JP2015534545A - Novel spiro compounds and their use in organic electronics applications and devices - Google Patents

Abstract

In the present invention, the variables R11, R12, R21, R22, R31, R32, R41 and R42 independently of one another have the meaning of aryl or hetaryl, provided that all of these groups 9,9′-spirobifluorene compounds in organic electronics applications, especially in organic field effect transistors, organic photodetectors and organic solar cells, especially dye-sensitized solar cells and bulk heterojunctions Disclosed is the use of the compound of formula I in solar cells, and organic field effect transistors, dye-sensitized solar cells and bulk heterojunction solar cells comprising the formula I.

Description

［式中、
可変記号Ｒ¹¹、Ｒ¹²、Ｒ²¹、Ｒ²²、Ｒ³¹、Ｒ³²、Ｒ⁴¹及びＲ⁴²は、互いに独立して、アリール又はヘタリールの意味を有するが、但し、基Ｒ¹¹、Ｒ¹²、Ｒ²¹、Ｒ²²、Ｒ³¹、Ｒ³²、Ｒ⁴¹及びＲ⁴²の全てが同じになることはない］
の９，９'−スピロビフルオレン化合物、
有機エレクトロニクス用途での、特に有機電界効果トランジスタにおける、有機光検出器及び有機太陽電池における、特に色素増感太陽電池及びバルクヘテロ接合太陽電池における、一般式Ｉの化合物の使用、及び
一般式Ｉの化合物を含む有機電界効果トランジスタ、色素増感太陽電池及びバルクヘテロ接合太陽電池
に関する。 The present invention relates to general formula I

[Where:
The variables R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² independently of one another have the meaning of aryl or hetaryl, provided that the groups R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² are not all the same]
9,9′-spirobifluorene compound of
Use of compounds of general formula I in organic electronics applications, especially in organic field effect transistors, in organic photodetectors and organic solar cells, in particular in dye-sensitized solar cells and bulk heterojunction solar cells, and compounds of general formula I In particular, the present invention relates to an organic field effect transistor, a dye-sensitized solar cell, and a bulk heterojunction solar cell.

  Dye-sensitized solar cells (“DSC”) are currently one of the most efficient alternative solar cell technologies. In liquid variations of this technology, efficiencies as high as 11% have been achieved so far (eg Graetzel M. et al., J. Photochem. Photobio. C, 2003, 4, 145; Chiba et al., Japanese Journal of Appl. Phys., 2006, 45, L638-L640).

The structure of DSC is generally based on a glass substrate, which is covered with a transparent conductive layer and serves as a working electrode. An n-type conductive metal oxide, for example, a nanoporous titanium dioxide layer (TiO ₂ ) having a thickness of about 2 to 20 μm is applied to the electrode or the vicinity thereof. On the surface is further adsorbed a monolayer of a photosensitive dye, for example, generally a ruthenium complex, which can be transferred to an excited state by light absorption. The counter electrode may optionally have a metal catalyst layer, for example, a platinum layer having a thickness of several μm. The region between these two electrodes is filled with a redox electrolyte, such as a solution of iodine (I ₂ ) and lithium iodide (LiI).

  The function of DSC is based on the fact that light is absorbed by the dye and electrons are transported from the excited dye to the n-type semiconducting metal oxide semiconductor and then move to the anode, The electrolyte ensures charge balance through the cathode. Thus, although n-type semiconducting metal oxides, dyes, and (generally liquid) electrolytes are the most important components of DSC, batteries containing liquid electrolytes often have suboptimal encapsulation. As a drawback, this leads to stability problems. Accordingly, various materials have been studied for their suitability as solid electrolyte / p-type semiconductors.

Various inorganic p-type semiconductors such as CuI, CuBr · 3 (S (C ₄ H ₉ ) ₂ ) or CuSCN have been used in the DSC in the solid state. With a solid DSC based on CuI, efficiencies, for example, greater than 7% have been reported by Hitoshi Sakamoto et al. (Organic Electronics 13 (2012), 514-518).

A solid DSC containing CsSnI ₃ doped with fluorine and tin difluoride as a hole conducting material and showing an efficiency of about 10% has been reported by In Chung et al. (Nature Vol.485, May 2012) 24th, 486-490).

  Organic polymers are also used as solid p-type semiconductors. Examples thereof include polypyrrole, poly (3,4-ethylenedioxythiophene), carbazole-based polymer, polyaniline, poly (4-undecyl-2,2′-bithiophene), poly (3-octylthiophene), poly ( Triphenyldiamine) and poly (N-vinylcarbazole). In the case of poly (N-vinylcarbazole) the efficiency reaches 2%; in addition, in the case of PEDOT (poly (3,4-ethylenedioxythiophene)) polymerized in-situ, 2.9. % Efficiency was achieved (Xia et al. J. Phys. Chem. C 2008, 112, 11569). These polymers are generally not in pure form and are usually used in admixture with additives. In addition, the idea that polymer p-type semiconductors bind directly to Ru dyes has been proposed (Peter, K., Appl. Phys. A 2004, 79, 65).

  High efficiency has also been achieved using low molecular weight organic p-type semiconductors. For example, WO 98/48433 A1 discloses an organic compound 2,2 ′, 7,7′-tetrakis (N, N-di-p-methoxyphenylamine) -9,9′- in DSC as a hole transport material. The use of spirobifluorene (“Spiro-MeOTAD”) has been reported.

  Spiro-MeOTAD is also similar to Snaith, HJ; Moule, AJ; Klein, C; Meerholz, K .; Friend, RH; Gratzel (M. Nano Lett .; (Letter); 2007; 7 (11); 3372-3376 ) As a hole transport material in DSC.

  Further spiro compounds as hole transport materials and hole injection materials used primarily in organic light emitting diodes (“OLEDs”) are described in WO 2011/116869 A1.

  A study by C. Jaeger et al. (Proc. SPIE 4108, 104-110 (2001)) shows that spiro-MeOTAD exists in a semi-crystalline form and is strong in the processed form, ie DSC (re). It shows a tendency to crystallize.

  Furthermore, the solubility in ordinary process solvents is relatively low, and the pore filling level is correspondingly reduced.

  Durrant et al., Adv. Func. Mater. 2006, 16, 1832-1838, in many cases, photocurrent is directly related to the yield of holes transferred from an oxidative dye to a solid p-type semiconductor. States that it depends on This mainly depends on two factors: the first is the degree to which the p-type semiconductor penetrates into the oxide holes, and the second is the thermodynamic driving force for charge transport, in particular It depends on the difference in free enthalpy ΔG between the dye and the p-type semiconductor.

  Recent developments in organic photovoltaics have been directed to so-called “bulk heterojunction” (“BHJ”) solar cells; in this case, the photoactive layer contains acceptor and donor compounds as a bicontinuous phase. ing. As a result of photoinduced charge transfer from the excited state of the donor compound to the acceptor compound, the spatial proximity of the compound results in faster charge separation than other relaxation processes, and the generated holes and electrons correspond to the corresponding electrodes. Removed through. To increase the efficiency of such batteries, additional layers, such as hole or electron transport layers, are often applied between the electrode and the photoactive layer.

