JP2003308630A - Rewritable optical information recording medium and recording/reproducing method, recording/reproducing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new rewritable optical recording medium having a recording layer comprising an organic dye film and capable of reversibly recording/ erasing information by laser beam radiation. <P>SOLUTION: The new rewritable optical information recording medium having as a recording film at least one layer of organic dye film comprising practically at least one kind of organic dye compound. Information is recorded and erased by reversible physical changes caused by laser beam irradiation on an organic dye film single element. Specifically, data are recorded by a local physical change by recording laser ray irradiation, data are reproduced by detecting the returned optical intensity change of a reproducing laser beam less powerful than a recording laser beam, and data are erased by at least one application of a continuous beam or a pulse beam more powerful than a recording laser beam and less powerful than the recording laser beam. A physical change involves a shape change. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel rewritable optical information recording medium having a recording layer made of an organic dye film and capable of reversibly recording and erasing information by laser light irradiation. The present invention also relates to a recording / reproducing method and a recording / reproducing apparatus using the same.

[0002]

2. Description of the Related Art Today, a write-once type organic optical disc (so-called CD
-R, DVD-R, etc.), rewritable phase-change optical disks (so-called CD-RW, DVD-RW, etc.), and further magneto-optical disks.

The CD-RW or DVD-RW is a phase-change type optical recording medium for a material containing a chalcogen element, for example, Te.
-Ge-Sb alloy, Ag-In-Sb-Te alloy, etc., but these are toxic. Further, in order to induce a phase change and form a stable recording mark and erase the recording mark, ZnS and ZnS adjacent to the recording film are used.
_{-SiO 2, SiO 2, Si 3} N 4, AlN , etc. sulfide, oxide, dielectric film made of nitride, and modulation factor of the recorded signal (contrast) improvement and Ag for the thermal properties improve, Al
Alternatively, a reflective film such as Ag alloy or Al alloy is required. To form these thin films, it is necessary to use a vacuum film forming method such as a sputtering method, and the film structure of the recording medium is complicated and
Since the film thickness of each thin film must be precisely controlled, it is difficult to manufacture an inexpensive optical recording medium.

Magneto-optical recording media are generally composed of alloy thin films of rare earth elements such as Gd and Tb and transition metals such as Fe, Ni and Co. These alloy thin films include moisture and oxygen in the atmosphere. Easily oxidized by SiO ₂ and Si ₃
A protective film such as N ₄ must prevent contact with the outside air, resulting in a problem of long-term recording stability. Further, in principle, there is a drawback that an external magnetic field is required for recording, and the polarization optical system must be used because the optical Kerr effect is used for the principle of reproducing recorded information.

On the other hand, the CD-R or DVD-R is an optical recording medium having an organic dye material as a recording film, but it is a write-once type in which writing is possible only once and cannot be rewritten.

A rewritable optical recording medium made of an organic material is capable of molecular design and synthesis as an optical functional material.
In addition, it is actively researched because it is excellent in non-toxicity and low cost.

Up to now, as a rewritable optical recording medium using an organic material, a photon mode type optical recording medium and a thermal mode (or heat mode) type optical recording medium have been reported.

For example, as a photon mode type, there is a rewritable type optical recording medium utilizing the photochromism of fulgide, spiropyran and diarylethene. For information on this rewritable optical recording medium, see Yasushi Yokoyam.
a: 'Fulgides for Memories and Switches', Chem. Rev. 2
000, 100, 1717-1739, Garry Berkovic, Valeri Krongau
z, Victor Weiss: 'Spiropyrans and Spirooxazines fo
r Memories and Switches', Chem. Rev. 2000, 100, 17
41 -1753, Masahiro Irie: 'Diarylethenes for Memori
es andSwitches', Chem. Rev. 2000, 100, 1685-1716
Details are described in. However, these optical recording media need to use laser beams of different wavelengths for recording and reproduction.

Further, since the photochromic reaction is used for both recording and reproduction, the light resistance to reproducing light is small, and there are problems in stability and repeatability. Also, since these are photon modes, they have high sensitivity and high speed, but
Some have poor light stability as well as thermal stability.

As a rewritable optical recording medium of a thermal mode type, for example, an optical recording medium described in JP-A-6-60421 is a polyurethane containing an optical absorbent such as an inorganic or organic pigment or a dye. Shape memory resin such as styrene-butadiene copolymer is used as the recording layer.The portion recorded by laser light is thermally expanded to form convex ridges and rapidly solidifies. Irradiating with erasing light of stronger power than
This is done by irradiating the laser light for a longer time than during recording. Further, JP-A-6-1073 discloses an optical recording medium using a recording layer containing a conjugated polymer whose conformation is changed by thermal energy and a dye having a light absorbing ability.

Further, Japanese Patent Laid-Open No. 9-226249 proposes rewriting of information by reversibly changing the cohesive force between the substituents of the central metal in the metal phthalocyanine compound. Only examples in which a metal phthalocyanine compound is dissolved in a polymer compound such as polystyrene or polyamide are described.

Further, Japanese Patent Laid-Open No. 9-147414 proposes an optical recording medium using a photochromism material, a thermochromism material, and an associative dye such as an azaannulene compound such as phthalocyanine as a recording layer and using the change in the absorbance of the recording layer. However, only the examples mixed with a polymer compound such as polystyrene and polymethylmethacrylate are described.

In all of these examples, there is described the case where a recording film in which an organic dye having a light absorption ability is dispersed and mixed or polymerized in a polymer compound is used, and the mixing ratio (or polymerization ratio) thereof is 20-80. %. In such cases,
If the mixing ratio of the light-absorbing dye dispersed in the system is small, the amount of energy absorbed and converted into heat is small and the recording sensitivity is lowered. In addition, since the proportion of the dye is small, it is difficult to obtain a large degree of modulation. Become. On the other hand, if the mixing ratio is large, the aggregation, segregation, crystallization and association of the dyes occur nonuniformly, which becomes a source of signal noise. Further, unless proper polymer compounds and polymers are selected, there is a drawback that the dispersed state is likely to change with time in the stored state even if the dispersed state is uniform during film formation. Furthermore, even in the production of disks, it is necessary to select a polymer compound with low hygroscopicity in order to obtain long-term storage stability, so a solvent that dissolves this polymer compound and does not attack the substrate is selected. In many cases, it is difficult to carry out the process, and the reproducibility of the production is also lacking.

[0014] Further, in the publication of Japanese Patent No. 3054770,
Fatty acid or fatty acid derivative, benzoic acid derivative or n
-A method for detecting a difference in polarization characteristics by causing a change in crystal state accompanied by a reversible change in the orientation direction of molecules in a recording layer made of an organic thin film crystal having optical anisotropy such as alkane is described. However, the crystallinity of these organic thin film crystals becomes non-uniform, and the signal noise level is likely to increase. Further, as in the case of the magneto-optical disk, there is a problem that the recording / reproducing apparatus needs a polarization optical system.

[0015]

In an optical information recording medium, high density recording is possible, appropriate recording sensitivity, low noise and large modulation degree, good reproducing performance, high erasing ratio and a large number of repetitions. It is necessary to have excellent rewriting performance, and it is practically important to have a simple structure with high mass productivity. Furthermore, currently used optical recording media, for example, a laser oscillation wavelength of 780 is used.
CD near 650 nm, DVD near 650 nm, and laser oscillation wavelength of 4 which is considered to be the next generation optical disc.
It is desirable to maintain compatibility with optical discs near 00 nm.

The present invention has been made in view of the above-mentioned problems of the conventional one, and is a rewritable optical information recording medium which employs only an organic dye thin film material as a recording film and can satisfy the above requirements. The present invention further aims to provide a recording / reproducing method and a recording / reproducing apparatus.

[0017]

DISCLOSURE OF THE INVENTION Conventionally, organic dyes for write-once type organic optical discs, which have been studied and partially put into practical use, include polymethine cyanine dyes, azulene dyes, squarylium dyes, and metal complexes. Metal naphthalocyanine series, metal phthalocyanine series, porphyrin series,
Azo dyes, indoaniline dyes, quinone anthraquinone dyes, and naphthoquinone dyes are available. In the early stage of development, a write-once type organic optical disc with a so-called punching mode as a recording principle was put into practical use.

