/JPH06773B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247576A (en) * | 2000-03-09 | 2001-09-11 | Tdk Corp | Thiophene derivative and its polymer |
| JP4543486B2 (en) * | 2000-03-09 | 2010-09-15 | Ｔｄｋ株式会社 | Thiophene derivatives and polymers thereof |
| WO2009022736A1 (en) | 2007-08-16 | 2009-02-19 | Fujifilm Corporation | Heterocyclic compound, ultraviolet ray absorbent, and composition comprising the ultraviolet ray absorbent |
| US8039532B2 (en) | 2007-08-16 | 2011-10-18 | Fujifilm Corporation | Heterocyclic compound, ultraviolet absorbent and composition containing the same |
| JP2018501225A (en) * | 2014-12-09 | 2018-01-18 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Device for controlling the passage of energy |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06773B2 (en) | 1994-01-05 |
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