So far, the donor material used in such BHJ batteries is generally a polymer, such as polyvinylphenylene or polythiophene, or a dye from the phthalocyanine class, such as zinc phthalocyanine or vanadyl phthalocyanine. Acceptor materials are fullerenes and fullerene derivatives or even various perylenes. The donor / acceptor pair poly (3-hexyl-thiophene) (“P3HT”) / [6,6] -phenyl-C ₆₁ -butyric acid methyl ester (“PCBM”), poly (2-methoxy-5- (3 , 7-dimethyloctyloxy) -1,4-phenylenevinylene) (“OC ₁ C ₁₀ -PPV”) / PCBM and zinc phthalocyanine / fullerene are being intensively studied.

  The object of the present invention was therefore to provide further compounds which can be advantageously used as p-type semiconductors in solar cells, in particular in DSC and BHJ cells. With regard to its characteristic profile, it is desirable for the compound to have good hole conduction properties, very low if there is a tendency to crystallize, and good solubility in common solvents. It is desirable.

［式中、
可変記号Ｒ¹¹、Ｒ¹²、Ｒ²¹、Ｒ²²、Ｒ³¹、Ｒ³²、Ｒ⁴¹及びＲ⁴²は、互いに独立して、アリール又はヘタリールの意味を有するが、但し、基Ｒ¹¹、Ｒ¹²、Ｒ²¹、Ｒ²²、Ｒ³¹、Ｒ³²、Ｒ⁴¹及びＲ⁴²の全てが同じになることはない］
の化合物が合成された。 Accordingly, the general formula I

[Where:
The variables R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² independently of one another have the meaning of aryl or hetaryl, provided that the groups R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² are not all the same]
Was synthesized.

In the general formula I, the moieties N (R ¹¹ R ¹² ), N (R ²¹ R ²² ), N (R ³¹ R ³² ) and N (R ⁴¹ R ⁴² ) are the 2nd position of the 9,9′-spirobifluorene skeleton. , Preferred are compounds of the general formula I which are bonded in the 7-position, 2′-position and 7′-position.

［式中、可変記号は以下の意味を有する：
Ｒ⁵は、水素、アルキル、アリール、アルコキシ、アルキルチオ又は−ＮＲ⁶Ｒ⁷を表し、その際、置換基が２つ以上（ｐが２以上）の場合には、該置換基は同じであっても異なっていてもよく、
ｐは、０、１、２、３、４又は５を表し、
Ｘは、Ｃ（Ｒ⁸Ｒ⁹）₂、ＮＲ¹⁰、酸素又は硫黄を表し、
かつ、
Ｒ⁶からＲ¹⁰は、水素、アルキル、シクロアルキル、アリール又はヘタリールを表す］
の部分である化合物である。 Particularly preferred compounds related also to the above preferred are those in the general formula I in which the variables R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² are independently of each other Formula Ia or Ib

[Wherein the variable symbols have the following meanings:
R ⁵ represents hydrogen, alkyl, aryl, alkoxy, alkylthio, or —NR ⁶ R ^7. When two or more substituents are present (p is 2 or more), the substituents are the same. May be different,
p represents 0, 1, 2, 3, 4 or 5;
X represents C (R ⁸ R ⁹ ) ₂ , NR ¹⁰ , oxygen or sulfur;
And,
R ⁶ to R ¹⁰ represent hydrogen, alkyl, cycloalkyl, aryl or hetaryl]
It is a compound that is a part of

Further preferred is also related to the above preferred ones. In the general formula I, the variable symbols R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ are the same as each other, and the variable symbols R ¹² , R ²² , R ³² and R ⁴² are the same compounds. Since the general precondition that not all of the variable symbols R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² are the same is maintained, the variable symbol R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ and the variable symbols R ¹² , R ²² , R ³² and R ⁴² are both different from each other.

Furthermore, the present invention includes not only compounds having specific substituents R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² but also substituents R ¹¹ , R ¹² , R ^42. Also included are mixtures of compounds having a random distribution of ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² .

の化合物と、式ＨＮＲ¹¹Ｒ¹²、ＨＮＲ²¹Ｒ²²、ＨＮＲ³¹Ｒ³²及びＨＮＲ⁴¹Ｒ⁴²の適したアミンの混合物とを、パラジウム含有触媒の存在下にブッフバルト・ハートウィッグアミノ化反応の条件下に反応させることを含み、その際、可変記号Ｒ¹¹、Ｒ¹²、Ｒ²¹、Ｒ²²、Ｒ³¹、Ｒ³²、Ｒ⁴¹及びＲ⁴²は上記の意味を有し、かつＬ_gは典型的に当業者に公知の脱離基を表す。そのような基Ｌ_gの例については、以下に示す。典型的には、この反応は、相応する置換基−Ｒ¹¹Ｒ¹²、−ＮＲ²¹Ｒ²²、−ＮＲ³¹Ｒ³²及び−ＮＲ⁴¹Ｒ⁴²のランダム分布を有する式Ｉの化合物の混合物をもたらす。 One route for preparing the compounds of formula I of this application is the general formula IIa

And a mixture of suitable amines of the formulas HNR ¹¹ R ¹² , HNR ²¹ R ²² , HNR ³¹ R ³² and HNR ⁴¹ R ⁴² under the conditions of the Buchwald-Hartwig amination reaction in the presence of a palladium-containing catalyst. Wherein the variables R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² have the above meanings, and L _g typically Represents leaving groups known to those skilled in the art. For examples of such groups L _g is given below. Typically, this reaction results in a mixture of compounds of formula I having a random distribution of the corresponding substituents —R ¹¹ R ¹² , —NR ²¹ R ²² , —NR ³¹ R ³² and —NR ⁴¹ R ⁴² .

［式中、
可変記号Ｒ¹¹及びＲ¹²は、互いに異なっており、かつアリール又はヘタリールの意味を有する］
により示される。 A formula that does not exhibit substituent randomization while following the precondition that the groups R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² are not all the same. The compounds of I have the following formula II

[Where:
Variable symbols R ¹¹ and R ¹² are different from each other and have the meaning of aryl or hetaryl]
Indicated by.

の化合物と一般式ＩＩｂ

の化合物とを、パラジウム含有触媒の存在下にブッフバルト・ハートウィッグアミノ化反応の条件下に反応させることにより製造されることができ、その際、可変記号は以下の意味を有する：
Ｒ¹¹、Ｒ¹²は、互いに異なって、アリール又はヘタリールを表し、かつ
Ｌ_gは、脱離基を表す。 Similar to the above synthesis, this compound of formula II is for example represented by the general formula IIa

And a compound of the general formula IIb

In the presence of a palladium-containing catalyst under the conditions of the Buchwald-Hartwig amination reaction, where the variable symbols have the following meanings:
R ¹¹ and R ¹² are different from each other and represent aryl or hetaryl, and L _g represents a leaving group.

In general, the leaving group L _g may be any group known to those skilled in the art as a proton that is easily removed from the molecule. Typically, L _g consists of an atom or moiety that exhibits a strong electron withdrawing property, or contains an atom or a moiety that exhibits a strong electron withdrawing property, and thus is usually eliminated as an anionic species.