CD-R and DVD-which are widely used today
The organic dye optical recording material used for R changes its optical constant due to thermal decomposition of the organic dye recording film by local energy by laser irradiation, and reproduces it by phase modulation or amplitude modulation of complex reflectance. It is a recording / reproducing principle that the return light (reflectance) of the laser light changes, and it is generally considered that rewriting is not possible.

For the above-mentioned purpose, the inventors of the present invention have used an organic dye recording by using a compound selected from, for example, an azaannulene compound having a molecular weight of less than 3000 or at least one of these metal complexes as an organic dye by irradiation with a predetermined laser beam. The film is reversibly deformed without thermal decomposition and without mixing or dispersing in the polymer compound, by selecting the irradiation conditions of the beam light at the time of recording and erasing with these organic dyes alone. It was found that the above-mentioned object can be achieved by physically changing such as.

The present invention has been completed based on such findings. That is, the rewritable optical information recording medium of the present invention is substantially composed of at least one or more kinds of light-absorbing organic compounds (including those which are metal-complexed) (for example, organic dye compounds). At least one layer of film (organic dye film) is used as a recording film, and information can be recorded and erased by reversible physical change (for example, shape change such as deformation) of the organic dye film alone due to laser light irradiation. It is characterized by being called. In addition, the recording / reproducing method of the present invention is a rewrite having at least one light-absorbing organic compound film as a recording film, the light-absorbing organic compound film substantially consisting of at least one or more light-absorbing organic compounds (including those that are metal complexed). The present invention is characterized in that a feasible optical information recording medium is used to record and erase information by a reversible physical change of the light-absorbing organic compound film simple substance associated with laser light irradiation. Further, the recording / reproducing apparatus of the present invention is a rewrite device having at least one light-absorbing organic compound film as a recording film, the light-absorbing organic compound film substantially consisting of at least one or more light-absorbing organic compounds (including those that are metal complexed). The present invention is characterized in that a feasible optical information recording medium is provided, and information is recorded and erased by a reversible physical change of the light-absorbing organic compound film simple substance associated with laser light irradiation.

Recording on the information recording medium in the present invention is
This is performed by irradiating a laser beam corresponding to the absorption wavelength of the light-absorbing organic compound (for example, an organic dye) to heat the laser beam irradiation part and then rapidly cooling it. As the laser light, it is preferable to use a small and lightweight semiconductor laser according to the absorption wavelength of the dye used. The organic dye thin film in the laser light irradiation portion of the recording layer first has a low viscosity with a rise in temperature, and in some cases, with expansion or contraction due to melting or sublimation,
Bending or hollowing results in deformation with volume change or mass transfer. In the case of an optical disc in which a medium is rotated at a high speed, the heating portion is rapidly cooled immediately after the laser spot passes, as soon as the irradiation of the laser light is stopped for a short time and the irradiation of the laser light is stopped. At this time, if the cooling rate is equal to or higher than a certain critical cooling rate, the deformed portion is solidified in its shape and becomes a recording mark.

In reproducing the information signal of the recording mark recorded as described above, light which is weaker than the power of light used at the time of recording and at the time of erasing which will be described later is applied to the conventional CD-R and DVD.
Similar to the case of -R, it can be performed by detecting the difference in the amount of return light between the recorded portion and the unrecorded portion. For example, if the recording mark is deformed due to cavitation, the optical constants of the cavity should be close to n = 1.0 and k = 0.0 even if the thermal decomposition reaction of the organic dye does not occur. The value is different from the optical constant of the organic dye. In addition, even when a depression such as a protrusion due to mass transfer or a deformation such as a protrusion is accompanied, a model is established in which the film thickness of the organic dye recording film locally changes at the recording mark portion, and the optical optical path length (refractive index of the recording layer) (× film thickness) locally changes, the phase of the incident wavefront of the laser light changes even when there is no change in the optical constant, causing a change in reflectance and a diffraction phenomenon. Is modulated. Therefore, depending on the groove shape of the substrate, either the amplitude modulation mode or the phase modulation mode can be selected, and a sufficient modulation degree (contrast) can be obtained.

Further, the recorded information, that is, the recording mark can be erased by heating the recording portion and then cooling it. The recording portion or the recording portion and the unrecorded portion may be heated by laser light irradiation. Therefore, it is possible to erase only by continuously scanning the track on which the information is recorded by using the laser light whose output is stronger than the laser light during reproduction and weaker than the laser light during recording. In the case of an optical disc in which the medium is rotated at a high speed, it can be performed by irradiating the track in which the recording mark is written or a part thereof with the continuous laser light once or more than once. When the erasing light is continuously irradiated, the cooling rate becomes equal to or less than the above-mentioned critical cooling rate, that is, so-called gradual cooling, and the viscosity of the recording film portion where the temperature near the laser spot rises becomes low and mass transfer easily occurs. The state becomes possible, the deformed portion is flattened, the trace of the hollow portion of the recording mark disappears, and when it returns to the state before recording, it is solidified again. It is desirable that such physical deformation can occur reversibly only in the recording layer made of an organic dye, from the viewpoint of its recording / erasing / recording repeatability. Therefore, it is preferable that no plastic deformation mark is left on the interface adjacent to the dye layer which is the recording layer.

However, it is difficult to conclude that the recording principle is only due to deformation, and further detailed analysis is required for the submicron-sized minute portion as described above. There is a possibility that physical changes other than deformation, such as changes in the orientation state, phase changes in the crystalline state, and conformational changes, may occur at the same time. In any case,
It was surprisingly found for the first time that a rewritable optical recording medium utilizing the reversible physical change of the organic dye film itself can be realized.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. In the following description, as an optical recording medium, it is an optical disc, and has, for example, a guide groove on a substrate and a reflective layer and a recording layer containing an organic dye as a main component on the guide groove,
The medium for recording / reproducing a signal by irradiating a blue-violet laser beam having a wavelength of 350 to 450 nm will be described. Sheets and other various shapes, those without a reflective layer, wavelengths 630-68
It can also be applied to recording / reproducing with a 0 nm red laser light, a near infrared laser light with a wavelength of 750 to 850 nm, and a short wavelength laser with a wavelength of 350 nm or less.

As an example in which the present invention is applied to an optical disk,
As shown in FIG. 1, the substrate 1, the recording layer 2, the reflective layer 3, and the protective film 4 are laminated in this order, and in the optical disc of FIG. 1, recording and reproduction are performed from the substrate 1 side. Between the substrate 1 and the recording layer 2, between the recording layer 2 and the reflective layer 3, the reflective layer 3 and the protective film 4
2 may be present between the substrate 1 and the recording layer 2, and in the example of FIG. 2, the transparent protective films 5 and 6 are formed between the substrate 1 and the recording layer 2 and between the recording layer 2 and the reflective layer 3. ing. As another embodiment, an optical disc (hereinafter, referred to as DVR-Blue) for recording / reproducing information via a light transmission layer having a thickness of 10 to 177 μm.
Called. ) (Disclosed in Japanese Patent Laid-Open No. 10-302310), for example, as shown in FIG. 3, a reflective layer 2 and a recording layer 3 are formed in this order on a substrate 1 in which guide grooves are formed. A transparent protective layer 7 optionally formed on the recording layer 3.
The light transmissive layer 8 is formed through the recording layer and the information is recorded and reproduced from the light transmissive layer 8 side. As for the material of the substrate, considering the case where blue-violet laser light is irradiated through the substrate 1 as shown in FIG. 1, for example, a polymer material such as acrylic resin, polyethylene resin, polycarbonate resin, polyolefin resin, epoxy resin, or the like. Transparent materials such as inorganic materials such as glass and glass are used. On the other hand, FIG.
When the laser irradiation is performed from the side of the light transmission layer 8 opposite to the substrate 1 as in the configuration shown in (1), it is not necessary to satisfy various optical requirements as the material of the substrate, and it is possible to select from a wider range of materials. it can. Injection-moldable materials such as acrylic resin, polycarbonate resin, and polyolefin resin are preferable from the viewpoint of mechanical properties and productivity required for the substrate. Guide grooves and / or prepits of 1 μm or less may be formed in a spiral or concentric circles on the surface layer of these substrates.
These guide grooves and prepits are preferably provided at the time of forming the substrate, and they can be provided by injection molding using a stamper master or thermal transfer method using photopolymer. A guide groove and / or a prepit may be formed in the light transmitting layer 8 in FIG. For example, in the case of DVR-Blue, the pitch and the depth of the guide groove are 0.2 to
It is preferably selected from the range of 0.80 μm and the depth of 20 to 150 nm.