The preferred groups L _g are chlorine, bromine, iodine, brosylate, nosylate, tosylate, mesylate and triflate, which in this respect are molecules that are chloride anions, bromide anions, iodide anions, brosylate anions. , Desorbed as nosylate anion, tosylate anion, mesylate anion or triflate anion.

The structure of brosylate, nosylate and tosylate is as follows in each order:

の部分であり、その際、式Ｉａ及びＩｂ中の可変記号は、以下の意味を有する：
Ｒ⁵は、水素、アルキル、アリール、アルコキシ、アルキルチオ又は−ＮＲ⁶Ｒ⁷を表し、その際、置換基が２つ以上（ｐが２以上）の場合には、該置換基は同じであっても異なっていてもよく、
ｐは、０、１、２、３、４又は５を表し、
Ｘは、Ｃ（Ｒ⁸Ｒ⁹）₂、ＮＲ¹⁰、酸素又は硫黄を表し、
かつ、
Ｒ⁶からＲ¹⁰は、水素、アルキル、シクロアルキル、アリール又はヘタリールを表す。 According to the above synthetic route, particularly preferred compounds of formula I or formula II can be prepared, wherein the variables R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² , And each of the variable symbols R ¹¹ and R ¹² , independently of one another, has the formula Ia or Ib

Wherein the variables in formulas Ia and Ib have the following meanings:
R ⁵ represents hydrogen, alkyl, aryl, alkoxy, alkylthio, or —NR ⁶ R ^7. When two or more substituents are present (p is 2 or more), the substituents are the same. May be different,
p represents 0, 1, 2, 3, 4 or 5;
X represents C (R ⁸ R ⁹ ) ₂ , NR ¹⁰ , oxygen or sulfur;
And,
R ⁶ to R ¹⁰ represent hydrogen, alkyl, cycloalkyl, aryl or hetaryl.

  The Buchwald-Hartwig amination reaction is a well-established synthetic route and the reaction conditions can be easily determined by those skilled in the art. Conversion of aryl bromides to arylamines is notably described in the publication “A Simple Catalytic Method for the Conversion of Aryl Bromides to Arylamines”, Angewandte Chemie International Edition 34 (Guram, AS; Rennels, RA; Buchwald, SL (1995). 12): Handled in 1348-1350.

  The above compounds of general formulas I and II and preferred embodiments thereof generally have a low tendency to crystallize and thus have increased long-term stability of the resulting organic electronic device, especially for organic field effect transistors, dyes It is particularly suitable for sensitized solar cells and bulk heterojunction solar cells. In the above devices, these compounds typically function as hole transport materials.

  Accordingly, another object of the present invention is the use of compounds of general formula I and preferred embodiments thereof in organic electronics applications. In particular, the compounds of general formula I and their preferred embodiments are used in organic field effect transistors, organic solar cells and organic photodetectors.

  Another preferred subject of the present invention is the use of compounds of general formula I and preferred embodiments thereof in dye-sensitized solar cells and bulk heterojunction solar cells.

  A further subject of the present invention relates to field effect transistors, dye-sensitized solar cells and bulk heterojunction solar cells comprising compounds of general formula I and preferred embodiments thereof.

In the present invention, alkyl, aryl or heteroaryl represents unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl. Alkyl includes linear or branched alkyl. Alkyl is preferably C ₁ -C ₃₀ alkyl, especially C ₁ -C ₂₀ alkyl, most preferably C ₁ -C ₁₂ alkyl. Examples of alkyl groups are in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

［式中、
＃は、結合部位を示し、かつ、
Ｒ^aは、Ｃ₁〜Ｃ₂₈アルキルから選択されており、その際、このＲ^a基の炭素原子の総和は、２〜２９の整数である］
により示すことができる。 Further examples of branched alkyl groups are:

[Where:
# Indicates a binding site, and
R ^a is selected from C ₁ -C ₂₈ alkyl, wherein the sum of carbon atoms of this R ^a group is an integer from 2 to 29]
Can be shown.

In the above formula, the R ^a group is preferably selected from C ₁ -C ₁₂ alkyl, in particular C ₁ -C ₈ alkyl.