The constituent material of the recording layer in the optical recording medium of the present invention has sufficient absorption in the laser wavelength range of interest, for example, the oscillation wavelength range of the semiconductor laser mounted in the recording / reproducing apparatus used, and has a predetermined content. The recording film must be locally heated by irradiation with laser light having energy. The light-absorbing organic compound described in the present invention is a compound that absorbs light, and preferably has a wavelength range of 180 to 20.
An organic compound that interacts with 00 nm light to cause absorption, emission, chemical / physical changes, etc., and is used as a material satisfying the above conditions. As the light-absorbing organic compound, in particular, ultraviolet light, visible light and / or light in the near-infrared light wavelength region (preferably ultraviolet light, visible light and / or near-infrared light in the wavelength range of 350 nm to 850 nm) and Organic dye compounds that act are preferably used.

Specifically, a blue-violet nitride semiconductor laser has an oscillation wavelength range of 350 to 450 nm, a red semiconductor laser used in DVD-R has a wavelength of 600 to 650 nm, and a CD-
Near infrared semiconductor laser wavelength used in R 750-850
Examples of the organic dye compound of the present invention used in the optical recording medium of the present invention recorded in nm are preferably azaannulene compounds, further phthalocyanine, naphthalocyanine, tetraazaporphyrin, triazaporphyrin,
It can be found in azaporphyrin compounds such as diazaporphyrin and monoazaporphyrin, metal complexes such as porphyrin compounds, and mixtures of two or more thereof.

The azaannulene compound described in the present invention is, in the cyclic hydrocarbon compound having a conjugated double bond, at least one azaannulene ring in which at least one carbon atom constituting the ring is substituted with a nitrogen atom. The present invention includes compounds having one or more compounds, and the present invention also includes compounds complexed with metal atoms and / or metalloid atoms. In addition, a plurality of azaannulene rings may be bound to each other via one or two or more linking groups. Examples of suitable compounds include azaporphyrin compounds having phthalocyanine ring, naphthalocyanine ring, subphthalocyanine ring, monoazaporphyrin ring, diazaporphyrin ring, triazaporphyrin ring, tetraazaporphyrin ring, porphyrin compounds, and the like. Has a pyrrole ring structure (aza)
A porphyrin compound etc. are mentioned. Each of the pyrrole rings in these ring structures may have a condensed ring,
Substituents on the pyrrole ring and / or the condensed ring may be bonded to each other via a linking group. Examples of the condensed ring compound include compounds having a condensed benzene ring such as a dibenzotetraazaporphyrin compound, a phthalocyanine compound, and a naphthalocyanine compound. Further, as other exemplary compounds, for example, a porphycene ring,
Examples thereof include compounds having an azaannulene ring having a structure in which pyrrole rings having a ring structure such as a corrole ring are directly single-bonded to each other.

The azaannulene compound used in the present invention is preferably a divalent metal atom which may have a ligand,
Alternatively, a compound having a monomer structure in which a trivalent to tetravalent metal atom or a semimetal atom having a substituent and / or a ligand is coordinated, and a central metal atom is per trivalent to tetravalent metal atom It is a compound having in the molecule a dimer structure in which two azaannulene rings are bonded, and also includes a multimer structure of a trimer or more. In particular, the azaannulene compound having a molecular weight of less than 3000, which may be metal-complexed, has an absorption wavelength that can be arbitrarily selected in a state where the absorption coefficient is retained by selecting a substituent. It is an extremely useful organic dye that can satisfy the constant.

The compound of the recording layer described in the present invention will be described in more detail below.

In the present invention, as the azaannulene compound, the compounds exemplified by the general formula (1) are mentioned as preferable examples.

[0033]

[Chemical 5]

[In the formula, R ^{1 to} R ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted Represents a mercapto group, a substituted or unsubstituted amino group, X ^{1 to} X ⁸ each independently represent a nitrogen atom, or a substituted or unsubstituted methine group,
Each of the substituents on R ^{1 to} R ¹⁶ and the methine group may be bonded together via a linking group. In a substituted or unsubstituted hydrocarbon group, a hydrocarbon group-substituted hydroxyl group,
A hydrocarbon group-substituted mercapto group and / or a hydrocarbon group-substituted amino group may have an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom between the carbon and carbon atoms. . N represents 0 or 1,
When n is 0, M represents a divalent metal atom which may have a ligand, or a trivalent or tetravalent metal atom or a metalloid atom having a substituent and / or a ligand, When n is 1, M represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ]

In the compound represented by the general formula (1) of the present invention, specific examples of R ^{1 to} R ¹⁶ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group and the like can be mentioned.

Specific examples of the substituted or unsubstituted hydrocarbon group represented by R ^{1 to} R ¹⁶ include carbon atoms in the hydrocarbon group.
Between carbon atoms, it may have an oxygen atom, a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom,
Examples thereof include a substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group and the like.

The substituted or unsubstituted alkyl group represented by R ^{1 to} R ¹⁶ includes a methyl group, an ethyl group, an n-propyl group, and i.
so-propyl group, n-butyl group, iso-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, i
so-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl group,
n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethyl Butyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group,
1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2
-Methylpropyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4
-Methylhexyl group, 5-methylhexyl group, 2,4-
Dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group,
2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-
Ethyloctyl group, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1,3,3
5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group,
6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5, 5-tetramethylhexyl group,
1-cyclopentyl-2,2-dimethylpropyl group, 1
An unsubstituted linear, branched or cyclic alkyl group having 1 to 15 carbon atoms such as cyclohexyl-2,2-dimethylpropyl group;

Chloromethyl group, chloroethyl group, bromoethyl group, iodoethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,2.
2-trichloroethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, nonafluorobutyl group, perfluorodecyl group, or other alkyl group having 1 to 10 carbon atoms substituted with a halogen atom ;

Hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-3-methoxypropyl group, 2-
Hydroxy-3-chloropropyl group, 2-hydroxy-
With a hydroxyl group such as 3-ethoxypropyl group, 3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-cyclohexyloxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 4-hydroxydecalyl group. A substituted alkyl group having 1 to 10 carbon atoms;

Hydroxymethoxymethyl group, hydroxyethoxyethyl group, 2- (2'-hydroxy-1'-methylethoxy) -1-methylethyl group, 2- (3'-fluoro-2'-hydroxypropoxy) ethyl group , 2-
(3'-chloro-2'-hydroxypropoxy) ethyl group, an alkyl group having 2 to 10 carbon atoms substituted with a hydroxyalkoxy group such as hydroxybutoxycyclohexyl group;

Hydroxymethoxymethoxymethyl group, hydroxyethoxyethoxyethyl group, [2 '-(2'-hydroxy-1'-methylethoxy) -1'-methylethoxy] ethoxyethyl group, [2'-(2'- Fluoro-1 '
-Hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group, [2 '-(2'-chloro-1'-hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group and other substituted hydroxyalkoxyalkoxy groups An alkyl group having 3 to 10 carbon atoms;

Cyanomethyl group, 2-cyanoethyl group, 3
-Cyanopropyl group, 4-cyanobutyl group, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group, 2-cyano-3-ethoxypropyl group, 3-
Butoxy-2-cyanopropyl group, 2-cyano-3-cyclohexylpropyl group, 2-cyanopropyl group, 2-
2 to 1 carbon atoms substituted with a cyano group such as a cyanobutyl group
An alkyl group of 0;

Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, n-hexyloxyethyl group, (4-methylpentoxy) ethyl Group, (1,3-dimethylbutoxy)
Ethyl group, (2-ethylhexyloxy) ethyl group, n
-Octyloxyethyl group, (3,5,5-trimethylhexyloxy) ethyl group, (2-methyl-1-iso
-Propylpropoxy) ethyl group, (3-methyl-1-
iso-propylbutyloxy) ethyl group, 2-ethoxy-1-methylethyl group, 3-methoxybutyl group,
(3,3,3-trifluoropropoxy) ethyl group,
An alkyl group having 2 to 15 carbon atoms substituted with an alkoxy group such as (3,3,3-trichloropropoxy) ethyl group;

Methoxymethoxymethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, butoxyethoxyethyl group, cyclohexyloxyethoxyethyl group, decalyloxypropoxyethoxy group, (1,2-dimethylpropoxy) ethoxy Ethyl group, (3-methyl-1-iso-butylbutoxy) ethoxyethyl group, (2-methoxy-1-methylethoxy) ethyl group, (2-butoxy-1-methylethoxy) ethyl group, 2- (2 ′) -Ethoxy-1'-methylethoxy) -1-methylethyl group, (3,3,3-trifluoropropoxy) ethoxyethyl group, (3,3,3
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxyalkoxy group such as trichloropropoxy) ethoxyethyl group;

Methoxymethoxymethoxymethyl group, methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, cyclohexyloxyethoxyethoxyethyl group, propoxypropoxypropoxyethyl group, (2,2,2-trifluoroethoxy ) Ethoxyethoxyethyl group,
An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxyalkoxy group such as (2,2,2-trichloroethoxy) ethoxyethoxyethyl group;

Formylmethyl group, 2-oxobutyl group,
3-oxobutyl group, 4-oxobutyl group, 2,6-dioxocyclohexan-1-yl group, 2-oxo-5-
an alkyl group having 2 to 10 carbon atoms substituted with an acyl group such as t-butylcyclohexane-1-yl group;

Formyloxymethyl group, acetoxyethyl group, propionyloxyethyl group, butanoyloxyethyl group, valeryloxyethyl group, (2-ethylhexanoyloxy) ethyl group, (3,5,5-trimethylhexanoyl) Number of carbon atoms substituted with an acyloxy group such as (oxy) ethyl group, (3,5,5-trimethylhexanoyloxy) hexyl group, (3-fluorobutyryloxy) ethyl group, (3-chlorobutyryloxy) ethyl group Two
~ 15 alkyl groups;

Formyloxymethoxymethyl group, acetoxyethoxyethyl group, propionyloxyethoxyethyl group, valeryloxyethoxyethyl group, (2-ethylhexanoyloxy) ethoxyethyl group, (3,5,5
5-trimethylhexanoyl) oxybutoxyethyl group, (3,5,5-trimethylhexanoyloxy) ethoxyethyl group, (2-fluoropropionyloxy)
Ethoxyethyl group, (2-chloropropionyloxy)
An alkyl group having 3 to 15 carbon atoms substituted with an acyloxyalkoxy group such as an ethoxyethyl group;

Acetoxymethoxymethoxymethyl group, acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, (2-ethylhexanoyloxy)
Ethoxyethoxyethyl group, (3,5,5-trimethylhexanoyloxy) ethoxyethoxyethyl group, (2
An alkyl group having 5 to 15 carbon atoms, which is substituted with an acyloxyalkoxyalkoxyalkoxy group such as -fluoropropionyloxy) ethoxyethoxyethyl group and (2-chloropropionyloxy) ethoxyethoxyethyl group;

Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, butoxycarbonylethyl group, (p-ethylcyclohexyloxycarbonyl) cyclohexyl group, (2,
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyl group such as a 2,3,3-tetrafluoropropoxycarbonyl) methyl group or a (2,2,3,3-tetrachloropropoxycarbonyl) methyl group;

8 to 15 carbon atoms substituted with an aryloxycarbonyl group such as a phenoxycarbonylmethyl group, a phenoxycarbonylethyl group, a (4-t-butylphenoxycarbonyl) ethyl group, a naphthyloxycarbonylmethyl group and a biphenyloxycarbonylethyl group. An alkyl group of

An alkyl group having 9 to 15 carbon atoms substituted with an aralkyloxycarbonyl group such as a benzyloxycarbonylmethyl group, a benzyloxycarbonylethyl group, a phenethyloxycarbonylmethyl group and a (4-cyclohexyloxybenzyloxycarbonyl) methyl group;

4 to 10 carbon atoms substituted with an alkenyloxycarbonyl group such as a vinyloxycarbonylmethyl group, a vinyloxycarbonylethyl group, an allyloxycarbonylmethyl group, a cyclopentadienyloxycarbonylmethyl group and an octenoxycarbonylmethyl group. An alkyl group of

Methoxycarbonyloxymethyl group, methoxycarbonyloxyethyl group, ethoxycarbonyloxyethyl group, butoxycarbonyloxyethyl group,
An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyloxy group such as a (2,2,2-trifluoroethoxycarbonyloxy) ethyl group and a (2,2,2-trichloroethoxycarbonyloxy) ethyl group;

Methoxymethoxycarbonyloxymethyl group, methoxyethoxycarbonyloxyethyl group, ethoxyethoxycarbonyloxyethyl group, butoxyethoxycarbonyloxyethyl group, (2,2,2-trifluoroethoxy) ethoxycarbonyloxyethyl group,
An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxycarbonyloxy group such as (2,2,2-trichloroethoxy) ethoxycarbonyloxyethyl group;

Dimethylaminomethyl group, diethylaminomethyl group, di-n-butylaminomethyl group, di-n-hexylaminomethyl group, di-n-octylaminomethyl group, di-n-decylaminomethyl group, N- Isoamyl-
N-methylaminomethyl group, piperidinomethyl group, di (methoxymethyl) aminomethyl group, di (methoxyethyl) aminomethyl group, di (ethoxymethyl) aminomethyl group, di (ethoxyethyl) aminomethyl group, di (propoxyethyl) ) Aminomethyl group, di (butoxyethyl)
Aminomethyl group, bis (2-cyclohexyloxyethyl) aminomethyl group, dimethylaminoethyl group, diethylaminoethyl group, di-n-butylaminoethyl group, di-n-hexylaminoethyl group, di-n-octylaminoethyl Group, di-n-decylaminoethyl group, N-isoamyl-N-methylaminoethyl group, piperidinoethyl group, di (methoxymethyl) aminoethyl group, di (methoxyethyl) aminoethyl group, di (ethoxymethyl) aminoethyl Group, di (ethoxyethyl) aminoethyl group, di (propoxyethyl) aminoethyl group, di (butoxyethyl) aminoethyl group, bis (2-cyclohexyloxyethyl) aminoethyl group, dimethylaminopropyl group, diethylaminopropyl group, Di-n-butylaminopropyl group, di-n Hexyl aminopropyl group, di -
n-octylaminopropyl group, di-n-decylaminopropyl group, N-isoamyl-N-methylaminopropyl group, piperidinopropyl group, di (methoxymethyl) aminopropyl group, di (methoxyethyl) aminopropyl group , Di (ethoxymethyl) aminopropyl group, di (ethoxyethyl) aminopropyl group, di (propoxyethyl) aminopropyl group, di (butoxyethyl) aminopropyl group, bis (2-cyclohexyloxyethyl) aminopropyl group, dimethyl Aminobutyl group, diethylaminobutyl group, di-n-butylaminobutyl group, di-n
-Hexylaminobutyl group, di-n-octylaminobutyl group, di-n-decylaminobutyl group, N-isoamyl-N-methylaminobutyl group, piperidinobutyl group,
Di (methoxymethyl) aminobutyl group, di (methoxyethyl) aminobutyl group, di (ethoxymethyl) aminobutyl group, di (ethoxyethyl) aminobutyl group, di (propoxyethyl) aminobutyl group, di (butoxyethyl) An alkyl group having 3 to 20 carbon atoms, which is substituted with a dialkylamino group such as an aminobutyl group and a bis (2-cyclohexyloxyethyl) aminobutyl group;

Substituted with an acylamino group such as acetylaminomethyl group, acetylaminoethyl group, propionylaminoethyl group, butanoylaminoethyl group, cyclohexanecarbonylaminoethyl group, p-methylcyclohexanecarbonylaminoethyl group and succiniminoethyl group. An alkyl group having 3 to 10 carbon atoms;

An alkyl group having 2 to 10 carbon atoms substituted with an alkylsulfonamino group such as a methylsulfonaminomethyl group, a methylsulfonaminoethyl group, an ethylsulfonaminoethyl group, a propylsulfonaminoethyl group, an octylsulfonaminoethyl group;