Preferred branched alkyl groups of the above formula are for example:
1-ethylpropyl, 1-methylpropyl, 1-propylbutyl, 1-ethylbutyl, 1-methylbutyl, 1-butylpentyl, 1-propylpentyl, 1-ethylpentyl, 1-methylpentyl, 1-pentylhexyl, 1- Butylhexyl, 1-propylhexyl, 1-ethylhexyl, 1-methylhexyl, 1-hexylheptyl, 1-pentylheptyl, 1-butylheptyl, 1-propylheptyl, 1-ethylheptyl, 1-methylheptyl, 1-heptyl Octyl, 1-hexyloctyl, 1-pentyloctyl, 1-butyloctyl, 1-propyloctyl, 1-ethyloctyl, 1-methyloctyl, 1-octylnonyl, 1-heptylnonyl, 1-hexylnonyl, 1-pentylnonyl , 1-butylnonyl, 1-propyl Nyl, 1-ethylnonyl, 1-methylnonyl, 1-nonyldecyl, 1-octyldecyl, 1-heptyldecyl, 1-hexyldecyl, 1-pentyldecyl, 1-butyldecyl, 1-propyldecyl, 1-ethyldecyl, 1-methyldecyl, 1-decylundecyl, 1-nonylundecyl, 1-octylundecyl, 1-heptylundecyl, 1-hexylundecyl, 1-pentylundecyl, 1-butylundecyl, 1-propylundecyl, 1-ethylundecyl, 1-methylundecyl, 1-undecyldodecyl, 1-decyldodecyl, 1-nonyldodecyl, 1-octyldodecyl, 1-heptyldodecyl, 1-hexyldecyl, 1-pentyldecyl, 1-butyldodecyl, 1-propyl Dodecyl, 1-ethyldodecyl, 1-me Ludodecyl, 1-dodecyltridecyl, 1-undecyltridecyl, 1-decyltridecyl, 1-nonyltridecyl, 1-octyltridecyl, 1-heptyltridecyl, 1-hexyltridecyl, 1-pentyltridecyl, 1-butyl Tridecyl, 1-propyltridecyl, 1-ethyltridecyl, 1-methyltridecyl, 1-tridecyltetradecyl, 1-undecyltetradecyl, 1-decyltetradecyl, 1-nonyltetradecyl, 1-octyl Tetradecyl, 1-heptyltetradecyl, 1-hexyltetradecyl, 1-pentyltetradecyl, 1-butyltetradecyl, 1-propyltetradecyl, 1-ethyltetradecyl, 1-methyltetradecyl, 1-pentadecylhexa Decyl, 1-tetradecylhexadecyl, 1-tri Decyl hexadecyl, 1-dodecyl hexadecyl, 1-undecyl hexadecyl, 1-decyl hexadecyl, 1-nonyl hexadecyl, 1-octyl hexadecyl, 1-heptyl hexadecyl, 1-hexyl hexadecyl, 1-pentyl Hexadecyl, 1-butylhexadecyl, 1-propylhexadecyl, 1-ethylhexadecyl, 1-methylhexadecyl, 1-hexadecyloctadecyl, 1-pentadecyloctadecyl, 1-tetradecyloctadecyl, 1-tridecyloctadecyl 1-dodecyloctadecyl, 1-undecyloctadecyl, 1-decyloctadecyl, 1-nonyloctadecyl, 1-octyloctadecyl, 1-heptyloctadecyl, 1-hexyloctadecyl, 1-pentyloctadecyl, 1-butyloctadecyl 1-propyloctadecyl, 1-ethyloctadecyl, 1-methyloctadecyl, 1-nonadecyleicosanyl, 1-octadecyleicosanyl, 1-heptadecyleicosanyl, 1-hexadecyleicosanyl, 1- Pentadecyleicosanil, 1-tetradecyleicosanyl, 1-tridecyleicosanil, 1-dodecyleicosanil, 1-undecyleicosanyl, 1-decyleicosanil, 1-nonyleicosanyl 1-octyleicosanyl, 1-heptyleicosanyl, 1-hexyleicosanyl, 1-pentyleicosanyl, 1-butyleicosanyl, 1-propyleicosanil, 1-ethyleicosanyl, 1-methyleicosanil, 1-eicosanil docosanyl, 1-nonadecyl docosanyl, 1-octadecyl docosa 1-heptadecyl docosanyl, 1-hexadecyl docosanyl, 1-pentadecyl docosanyl, 1-tetradecyl docosanyl, 1-tridecyl docosanyl, 1-undecyl docosanyl, 1-decyl docosanyl, 1- Nonyldocosanyl, 1-octyldocosanyl, 1-heptyldocosanyl, 1-hexyldocosanyl, 1-pentyldocosanyl, 1-butyldocosanyl, 1-propyldocosanyl, 1-ethyldocosanyl, 1-methyldocosanyl, 1-tricosaniltetra Cosanyl, 1-docosanyltetracosanyl, 1-nonadecyltetracosanyl, 1-octadecyltetracosanyl, 1-heptadecyltetracosanyl, 1-hexadecyltetracosanyl, 1-pentadecyltetracosanyl, 1-pentadecyltetracosanyl, 1-tetradecyl Tetracosanyl, 1-tridecyltetracosanyl, 1-dodecyltetracosanyl, 1-undecyltetracosanyl, 1-decyltetracosanyl, 1-nonyltetracosanyl, 1-octyltetracosanyl, 1-heptyltetra Cosanyl, 1-hexyltetracosanyl, 1-pentyltetracosanyl, 1-butyltetracosanyl, 1-propyltetracosanyl, 1-ethyltetracosanyl, 1-methyltetracosanyl, 1-heptacosanyl Octacosanyl, 1-hexacosanyl octacosanyl, 1-pentacosanyl octacosanyl, 1-tetracosanyl octacosanyl, 1-tricosanyl octacosanyl, 1-docosanyl octacosanyl, 1- Nonadecyl octacosanyl, 1-octadecyl octacosanyl, 1-heptadecyl octacosanyl, -Hexadecyl octacosanyl, 1-hexadecyl octacosanyl, 1-pentadecyl octacosanyl, 1-tetradecyl octacosanyl, 1-tridecyl octacosanyl, 1-dodecyl octacosanyl, 1-undecyl Octacosanyl, 1-decyloctacosanyl, 1-nonyloctacosanyl, 1-octyloctacosanyl, 1-heptyloctacosanyl, 1-hexyloctacosanyl, 1-pentyloctacosanyl, 1-butylocta Cosanyl, 1-propyloctacosanyl, 1-ethyloctacosanyl, 1-methyloctacosanyl.

Alkyl includes alkyl whose carbon chain may be interrupted by one or more non-adjacent groups selected from oxygen, sulfur, —CO—, —NR ^b —, —SO— and / or —SO ₂ —. A group is also included, wherein R ^b is preferably hydrogen, unsubstituted linear or branched alkyl as described above, or unsubstituted aryl as described below.

  A substituted alkyl group may have one or more (eg, more than 1, 2, 3, 4, 5, or 5) substituents depending on the alkyl chain length. These substituents are preferably independently of one another selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro.

An aryl-substituted alkyl group (aralkyl) has at least one unsubstituted or substituted aryl group as defined below. The alkyl group of the aralkyl group may have at least one further substituent and / or selected from oxygen, sulfur, —CO—, —NR ^b —, —SO— and / or —SO ₂ —. May be interrupted by one or more non-adjacent groups, wherein R ^b is preferably hydrogen, unsubstituted linear or branched alkyl as described above, or non-substituted as described below. Substituted aryl. Aralkyl is preferably phenyl-C ₁ -C ₁₀ alkyl, more preferably phenyl-C ₁ -C ₄ alkyl, such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop- 1-yl, 3-phenprop-1-yl, 1-fenbut-1-yl, 2-fenbut-1-yl, 3-fenbut-1-yl, 4-fenbut-1-yl, 1-fenbut-2- Yl, 2-fenbut-2-yl, 3-fenbut-2-yl, 4-fenbut-2-yl, 1- (phenmeth) eth-1-yl, 1- (phenmethyl) -1- (methyl) eth -1-yl or-(phenmethyl) -1- (methyl) prop-1-yl, preferably benzyl and 2-phenethyl.

The halogen-substituted alkyl group (haloalkyl) includes a linear or branched alkyl group in which at least one hydrogen atom or all hydrogen atoms are substituted with halogen. The halogen atom is preferably selected from fluorine, chlorine and bromine, in particular fluorine and chlorine. Examples of haloalkyl groups are in particular chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1 -Fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- Dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3 -Chloropropyl, 2,3-dichloropropyl Pills, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloro _{propyl, -CH 2 -C 2 F 5,} -CF 2 -C 2 F 5, - CF (CF ₃ ) ₂ , 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4 -Bromobutyl, nonafluorobutyl, 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl , Undecafluoropentyl, 6-fluoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6,6,6-tri Lolo-1-hexyl or dodecafluoro hexyl.

  The above explanations for unsubstituted or substituted alkyl also apply to unsubstituted or substituted alkoxy and unsubstituted or substituted dialkylamino.