Methylsulfonylmethyl group, ethylsulfonylmethyl group, butylsulfonylmethyl group, methylsulfonylethyl group, ethylsulfonylethyl group, butylsulfonylethyl group, 2-ethylhexylsulfonylethyl group, 2,2,3,3-tetrafluoro An alkyl group having 2 to 10 carbon atoms substituted with an alkylsulfonyl group such as a propylsulfonylmethyl group or a 2,2,3,3-tetrachloropropylsulfonylmethyl group;

Benzenesulfonylmethyl group, benzenesulfonylethyl group, benzenesulfonylpropyl group, benzenesulfonylbutyl group, toluenesulfonylmethyl group, toluenesulfonylethyl group, toluenesulfonylpropyl group, toluenesulfonylbutyl group, xylenesulfonylmethyl group, xylenesulfonyl group 7 to 1 carbon atoms substituted with an arylsulfonyl group such as ethyl group, xylenesulfonylpropyl group, xylenesulfonylbutyl group
An alkyl group of 2;

Thiadiazolinomethyl group, pyrrolinomethyl group, pyrrolidinomethyl group, pyrazolidinomethyl group, imidazolidinomethyl group, oxazolyl group, triazolinomethyl group, morpholinomethyl group, indolinomethyl group,
An alkyl group having 2 to 13 carbon atoms substituted with a heterocyclic group such as a benzimidazolinomethyl group or a carbazolinomethyl group;

Ferrocenylmethyl group, ferrocenylethyl group, ferrocenyl-n-propyl group, ferrocenyl-
iso-propyl group, ferrocenyl-n-butyl group, ferrocenyl-iso-butyl group, ferrocenyl-sec
-Butyl group, ferrocenyl-t-butyl group, ferrocenyl-n-pentyl group, ferrocenyl-iso-pentyl group, ferrocenyl-2-methylbutyl group, ferrocenyl-1-methylbutyl group, ferrocenyl neopentyl group,
Ferrocenyl-1,2-dimethylpropyl group, ferrocenyl-1,1-dimethylpropyl group, ferrocenylcyclopentyl group, ferrocenyl-n-hexyl group, ferrocenyl-4-methylpentyl group, ferrocenyl-3-methylpentyl group, ferrocenyl -2-methylpentyl group, ferrocenyl-1-methylpentyl group, ferrocenyl-3,3-dimethylbutyl group, ferrocenyl-2,3
-Dimethylbutyl group, ferrocenyl-1,3-dimethylbutyl group, ferrocenyl-2,2-dimethylbutyl group,
Ferrocenyl-1,2-dimethylbutyl group, ferrocenyl-1,1-dimethylbutyl group, ferrocenyl-3-ethylbutyl group, ferrocenyl-2-ethylbutyl group, ferrocenyl-1-ethylbutyl group, ferrocenyl-1,
2,2-trimethylbutyl group, ferrocenyl-1,1,
2-trimethylbutyl group, ferrocenyl-1-ethyl-
2-methylpropyl group, ferrocenylcyclohexyl group, ferrocenyl-n-heptyl group, ferrocenyl-2
-Methylhexyl group, ferrocenyl-3-methylhexyl group, ferrocenyl-4-methylhexyl group, ferrocenyl-5-methylhexyl group, ferrocenyl-2,4-
Dimethylpentyl group, ferrocenyl-n-octyl group,
Ferrocenyl-2-ethylhexyl group, ferrocenyl-
2,5-dimethylhexyl group, ferrocenyl-2,5
5-trimethylpentyl group, ferrocenyl-2,4-dimethylhexyl group, ferrocenyl-2,2,4-trimethylpentyl group, ferrocenyl-3,5,5-trimethylhexyl group, ferrocenyl-n-nonyl group, ferrocenyl-n -Decyl group,

Cobaltcenylmethyl group, cobaltcenylethyl group, cobaltcenyl-n-propyl group, cobaltcenyl-iso-propyl group, cobaltcenyl-n-butyl group, cobaltcenyl-iso-butyl group, cobaltcenyl-sec-butyl group, Cobalt cenyl-t-butyl group, cobalt cenyl-n-pentyl group, cobalt cenyl-iso-pentyl group, cobalt cenyl-2-methylbutyl group, cobalt cenyl-1-methylbutyl group, cobalt cenyl neopentyl group, cobalt cenyl-1,2-
Dimethylpropyl group, cobaltcenyl-1,1-dimethylpropyl group, cobaltcenylcyclopentyl group, cobaltcenyl-n-hexyl group, cobaltcenyl-4-methylpentyl group, cobaltcenyl-3-methylpentyl group, cobaltcenyl-2-methylpentyl group , Cobaltcenyl-1-methylpentyl group, cobaltcenyl-3,
3-dimethylbutyl group, cobaltcenyl-2,3-dimethylbutyl group, cobaltcenyl-1,3-dimethylbutyl group, cobaltcenyl-2,2-dimethylbutyl group, cobaltcenyl-1,2-dimethylbutyl group, cobaltcenyl-1, 1-dimethylbutyl group, cobalt cenyl-3
-Ethylbutyl group, cobaltcenyl-2-ethylbutyl group, cobaltcenyl-1-ethylbutyl group, cobaltcenyl-1,2,2-trimethylbutyl group, cobaltcenyl-1,1,2-trimethylbutyl group, cobaltcenyl-1-ethyl-2- Methylpropyl group, cobaltcenylcyclohexyl group, cobaltcenyl-n-heptyl group,
Cobalt cenyl-2-methylhexyl group, cobalt cenyl-3-methylhexyl group, cobalt cenyl-4-methylhexyl group, cobalt cenyl-5-methylhexyl group, cobalt cenyl-2,4-dimethylpentyl group, cobalt cenyl-n-octyl group, cobalt cenyl -2-
Ethylhexyl group, cobaltcenyl-2,5-dimethylhexyl group, cobaltcenyl-2,5,5-trimethylpentyl group, cobaltcenyl-2,4-dimethylhexyl group, cobaltcenyl-2,2,4-trimethylpentyl group, cobaltcenyl-3 , 5,5-trimethylhexyl group, cobaltcenyl-n-nonyl group, cobaltcenyl-n-decyl group,

Nickelocenylmethyl group, nickelocenylethyl group, nickelocenyl-n-propyl group, nickelocenyl-iso-propyl group, nickelocenyl-n-butyl group, nickelocenyl-iso-butyl group, nickelocenyl-sec-butyl group, Nickelocenyl-t-butyl group, nickelocenyl-n-pentyl group, nickelocenyl-iso-pentyl group, nickelocenyl-2-methylbutyl group, nickelocenyl-1-methylbutyl group, nickelocenyl neopentyl group, nickelocenyl-1,2-
Dimethylpropyl group, nickelocenyl-1,1-dimethylpropyl group, nickelocenylcyclopentyl group, nickelocenyl-n-hexyl group, nickelocenyl-4-methylpentyl group, nickelocenyl-3-methylpentyl group, nickelocenyl-2-methylpentyl group , Nickelocenyl-1-methylpentyl group, nickelocenyl-3,
3-dimethylbutyl group, nickelocenyl-2,3-dimethylbutyl group, nickelocenyl-1,3-dimethylbutyl group, nickelocenyl-2,2-dimethylbutyl group, nickelocenyl-1,2-dimethylbutyl group, nickelocenyl-1, 1-dimethylbutyl group, nickelocenyl-3
-Ethylbutyl group, nickelocenyl-2-ethylbutyl group, nickelocenyl-1-ethylbutyl group, nickelocenyl-1,2,2-trimethylbutyl group, nickelocenyl-1,1,2-trimethylbutyl group, nickelocenyl-1-ethyl-2- Methylpropyl group, nickelocenylcyclohexyl group, nickelocenyl-n-heptyl group,
Nickelocenyl-2-methylhexyl group, nickelocenyl-3-methylhexyl group, nickelocenyl-4-methylhexyl group, nickelocenyl-5-methylhexyl group, nickelocenyl-2,4-dimethylpentyl group, nickelocenyl-n-octyl group, nickelocenyl -2-
Ethylhexyl group, nickelocenyl-2,5-dimethylhexyl group, nickelocenyl-2,5,5-trimethylpentyl group, nickelocenyl-2,4-dimethylhexyl group, nickelocenyl-2,2,4-trimethylpentyl group, nickelocenyl-3 , 5,5-trimethylhexyl group, nickelocenyl-n-nonyl group, nickelocenyl-n-decyl group;

Dichlorotitanocenylmethyl group, trichlorotitanium cyclopentadienylmethyl group, bis (trifluoromethanesulfonato) titanocene methyl group, dichlorozirconocenylmethyl group, dimethylzirconocenylmethyl group, diethoxyzirconocenylmethyl group. Group, bis (cyclopentadienyl) chromium methyl group, bis (cyclopentadienyl) dichloromolybdenum methyl group, bis (cyclopentadienyl) dichlorohafnium methyl group, bis (cyclopentadienyl) dichloroniobium methyl group, bis An alkyl group having 11 to 20 carbon atoms substituted with a metallocenyl group such as a (cyclopentadienyl) rutheniummethyl group, a bis (cyclopentadienyl) vanadium methyl group, a bis (cyclopentadienyl) dichlorovanadiummethyl group;

Ferrocenyl methoxymethyl group, ferrocenyl methoxyethyl group, ferrocenyl methoxypropyl group, ferrocenyl methoxybutyl group, ferrocenyl methoxypentyl group, ferrocenyl methoxyhexyl group, ferrocenyl methoxyheptyl group Group, ferrocenyl methoxyoctyl group, ferrocenyl methoxynonyl group, ferrocenyl methoxydecyl group, ferrocenyl ethoxymethyl group, ferrocenyl ethoxyethyl group, ferrocenyl ethoxypropyl group, ferrocenyl ethoxybutyl group , Ferrocenylethoxypentyl group, ferrocenylethoxyhexyl group, ferrocenylethoxyheptyl group, ferrocenylethoxyoctyl group, ferrocenylethoxynonyl group, ferrocenylethoxydecyl group, ferrocenylpropoxymethyl group, F Rose cycloalkenyl propoxyethyl group, ferrocenyl propoxypropyl group, ferrocenyl-propoxybutyl group, ferrocenyl propoxy pentyl group, ferrocenyl propoxy hexyl, ferrocenyl propoxy heptyl group, ferrocenyl propoxy octyl group,
Ferrocenylpropoxynonyl group, ferrocenylpropoxydecyl group, ferrocenylbutoxymethyl group, ferrocenylbutoxyethyl group, ferrocenylbutoxypropyl group, ferrocenylbutoxybutyl group, ferrocenylbutoxypentyl group, ferroc Cenylbutoxyhexyl group,
Ferrocenylbutoxyheptyl group, ferrocenylbutoxyoctyl group, ferrocenylbutoxynonyl group, ferrocenylbutoxydecyl group, ferrocenyldecyloxymethyl group, ferrocenyldecyloxyethyl group, ferrocenyldecyloxypropyl group Group, ferrocenyldecyloxybutyl group, ferrocenyldecyloxypentyl group, ferrocenyldecyloxyhexyl group, ferrocenyldecyloxyheptyl group, ferrocenyldecyloxyoctyl group, ferrocenyldecyloxynonyl group, Ferrocenyldecyloxydecyl group;

Cobalt cenyl methoxymethyl group, cobalt cenyl methoxyethyl group, cobalt cenyl methoxypropyl group, cobalt cenyl methoxybutyl group, cobalt cenyl methoxypentyl group, cobalt cenyl methoxyhexyl group, cobalt cenyl methoxyheptyl group. Group, cobalt cenyl methoxyoctyl group, cobalt cenyl methoxy nonyl group, cobalt cenyl methoxydecyl group, cobalt cenyl ethoxymethyl group, cobalt cenyl ethoxyethyl group, cobalt cenyl ethoxypropyl group, cobalt cenyl ethoxybutyl group , Cobaltcenylethoxypentyl group, cobaltcenylethoxyhexyl group, cobaltcenylethoxyheptyl group, cobaltcenylethoxyoctyl group, cobaltcenylethoxynonyl group, cobaltcenylethoxydecyl group Group, cobaltcenylpropoxymethyl group, cobaltcenylpropoxyethyl group, cobaltcenylpropoxypropyl group, cobaltcenylpropoxybutyl group, cobaltcenylpropoxypentyl group, cobaltcenylpropoxyhexyl group, cobaltcenylpropoxyheptyl group , A cobalt cenyl propoxy octyl group, a cobalt cenyl propoxy nonyl group, a cobalt cenyl propoxydecyl group, a cobalt cenyl butoxymethyl group, a cobalt cenyl butoxyethyl group, a cobalt cenyl butoxypropyl group, a cobalt cenyl butoxy butyl group, Cobalt cenyl butoxypentyl group, cobalt cenyl butoxy hexyl group, cobalt cenyl butoxy heptyl group, cobalt cenyl butoxy octyl group, cobalt cenyl butoxy nonyl group, cobalt ceni Butokishideshiru group, cobalt Se sulfonyl decyl oxymethyl group, cobalt Se sulfonyl decyl oxyethyl groups, cobalt Se sulfonyl decyloxy propyl, cobalt Se sulfonyl decyloxy-butyl group,
Cobalt cenyldecyloxypentyl group, cobaltcenyldecyloxyhexyl group, cobaltcenyldecyloxyheptyl group, cobaltcenyldecyloxyoctyl group, cobaltcenyldecyloxynonyl group, cobaltcenyldecyloxydecyl group;

Nickelocenyl methoxymethyl group, nickelocenyl methoxyethyl group, nickelocenyl methoxypropyl group, nickelocenyl methoxybutyl group, nickelocenyl methoxypentyl group, nickelocenyl methoxyhexyl group, nickelocenyl methoxyheptyl group Group, nickelocenylmethoxyoctyl group, nickelocenylmethoxynonyl group, nickelocenylmethoxydecyl group, nickelocenylethoxymethyl group, nickelocenylethoxyethyl group, nickelocenylethoxypropyl group, nickelocenylethoxybutyl group , Nickelocenylethoxypentyl group, nickelocenylethoxyhexyl group, nickelocenylethoxyheptyl group, nickelocenylethoxyoctyl group, nickelocenylethoxynonyl group, nickelocenylethoxydecyl group Group, nickelocenylpropoxymethyl group, nickelocenylpropoxyethyl group, nickelocenylpropoxypropyl group, nickelocenylpropoxybutyl group, nickelocenylpropoxypentyl group, nickelocenylpropoxyhexyl group, nickelocenylpropoxyheptyl group , Nickelocenylpropoxyoctyl group, nickelocenylpropoxynonyl group, nickelocenylpropoxydecyl group, nickelocenylbutoxymethyl group, nickelocenylbutoxyethyl group, nickelocenylbutoxypropyl group, nickelocenylbutoxybutyl group, Nickelocenyl butoxypentyl group, nickelocenyl butoxyhexyl group, nickelocenyl butoxyheptyl group, nickelocenyl butoxyoctyl group, nickelocenyl butoxynonyl group, nickelocenyl Butokishideshiru group, nickel Rose sulfonyl decyl oxymethyl group, nickel Rose sulfonyl decyl oxyethyl group, nickel Rose sulfonyl decyloxy propyl, nickel Rose sulfonyl decyloxy-butyl group,
Nickelocenyldecyloxypentyl group, nickelocenyldecyloxyhexyl group, nickelocenyldecyloxyheptyl group, nickelocenyldecyloxyoctyl group, nickelocenyldecyloxynonyl group, nickelocenyldecyloxydecyl group;

A dichlorotitanocenyl methoxymethyl group,
Trichlorotitanium cyclopentadienyl methoxyethyl group, bis (trifluoromethanesulfonato) titanocene methoxypropyl group, dichlorozirconocenyl methoxybutyl group, dimethylzirconocenyl methoxypentyl group, diethoxyzirconocenyl methoxymethyl group, bis (cyclo Pentadienyl) chromium methoxyhexyl group,
Bis (cyclopentadienyl) dichlorohafnium methoxymethyl group, bis (cyclopentadienyl) dichloroniobium methoxyoctyl group, bis (cyclopentadienyl) ruthenium methoxymethyl group, bis (cyclopentadienyl) vanadium methoxymethyl group, An alkyl group having 12 to 30 carbon atoms substituted with a metallocenylalkyloxy group such as a bis (cyclopentadienyl) dichlorovanadium methoxyethyl group or an osmocenylmethoxyethyl group;