Specific examples of unsubstituted and substituted alkyl groups which may be interrupted by one or more non-adjacent groups selected from oxygen, sulfur, —NR ^b —, —CO—, —SO— and / or —SO ₂ —. An example is as follows:
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n- Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 3-methoxypropyl , 3-ethoxypropyl, 3-propoxypropyl, 3-butoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8 -Dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7 Dioxaoctyl, 4,7-dioxanonyl, 2-butoxybutyl, 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6 , 9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;
2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-butylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-propylthiopropyl, 3-butylthiopropyl, 4-methylthiobutyl 4-ethylthiobutyl, 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithianonyl, 2-butylthiobutyl, 4 -Butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl, 3,6,9-trithiaundecyl, 3,6,9-trithiadecyl, 3,6,9,12-tetrathiatri Decyl and 3,6,9,12-tetrathiatetradecyl;
2-monomethylaminoethyl, 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2-monopropylaminobutyl, 4-monopropylamino Butyl, 2-dimethylaminobutyl, 4-dimethylaminobutyl, 6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl, 3,6-dimethyl-3, 6-diazaoctyl, 9-methyl-3,6,9-triazadecyl, 3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl -3,6,9-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl and , 6,9,12-tetramethyl-3,6,9,12-tetraazacyclododecane-tridecyl;
(1-ethylethylidene) aminoethylene, (1-ethylethylidene) aminopropylene, (1-ethylethylidene) aminobutylene, (1-ethylethylidene) aminodecylene and (1-ethylethylidene) aminododecylene;
Propan-2-one-1-yl, butan-3-one-1-yl, butan-3-on-2-yl and 2-ethylpentan-3-on-1-yl;
2-methylsulfinylethyl, 2-ethylsulfinylethyl, 2-propylsulfinylethyl, 2-isopropylsulfinylethyl, 2-butylsulfinylethyl, 2-methylsulfinylpropyl, 3-methylsulfinylpropyl, 2-ethylsulfinylpropyl, 3- Ethylsulfinylpropyl, 2-propylsulfinylpropyl, 3-propylsulfinylpropyl, 2-butylsulfinylpropyl, 3-butylsulfinylpropyl, 2-methylsulfinylbutyl, 4-methylsulfinylbutyl, 2-ethylsulfinylbutyl, 4-ethylsulfinyl Butyl, 2-propylsulfinylbutyl, 4-propylsulfinylbutyl and 4-butylsulfinylbutyl;
2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonylethyl, 2-butylsulfonylethyl, 2-methylsulfonylpropyl, 3-methylsulfonylpropyl, 2-ethylsulfonylpropyl, 3- Ethylsulfonylpropyl, 2-propylsulfonylpropyl, 3-propylsulfonylpropyl, 2-butylsulfonylpropyl, 3-butylsulfonylpropyl, 2-methylsulfonylbutyl, 4-methylsulfonylbutyl, 2-ethylsulfonylbutyl, 4-ethylsulfonyl Butyl, 2-propylsulfonylbutyl, 4-propylsulfonylbutyl and 4-butylsulfonylbutyl;
Carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxytetradecyl;
Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;
2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl and 8-hydroxyl-4-oxaoctyl;
2-cyanoethyl, 3-cyanopropyl, 3-cyanobutyl and 4-cyanobutyl;
2-chloroethyl, 2-chloropropyl, 3-chloropropyl, 2-chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 2-bromoethyl, 2-bromopropyl, 3-bromopropyl, 2-bromobutyl, 3-bromobutyl and 4- Bromobutyl;
2-nitroethyl, 2-nitropropyl, 3-nitropropyl, 2-nitrobutyl, 3-nitrobutyl and 4-nitrobutyl;
Methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy;
Methylthio, ethylthio, propylthio, butylthio, pentylthio and hexylthio;
Methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino;
Formylamino, acetylamino, propionylamino and benzoylamino;
Carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl, decylaminocarbonyl and phenylaminocarbonyl;
Aminosulfonyl, n-dodecylaminosulfonyl, Ν, Ν-diphenylaminosulfonyl and N, N-bis (4-chlorophenyl) aminosulfonyl;
Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, (4-tert-butylphenoxy) carbonyl and (4-chlorophenoxy) carbonyl;
Methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, butoxysulfonyl, hexoxysulfonyl, dodecyloxysulfonyl and octadecyloxysulfonyl.

  In the present invention, cycloalkyl preferably represents an alicyclic group having 3 to 10 carbon atoms, more preferably 5 to 8 carbon atoms. Examples of cycloalkyl groups are in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

A substituted cycloalkyl group may have one or more (eg, more than 1, 2, 3, 4, 5, or 5) substituents depending on the ring size. These substituents are preferably independently of one another selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. When substituted, the cycloalkyl group preferably has one or more, for example 1, 2, 3, 4, or 5, C ₁ -C ₆ alkyl groups. Examples of substituted cycloalkyl groups are in particular 2-methylcyclopentyl, 3-methylcyclopentyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2-ethylcyclohexyl, 3-ethyl cyclohexyl, 4-ethyl cyclohexyl, 2-propyl cyclohexyl, 3-propyl cyclohexyl, 4-propyl cyclohexyl, 2-isopropyl cyclohexyl, 3-isopropyl cyclohexyl, 4-isopropyl cyclohexyl, 2-butyl cyclohexyl, 3-butyl cyclohexyl, 4-butylcyclohexyl, 2-sec-butylcyclohexyl, 3-sec-butylcyclohexyl, 4-sec-butylcyclohexyl, 2-tert Butylcyclohexyl, 3-tert-butylcyclohexyl, 4-tert-butylcyclohexyl, 2-methylcycloheptyl, 3-methylcycloheptyl, 4-methylcycloheptyl, 2-ethylcycloheptyl, 3-ethylcycloheptyl, 4-ethyl Cycloheptyl, 2-propylcycloheptyl, 3-propylcycloheptyl, 4-propylcycloheptyl, 2-isopropylcycloheptyl, 3-isopropylcycloheptyl, 4-isopropylcycloheptyl, 2-butylcycloheptyl, 3-butylcycloheptyl 4-butylcycloheptyl, 2-sec-butylcycloheptyl, 3-sec-butylcycloheptyl, 4-sec-butylcycloheptyl, 2-tert-butylcycloheptyl, 3-tert-butyl Cycloheptyl, 4-tert-butylcycloheptyl, 2-methylcyclooctyl, 3-methylcyclooctyl, 4-methylcyclooctyl, 5-methylcyclooctyl, 2-ethylcyclooctyl, 3-ethylcyclooctyl, 4-ethyl Cyclooctyl, 5-ethylcyclooctyl, 2-propylcyclooctyl, 3-propylcyclooctyl, 4-propylcyclooctyl and 5-propylcyclooctyl.

  Specific examples of the substituted or unsubstituted cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2-ethylcyclopentyl, 3-ethylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, and 3-methylcyclohexyl. 4-methylcyclohexyl, 2-ethylcyclohexyl, 3-ethylcyclohexyl, 4-ethylcyclohexyl, 3-propylcyclohexyl, 4-propylcyclohexyl, 3-isopropylcyclohexyl, 4-isopropylcyclohexyl, 3-butylcyclohexyl, 4-butylcyclohexyl 3-sec-butylcyclohexyl, 4-sec-butylcyclohexyl, 3-tert-butylcyclohexyl, 4-tert-butylsilane Rohexyl, cycloheptyl, 2-methylcycloheptyl, 3-methylcycloheptyl, 4-methylcycloheptyl, 2-ethylcycloheptyl, 3-ethylcycloheptyl, 4-ethylcycloheptyl, 3-propylcycloheptyl, 4-propyl Cycloheptyl, 3-iso-propylcycloheptyl, 4-iso-propylcycloheptyl, 3-butylcycloheptyl, 4-butylcycloheptyl, 3-sec-butylcycloheptyl, 4-sec-butylcycloheptyl, 3-tert -Butylcycloheptyl, 4-tert-butylcycloheptyl, cyclooctyl, 2-methylcyclooctyl, 3-methylcyclooctyl, 4-methylcyclooctyl, 5-methylcyclooctyl, 2-ethylcyclooctyl, 3-ethylcyclooct Til, 4-ethylcyclooctyl, 5-ethylcyclooctyl, 3-propylcyclooctyl, 4-propylcyclooctyl and 5-propylcyclooctyl; 3-hydroxycyclohexyl, 4-hydroxycyclohexyl, 3-nitrocyclohexyl, 4-nitro Cyclohexyl, 3-chlorocyclohexyl and 4-chlorocyclohexyl.