Ferrocenecarbonyloxymethyl group, ferrocenecarbonyloxyethyl group, ferrocenecarbonyloxypropyl group, ferrocenecarbonyloxybutyl group, ferrocenecarbonyloxypentyl group, ferrocenecarbonyloxyhexyl group, ferrocenecarbonyloxyheptyl group, ferrocenecarbonyloxyoctyl group , Ferrocenecarbonyloxynonyl group, ferrocenecarbonyloxydecyl group;

Cobaltsencarbonyloxymethyl group,
Cobaltcene carbonyloxyethyl group, Cobaltcene carbonyloxypropyl group, Cobaltcene carbonyloxybutyl group, Cobaltcene carbonyloxypentyl group, Cobaltcene carbonyloxyhexyl group, Cobaltcene carbonyloxyheptyl group, Cobaltcene carbonyloxyoctyl group, Cobalt Sencarbonyloxynonyl group, cobalt sencarbonyloxydecyl group,

A nickelocenecarbonyloxymethyl group,
Nickelocene carbonyloxyethyl group, nickelocene carbonyloxypropyl group, nickelocene carbonyloxybutyl group, nickelocene carbonyloxypentyl group, nickelocene carbonyloxyhexyl group, nickelocene carbonyloxyheptyl group, nickelocene carbonyloxyoctyl group, nickel Rosenecarbonyloxynonyl group, nickelocenecarbonyloxydecyl group,

Dichlorotitanocenylcarbonyloxymethyl group, trichlorotitanium cyclopentadienylcarbonyloxyethyl group, bis (trifluoromethanesulfonato) titanocenecarbonyloxymethoxypropyl group, dichlorozirconocenecarbonyloxybutyl group,
Dimethylzirconocene carbonyloxypentyl group, diethoxyzirconocene carbonyloxymethyl group, bis (cyclopentadienyl) chromium carbonyloxyhexyl group, bis (cyclopentadienyl) dichlorohafnium carbonyloxymethyl group, bis (cyclopentadienyl) dichloro Niobium carbonyloxyoctyl group,
Bis (cyclopentadienyl) ruthenium carbonyloxymethyl group, bis (cyclopentadienyl) vanadium carbonyloxymethyl group, bis (cyclopentadienyl) dichlorovanadium carbonyloxyethyl group,
Examples thereof include an alkyl group having 12 to 30 carbon atoms which is substituted with a metallocenylcarbonyloxy group such as a bis (cyclopentadienyl) osmium carbonyloxyethyl group.

Examples of the substituted or unsubstituted aralkyl group represented by R ^{1 to} R ¹⁶ are aralkyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably,
Benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group And aralkyl groups having 7 to 15 carbon atoms such as a group, a methylnaphthylmethyl group, a trifluoromethylnaphthylmethyl group and a fluoren-9-ylethyl group.

Examples of the substituted or unsubstituted aryl group of R ^{1 to} R ¹⁶ are aryl groups which may have the same substituents as the above-mentioned alkyl groups, preferably a phenyl group and a nitro group. Phenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, ethylphenyl group, xylyl group, mesityl group, trifluoromethylphenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, An aryl group having 6 to 15 carbon atoms such as a trifluoromethylnaphthyl group, a methoxycarbonylphenyl group, a 4- (5′-methylbenzoxazol-2′-yl) phenyl group, and a dibutylaminocarbonylphenyl group can be given.

In addition, regarding an aryl group having an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom between carbon atoms, that is, a heteroaryl group, R ^{1 to} R ¹⁶ are substituted or unsubstituted. Specific examples of the substituted heteroaryl group are heteroaryl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably a furanyl group, a pyrrolyl group, a 3-pyrrolino group, a pyrazolyl group. , Imidazolyl group, oxazolyl group, thiazolyl group, 1,2,3-oxadiazolyl group, 1,2,3-
Triazolyl group, 1,2,4-triazolyl group, 1,
3,4-thiadiazolyl group, pyridinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indolyl group, thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, benzotriazol-2-yl group, Benzotriazol-1-yl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group,
An unsubstituted heteroaryl group such as a flavonyl group, a phthalimidyl group, a naphthylimidyl group;

Alternatively, the following substituents, ie, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano group; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group. , Octyl group, decyl group, methoxymethyl group, ethoxyethyl group,
Alkyl groups such as ethoxyethyl group and trifluoromethyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group;

Methoxy group, ethoxy group, propoxy group,
Butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group, 3,5,5
An alkoxy group such as a trimethylhexyloxy group, a ferrocenemethoxy group, a cobaltocenemethoxy group, a nickelocenemethoxy group;

Aralkyloxy groups such as benzyloxy group and phenethyloxy group; aryloxy groups such as phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group and methoxyphenoxy group; vinyl group, allyl group, Alkenyl groups such as butenyl group, butadienyl group, pentenyl group, cyclopentadienyl group, octenyl group; vinyloxy group,
Alkenyloxy groups such as allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, cyclopentadienyloxy group, octenyloxy group;

Methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, decylthio group,
Alkylthio groups such as methoxymethylthio group, ethoxyethylthio group, ethoxyethylthio group, trifluoromethylthio group; aralkylthio groups such as benzylthio group, phenethylthio group; phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, Arylthio groups such as chlorophenylthio group and methoxyphenylthio group; Dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group and dibutylamino group;

Acyl groups such as acetyl group, propionyl group, butanoyl group, ferrocenecarbonyl group, cobaltocenecarbonyl group and nickelocenecarbonyl group;

Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, ferrocenemethoxycarbonyl group, 1-methylferrocene-1'-ylmethoxycarbonyl group, cobaltcenylmethoxycarbonyl group, nickelocenylmethoxycarbonyl group and the like;

Aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group;

Aryloxycarbonyl groups such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group, methoxyphenoxycarbonyl group;

Alkenyloxycarbonyl groups such as vinyloxycarbonyl group, allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group, octenyloxycarbonyl group;

Methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, 3, Monoalkylaminocarbonyl group having 2 to 10 carbon atoms such as 5,5-trimethylhexylaminocarbonyl group and 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group , Dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinoca Boniru group, 4-methyl-piperazinocarbonyl group, an alkylamino group such as a dialkylaminocarbonyl group having 3 to 20 carbon atoms such as 4-ethyl piperazinocarbonyl group;

Furanyl group, pyrrolyl group, 3-pyrrolino group, pyrrolidino group, 1,3-oxolanyl group, pyrazolyl group, 2-pyrazolinyl group, pyrazolidinyl group, imidazolyl group, oxazolyl group, thiazolyl group, 1,2,3
-Oxadiazolyl group, 1,2,3-triazolyl group,
1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group, pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group,
Triazinyl group, benzofuranyl group, indolyl group,
Thionaphthenyl group, benzimidazolyl group, benzothiazolyl group, purinyl group, quinolinyl group, isoquinolinyl group, coumarinyl group, cinnolinyl group, quinoxalinyl group, dibenzofuranyl group, carbazolyl group, phenanthronylyl group, phenothiazinyl group, flavonyl group, etc. A heterocyclic group;

Examples of the heteroaryl group include a metallocenyl group such as a ferrocenyl group, a cobaltcenyl group, a nickelocenyl group, a ruthenocenyl group, an osmocenyl group, and a titanocenyl group;

Examples of the substituted or unsubstituted alkenyl group represented by R ^{1 to} R ¹⁶ are alkenyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably,
Vinyl group, propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-
Methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group, 2-cyano-2- 2 to 2 carbon atoms such as methylsulfone vinyl group, styryl group, 4-phenyl-2-butenyl group
There may be mentioned 10 alkenyl groups.

Further, examples of the substituted hydrocarbon group represented by R ^{1 to} R ¹⁶ include a hydrocarbon group in which a carbon atom directly bonded to the azaannulene ring is substituted with an oxo group. Specific examples include a substituted or unsubstituted acyl group; a carboxyl group;
Substituted or unsubstituted hydrocarbon oxycarbonyl groups such as alkoxycarbonyl groups, aralkyloxycarbonyl groups, aryloxycarbonyl groups, alkenyloxycarbonyl groups; aminocarbonyl groups; An unsubstituted hydrocarbon aminocarbonyl group and the like can be mentioned.