  In the present invention, aryl is a monocyclic or polycyclic aromatic hydrocarbon group, and one or more non-condensed or condensed saturated or unsaturated carbocyclic or heterocyclic 5-membered or 6-membered ring. Includes monocyclic aromatic hydrocarbon groups that may be fused to the ring. Aryl preferably has 6 to 14, more preferably 6 to 10 carbon atoms. Examples of aryl are in particular phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl and pyrenyl, in particular phenyl, naphthyl and fluorenyl.

  A substituted aryl may have one or more (eg, more than 1, 2, 3, 4, 5, or 5) substituents depending on the number and size of the ring system. These substituents are preferably independently of one another selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. On the other hand, alkyl substituents, alkoxy substituents, alkylamino substituents, alkylthio substituents, cycloalkyl substituents, heterocycloalkyl substituents, aryl substituents and hetaryl substituents on aryl are substituted even if they are unsubstituted. May be. For these groups, reference is made to the above substituents. The substituents on aryl are preferably selected from alkyl, alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano and nitro. Substituted aryl is more preferably substituted phenyl generally having one, two, three, four or five, preferably one, two or three substituents.

  Substituted aryl is preferably aryl ([alkaryl]) substituted by at least one alkyl group. An alkaryl group can have one or more (eg, one, two, three, four, five, six, seven, eight, nine or nine, depending on the size of the aromatic ring system. More) alkyl substituents. This alkyl substituent may be unsubstituted or substituted. In this regard, reference is made to the above description regarding unsubstituted and substituted alkyl. In one preferred embodiment, the alkaryl group has exclusively unsubstituted alkyl substituents. Alkaryl is preferably phenyl with one, two, three, four or five, preferably one, two or three, more preferably one or two alkyl substituents.

  Aryl having one or more groups is, for example, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 2, 6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 3,5-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-propylphenyl, 3-propylphenyl, 4-propylphenyl, 2,4-dipropylphenyl, 2,5-dipropylphenyl, 3,5 -Dipropylphenyl, 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-isopropylpheny 3-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl, 2,5-diisopropylphenyl, 3,5-diisopropylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2 -Butylphenyl, 3-butylphenyl, 4-butylphenyl, 2,4-dibutylphenyl, 2,5-dibutylphenyl, 3,5-dibutylphenyl, 2,6-dibutylphenyl, 2,4,6-tributylphenyl 2-isobutylphenyl, 3-isobutylphenyl, 4-isobutylphenyl, 2,4-diisobutylphenyl, 2,5-diisobutylphenyl, 3,5-diisobutylphenyl, 2,6-diisobutylphenyl, 2,4,6- Triisobutylphenyl, 2-sec-butylphenyl Nyl, 3-sec-butylphenyl, 4-sec-butylphenyl, 2,4-di-sec-butylphenyl, 2,5-di-sec-butylphenyl, 3,5-di-sec-butylphenyl, 2 , 6-Di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 2,4-di- tert-butylphenyl, 2,5-di-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 3,5- Dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2,4-diethoxyphenyl, 2,5-diethoxyphenyl 3,5-diethoxyphenyl, 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-propoxyphenyl, 3-propoxyphenyl, 4-propoxyphenyl, 2,4-dipropoxyphenyl, 2,5-dipropoxyphenyl, 3,5-dipropoxyphenyl, 2,6-dipropoxyphenyl, 2-isopropoxyphenyl, 3-isopropoxyphenyl, 4-isopropoxyphenyl, 2,4-diisopropoxyphenyl 2,5-diisopropoxyphenyl, 3,5-diisopropoxyphene 2-cyanophenyl, 3-cyanophenyl and 4-cyanophenyl; le, 2,6-di-isopropoxyphenyl, 2-butoxyphenyl, 3-butoxyphenyl and 4-butoxyphenyl.

  The above description regarding unsubstituted or substituted aryl also applies to unsubstituted or substituted aryloxy and unsubstituted or substituted arylthio. Examples of aryloxy are phenoxy and naphthyloxy.

  In the present invention, hetaryl is a heteroaromatic monocyclic or polycyclic group and one or more non-condensed or condensed saturated or unsaturated carbocyclic or heterocyclic 5-membered or 6-membered ring. Including monocyclic groups which may be fused to In addition to the ring carbon atoms, they have 1, 2, 3, 4 or more than 4 ring heteroatoms. This heteroatom is preferably selected from oxygen, nitrogen, selenium and sulfur. A hetaryl group preferably has 5 to 18, for example 5, 6, 8, 9, 10, 11, 12, 13, or 14 ring atoms.

  The monocyclic hetaryl group is preferably a 5- or 6-membered hetaryl group, such as 2-furyl (furan-2-yl), 3-furyl (furan-3-yl), 2-thienyl (thiophen-2-yl). Yl), 3-thienyl (thiophen-3-yl), selenophen-2-yl, selenophen-3-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazole- 2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5- Isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, -Thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazole-2 -Yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H- [1,2,4] -triazole -3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridine-3 -Yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4 -Triazine-3- Is Le.

  Polycyclic hetaryl has 2, 3, 4, or more than 4 fused rings. This fused ring may be aromatic, saturated or partially unsaturated. Examples of polycyclic hetaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isobenzofuranyl, benzothiophenyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, benzoxiadiazolyl; Benzoxazinyl, benzopyrazolyl, benzoimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl, thienothiophenyl, thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofuranyl, dibenzothiophenyl, naphtho [ 2,3-b] thiophenyl, naphtha [2,3-b] furyl, dihydroindolyl, dihydroindolidinyl, dihydroisoindolyl, dihydroquinolinyl, dihydroyl It is quinolinyl.

A substituted heteroaryl may have one or more (eg, more than 1, 2, 3, 4, 5, or 5) substituents depending on the number and size of the ring system. These are preferably independently of one another selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, cyano and nitro. The halogen substituent is preferably fluorine, chlorine or bromine. Substituents are preferably, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, hydroxyl, carboxyl, selected from halogen and cyano.

  The above description regarding unsubstituted or substituted heteroaryl also applies to unsubstituted or substituted heteroaryloxy and unsubstituted or substituted heteroarylthio.

  Further details on the preparation of the compounds according to the invention can be obtained from the experimental part.

  A DSC generally consists of the following elements: a conductive layer (either part of or forming a working electrode or anode), generally a photosensitive layer comprising a semiconductive metal oxide and a photosensitive dye. Conductive layers, charge transport layers, and other conductive layers (which are part of or form a counter electrode or cathode).

  For further details of the construction of the DSC, reference is made in particular to WO 2012/001628 A1, which is hereby incorporated by reference.

It is a figure which shows the comparison with the lifetime of DSC containing hole transport material HTM1, HTM2, and HTM3 by this invention, and the lifetime of DSC containing spiro-MeOTAD. FIG. 3 shows the initial condition, ie, 25 ° C., of the spiro-MeOTAD coating on the silver back electrode of the battery after assembly and before heat treatment. FIG. 4 shows the state of a spiro-MeOTAD coating on the silver back electrode of the battery after heating at 100 ° C. for 240 minutes.

Experimental part A1) Preparation of compounds of general formula I according to the invention Using the Buchwald-Hartwig CN cross-coupling reaction, the corresponding diphenylamines M1 to M3 are synthesized from the respective aromatic amines and aryl halides. did. These diphenylamines M1 to M3 and 2,2 ′, 7,7′-tetrabromo-9,9′-spirobifluorene (for example, commercially available from TCI EUROPE NV, Zweindrecht, Belgium) The target hole transport materials HTM1, HTM2 and HTM3 were obtained by a palladium contact reaction with

Example 1: Production of HTM1

a) Preparation of 4,4′-dimethoxy-3-methyldiphenylamine (M1):

A mixture of dioxane (12 ml) and water (0.004 g, 0.22 mmol) was purged with argon for 20 minutes. Pd (OAc) ₂ (0.014 g, 0.06 mmol) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (“XPhos”; 0.086 g, 0.18 mmol) are added, The mixture was heated to 80 ° C. for 90 seconds. Then 5-bromo-2-methoxytoluene (2.44 g, 12.1 mmol), 4-methoxyaniline (1.79 g, 14.5 mmol) and NaOt-Bu (1.64 g, 17.1 mmol) were added, The mixture was stirred at 110 ° C. for 15 minutes. After completion of the reaction (monitored by TLC, acetone: n-hexane = 1: 4, v / v), the mixture was diluted with ethyl acetate and washed with water. The organic layer was dried over anhydrous Na ₂ SO ₄ , filtered and the solvent removed. The residue was purified by column chromatography using acetone: n-hexane (0.5: 24.5, v / v) as eluent. The product was obtained as whiteish crystals (2.7 g, 92%). Melting point: 55-56.5 ° C.

b) Preparation of HTM1 2,2 ', 7,7'-tetrabromo-9,9'-spirobifluorene (0.28 g, 0.44 mmol) and M1 (0.75 g, 3.5 g) in anhydrous toluene (5 ml). 08 mmol) was purged with argon for 20 minutes. Pd (OAc) ₂ (0.002 g, 0.009 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.004 g, 0.013 mmol) and NaOt-Bu (0.25 g, 2.60 mmol) were added, The mixture was refluxed for 4 hours. After completion of the reaction (monitored by TLC, Acetone: n-hexane = 7: 18, v / v ), the mixture was diluted with toluene, filtered through Celite ^(R), and extracted with water. The organic layer was dried over anhydrous Na ₂ SO ₄ , filtered and the solvent removed. The residue was purified by column chromatography using acetone: n-hexane (1:24 and 2:23, v / v) as eluent, then from a 20% solution in acetone in a 10-fold excess of methanol. Precipitated. The precipitate was filtered off and washed with methanol, yielding 0.45 g (80%) of a light yellow solid.

Example 2: Production of HTM2

を表す。 Here, R is an equimolar ratio and a partial distribution in a random distribution.

Represents.

a) Preparation of 4,4′-dimethoxy-3,5-dimethyldiphenylamine (M2)

A mixture of dioxane (6.5 ml) and water (0.002 g, 0.11 mmol) was purged with argon for 20 minutes. Pd (OAc) ₂ (0.007 g, 0.031 mmol) and 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (“SPhos”; 0.04 g, 0.097 mmol) are added and the mixture is added to 90 Heated to 80 ° C. for seconds. Then 4-iodo-1,3-dimethyl-2-methoxybenzene (1.7 g, 6.49 mmol), 4-methoxyaniline (0.96 g, 7.80 mmol) and NaOt-Bu (0.88 g, 9. 12 mmol) was added and the mixture was stirred at 110 ° C. for 15 min. After completion of the reaction (monitored by TLC, acetone: n-hexane = 1: 4, v / v), the mixture was diluted with ethyl acetate and washed with water. The organic layer was dried over anhydrous Na ₂ SO ₄ , filtered and the solvent removed. The residue was purified by column chromatography using acetone: n-hexane (0.9: 24.1, v / v) as eluent. The product was obtained as a light brown solid (1.60 g, 96%). Melting point: 84-85 ° C.

b) Preparation of HTM2 2,2 ′, 7,7′-Tetrabromo-9,9′-spirobifluorene (0.50 g, 0.79 mmol), M1 (0.41 g, 1.t) in anhydrous toluene (10 ml). 67 mmol) and M2 (0.43 g, 1.67 mmol) were purged with argon for 30 min. Pd (OAc) ₂ (0.004 g, 0.018 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.006 g, 0.021 mmol) and NaOt-Bu (0.46 g, 4.79 mmol) were added, The mixture was refluxed for 2 hours. After completion of the reaction (monitored by TLC, Acetone: n-hexane = 1: 4, v / v ), the mixture was diluted with toluene, filtered through Celite ^(R), and extracted with water. The organic layer was dried over anhydrous Na ₂ SO ₄ , filtered and the solvent removed. The residue was purified by column chromatography using acetone: n-hexane (2:23 and 3:22, v / v) as the eluent, followed by a 10-fold excess of n- from a 20% solution in toluene. Precipitated into hexane. The precipitate was filtered off and washed with n-hexane to give a pale yellow solid (0.75 g, 72%).

Example 3: Production of HTM3

a) Preparation of 3,4'-dimethoxydiphenylamine (M3)

A mixture of dioxane (10 ml) and water (0.004 g, 0.22 mmol) was purged with argon for 20 minutes. Pd (OAc) ₂ (0.011 g, 0.049 mmol) and 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (“SPhos”; 0.062 g, 0.15 mmol) are added and the mixture is added to 90 Heated to 80 ° C. for seconds. Then 4-methoxyiodobenzene (2.34 g, 10 mmol), 3-methoxyaniline (1.47 g, 11.94 mmol) and NaOt-Bu (1.35 g, 14.05 mmol) were added and the mixture was added for 20 minutes. Over a period of 110 ° C. After completion of the reaction (monitored by TLC, acetone: n-hexane = 1: 4, v / v), the mixture was diluted with ethyl acetate and washed with water. The organic layer was dried over anhydrous Na ₂ SO ₄ , filtered and the solvent removed. The residue was purified by column chromatography using acetone: n-hexane (0.5: 24.5, v / v) as eluent. The product was obtained as whiteish crystals (1.89 g, 96%). Melting point: 66-67.5 ° C.

b) Preparation of HTM3 2,2 ', 7,7'-tetrabromo-9,9'-spirobifluorene (0.4 g, 0.63 mmol) and 3,4'-dimethoxydiphenylamine (4 ml) in anhydrous toluene (6 ml) 0.88 g, 3.84 mmol) was purged with argon for 30 minutes. Pd (OAc) ₂ (0.003 g, 0.013 mmol), tri-tert-butylphosphonium tetrafluoroborate (0.005 g, 0.017 mmol) and NaOt-Bu (0.36 g, 3.75 mmol) were added, The mixture was refluxed for 3 hours. After completion of the reaction (monitored by TLC, Acetone: n-hexane = 1: 4, v / v ), the mixture was diluted with toluene, filtered through Celite ^(R), and extracted with water. The organic layer was dried over anhydrous Na ₂ SO ₄ , filtered and the solvent removed. The residue was purified by column chromatography using acetone: n-hexane (7:18, v / v) as eluent and then precipitated from a 20% solution in acetone into a 10-fold excess of methanol. . The precipitate was filtered off and washed with methanol, yielding 0.60 g (77%) of a yellow solid.

B) DSC fabrication and characterization General methods and materials Manufacture of solid dye-sensitized solar cells: TiO ₂ blocking layer is applied onto fluorine-doped tin oxide (FTO) coated glass substrate using spray pyrolysis method (See B. Peng, G. Jungmann, C. Jager, D. Haarer, HW Schmidt, M. Thelakkat, Coord. Chem. Rev. 2004, 248, 1479). Next, a TiO ₂ paste (pigment sol) diluted with terpineol was applied by a screen printing method to obtain a film thickness of 1.7 μm. All films were then fired at 450 ° C. for 45 minutes and then treated in a 40 mM aqueous solution of TiCl ₄ for 30 minutes at 60 ° C., followed by a further firing step. The prepared sample with this TiO ₂ layer was pretreated with a 5 mM solution of the additive 2- (p-butoxyphenyl) acetohydroxamic acid sodium salt (“ADD1”) in ethanol (this additive is WO 2012 / 001628 is described as “Example No. 6” on page 52 of A1). The electrode was then stained in a 0.5 mM dye solution in CH ₂ Cl ₂ . The hole transport material is a spiro-MeOTAD (commercially available as Darmstadt Merck KGaA company from SHT-263 livilux ^(R)) and compound HTM1, the HTM2 and _{HTM3, 20mM Li (CF 3 SO} 2) 2 Application was by spin coating from a solution in DCM (200 mg / mL) also containing N. Device assembly was completed by deposition of 200 nm silver as the counter electrode. The active area of the DSC was defined by the size of the contact surface (0.13 cm ² ) and the cell was masked with the same area aperture for measurement. The current-voltage characteristics of all the batteries were measured using a Keithley 2400 under 1000 W / m ² and AM1.5G conditions (LOT ORIEL 450 W). Quantum efficiency (IPCE) was obtained using an Acton Research Monochromator with additional white background light illumination.

This sample was irradiated with monochromatic light from a quartz monochromator using a deuterium lamp. The incident luminous flux output was (2-5) · 10 ⁻⁸ W. A negative voltage of −300 V was applied to this sample substrate. A counter electrode having a 4.5 × 15 mm ² slit for irradiation was placed at a distance of 8 mm from the sample surface. This counter electrode was connected to the input of a BK2-16 electrometer for photocurrent measurement and operated in an input open regime. A photocurrent with an intensity of 10 ^-15 to 10 ^-12 A flowed into the circuit under irradiation. The photocurrent J strongly depends on the photon energy hν of the incident light. J ^0.5 = f (hν) dependence was plotted. Usually, the dependence of the photocurrent on the incident photon energy is sufficiently expressed by the linear relationship between J ^0.5 and hν near the threshold (E. Miyamoto, Y. Yamaguchi, M. Yokoyama, Electrophotography 1989, 28, 364). And M. Cordona, L. Ley, Top. Appl. Phys. 1978, 26, 1). The linear part of this dependence is extrapolated to the hν axis, and the J _p value is determined as the photon energy at the intercept point.

  The DSC results using various hole transport materials (“HTM”) are shown in the following table, which corresponds to the AM1.5 standard conditions at 25 ° C.

The results in the table below were obtained at the start of the lifetime test under AM1.5 standard conditions and at 60 ° C. (values correspond to the case where the lifetime is 0 hours in FIG. 1). :

  FIG. 1 shows a comparison of the lifetime of a DSC containing hole transport materials HTM1, HTM2 and HTM3 according to the present invention and the lifetime of a DSC containing spiro-MeOTAD. In the case of HTM1, HTM2 and HTM3, the long-term stability of the corresponding DSC is significantly improved over DSCs including spiro-MeOTAD. Each DSC is sealed after assembly and kept constant at 60 ° C. and 30% humidity.

  In another series of experimental solar cells containing spiro-MeOTAD as a hole transport material, held at 100 ° C. for 240 minutes to elucidate the cause of lifetime reduction in cells containing spiro-MeOTAD (FIGS. 2 and 3).

  FIG. 2 is an illustration of the spiro-MeOTAD coating on the silver back electrode of the battery, at initial conditions, ie, 25 ° C., after assembly and before heat treatment. The spiro-MeOTAD crystal was not visible under an optical microscope using a crossed polarizer.

  FIG. 3 is an example of a state after heating at 100 ° C. for 240 minutes. Spiro-MeOTAD crystals became clearly visible under an optical microscope and the battery efficiency dropped dramatically to 0.02%. This photo was taken after cooling to 25 ° C.

Claims (9)

Formula I

[Where:
The variables R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² independently of one another have the meaning of aryl or hetaryl, provided that the groups R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² are not all the same]
9,9'-spirobifluorene compound. In the general formula I, the moieties N (R ¹¹ R ¹² ), N (R ²¹ R ²² ), N (R ³¹ R ³² ) and N (R ⁴¹ R ⁴² ) are the 2nd position of the 9,9′-spirobifluorene skeleton. The compound of claim 1, which is bonded to the 7-position, the 2′-position and the 7′-position. In the general formula I, the variable symbols R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² are independently of one another of the formula Ia or Ib

[Wherein the variable symbols have the following meanings:
R ⁵ represents hydrogen, alkyl, aryl, alkoxy, alkylthio, or —NR ⁶ R ^7. When two or more substituents are present (p is 2 or more), the substituents are the same. May be different,
p represents 0, 1, 2, 3, 4 or 5;
X represents C (R ⁸ R ⁹ ) ₂ , NR ¹⁰ , oxygen or sulfur;
And,
R ⁶ to R ¹⁰ represent hydrogen, alkyl, cycloalkyl, aryl or hetaryl]
The compound of Claim 1 or 2 which is a part of these. In general formula I, variable symbols R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ are the same as each other, and variable symbols R ¹² , R ²² , R ³² and R ⁴² are the same as each other. The compound according to any one of the above.   Use of a compound of general formula I according to any one of claims 1 to 4 in organic electronics applications.   Use of a compound of general formula I according to any one of claims 1 to 4 in an organic field effect transistor.   Use of a compound of general formula I according to any one of claims 1 to 4 in organic solar cells and organic photodetectors.   Use of a compound of general formula I according to any one of claims 1 to 4 in dye-sensitized solar cells and bulk heterojunction solar cells.   An organic field effect transistor, a dye-sensitized solar cell, and a bulk heterojunction solar cell comprising the compound of the general formula I according to any one of claims 1 to 4.

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