Examples of the substituted or unsubstituted acyl group represented by R ^{1 to} R ¹⁶ include acyl groups which may have the same substituents as the above-mentioned alkyl groups, preferably a formyl group and a methyl group. Carbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group,
n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neopentylcarbonyl group, 2-methylbutylcarbonyl group, benzoyl group , Methylbenzoyl group, ethylbenzoyl group, tolylcarbonyl group, propylbenzoyl group, 4-t-butylbenzoyl group, nitrobenzylcarbonyl group, 3-butoxy-2-naphthoyl group, cinnamoyl group, ferrocenecarbonyl group, 1-methylferrocene 1 to 1 carbon atoms such as carbonyl group
There may be mentioned 15 acyl groups.

Examples of the substituted or unsubstituted alkoxycarbonyl group represented by R ^{1 to} R ¹⁶ include alkoxycarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably a methoxycarbonyl group. , Ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, i
so-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, iso-pentoxycarbonyl group, neopentoxycarbonyl group, 2-pentoxycarbonyl group,
2-ethylhexyloxycarbonyl group, 3,5,5-
Trimethylhexyloxycarbonyl group, decalyloxycarbonyl group, cyclohexyloxycarbonyl group,
A C2-C11 alkoxycarbonyl group such as a chloroethoxycarbonyl group, a hydroxymethoxycarbonyl group, and a hydroxyethoxycarbonyl group;

Methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, pentoxyethoxycarbonyl group, hexyloxyethoxycarbonyl group, butoxybutoxycarbonyl group, hexyloxybutoxycarbonyl group. ,
An alkoxycarbonyl group having 3 to 11 carbon atoms, which is substituted with an alkoxy group such as a hydroxymethoxymethoxycarbonyl group or a hydroxyethoxyethoxycarbonyl group;

A methoxymethoxymethoxycarbonyl group,
4-11 carbon atoms substituted with an alkoxyalkoxy group such as methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, propoxyethoxyethoxycarbonyl group, butoxyethoxyethoxycarbonyl group, pentoxyethoxyethoxycarbonyl group, hexyloxyethoxyethoxycarbonyl group An alkoxycarbonyl group of

Ferrocenylmethoxycarbonyl group, ferrocenylethoxycarbonyl group, ferrocenylpropoxycarbonyl group, ferrocenylbutoxycarbonyl group,
Ferrocenylpentyloxycarbonyl group, ferrocenylhexyloxycarbonyl group, ferrocenylheptyloxycarbonyl group, ferrocenyloctyloxycarbonyl group, ferrocenylnonyloxycarbonyl group, ferrocenyldecyloxycarbonyl group, cobaltcenyl Methoxycarbonyl group, cobaltcenylethoxycarbonyl group, cobaltcenylpropoxycarbonyl group, cobaltcenylbutoxycarbonyl group, cobaltcenylpentyloxycarbonyl group, cobaltcenylhexyloxycarbonyl group, cobaltcenylheptyloxycarbonyl group, cobaltoce Nyloctyloxycarbonyl group,
Cobalt cenyl nonyloxycarbonyl group, cobalt cenyldecyloxycarbonyl group, nickelocenylmethoxycarbonyl group, nickelocenylethoxycarbonyl group, nickelocenylpropoxycarbonyl group, nickelocenylbutoxycarbonyl group, nickelocenylpentyloxycarbonyl group Group, nickelocenylhexyloxycarbonyl group, nickelocenylheptyloxycarbonyl group, nickelocenyloctyloxycarbonyl group, nickelocenylnonyloxycarbonyl group, nickelocenyldecyloxycarbonyl group, dichlorotitanocenylmethoxycarbonyl group, Trichlorotitanium cyclopentadienyl methoxycarbonyl group, bis (trifluoromethanesulfonato) titanocene methoxycarbonyl group, dichlorozirconocenyl methoxy group Xycarbonyl group, dimethylzirconocenylmethoxycarbonyl group, diethoxyzirconocenylmethoxycarbonyl group, bis (cyclopentadienyl) chromium methoxycarbonyl group, bis (cyclopentadienyl) dichlorohafnium methoxycarbonyl group, bis (cyclopenta Dienyl) dichloroniobium methoxycarbonyl group, bis (cyclopentadienyl) ruthenium methoxycarbonyl group, bis (cyclopentadienyl) vanadium methoxycarbonyl group, bis (cyclopentadienyl) dichlorovanadium methoxycarbonyl group, bis (cyclopenta And the like, and an alkoxycarbonyl group having 11 to 20 carbon atoms substituted with a metallocenyl group such as a dienyl) osmium methoxycarbonyl group.

Examples of the substituted or unsubstituted aralkyloxycarbonyl group of R ^{1 to} R ¹⁶ are aralkyloxycarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably, Benzyloxycarbonyl group, nitrobenzyloxycarbonyl group, cyanobenzyloxycarbonyl group, hydroxybenzyloxycarbonyl group, methylbenzyloxycarbonyl group,
Trifluoromethylbenzyloxycarbonyl group, naphthylmethoxycarbonyl group, nitronaphthylmethoxycarbonyl group, cyanonaphthylmethoxycarbonyl group, hydroxynaphthylmethoxycarbonyl group, methylnaphthylmethoxycarbonyl group, trifluoromethylnaphthylmethoxycarbonyl group, fluoren-9-yl Examples thereof include an aralkyloxycarbonyl group having 8 to 16 carbon atoms such as an ethoxycarbonyl group.

Examples of the substituted or unsubstituted aryloxycarbonyl group represented by R ^{1 to} R ¹⁶ include aryloxycarbonyl groups which may have the same substituents as the above-mentioned aryl groups, and preferably, Phenoxycarbonyl group, 2-methylphenoxycarbonyl group, 4-methylphenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 2-methoxyphenoxycarbonyl group, 4-
iso-propylphenoxycarbonyl group, naphthoxycarbonyl group, ferrocenyloxycarbonyl group, cobaltcenyloxycarbonyl group, nickelocenyloxycarbonyl group, zirconocenyloxycarbonyl group, octamethylferrocenyloxycarbonyl group, octa Examples thereof include an aryloxycarbonyl group having 7 to 11 carbon atoms such as a methylcobaltcenyloxycarbonyl group, an octamethylnickerocenyloxycarbonyl group and an octamethylzirconocenyloxycarbonyl group.

Examples of the substituted or unsubstituted alkenyloxycarbonyl group of R ^{1 to} R ¹⁶ are alkenyloxycarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, and are preferably Vinyloxycarbonyl group, propenyloxycarbonyl group, 1-butenyloxycarbonyl group, iso-butenyloxycarbonyl group, 1-pentenyloxycarbonyl group, 2-pentenyloxycarbonyl group, cyclopentadienyloxycarbonyl group, 2- Methyl-1-butenyloxycarbonyl group, 3-methyl-1-butenyloxycarbonyl group, 2-methyl-2-butenyloxycarbonyl group,
2,2-dicyanovinyloxycarbonyl group, 2-cyano-2-methylcarboxylvinyloxycarbonyl group, 2-cyano-2-methylsulfone vinyloxycarbonyl group, styryloxycarbonyl group, 4-phenyl-2-butenyloxy 3 to 1 carbon atoms such as carbonyl group
1 alkenyloxycarbonyl group.

Examples of the mono-substituted aminocarbonyl group represented by R ^{1 to} R ¹⁶ include mono-substituted aminocarbonyl groups which may have the same substituents as the above-mentioned alkyl groups, and preferably methylaminocarbonyl. Group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group,
Octylaminocarbonyl group, (2-ethylhexyl)
A monoalkylaminocarbonyl group having 2 to 11 carbon atoms such as an aminocarbonyl group, a cyclohexylaminocarbonyl group, a (3,5,5-trimethylhexyl) aminocarbonyl group, a nonylaminocarbonyl group and a decylaminocarbonyl group;

Benzylaminocarbonyl group, phenethylaminocarbonyl group, (3-phenylpropylaminocarbonyl group, (4-ethylbenzyl) aminocarbonyl group, (4-isopropylbenzyl) aminocarbonyl group, (4-methylbenzyl) aminocarbonyl group Group, (4
-Ethylbenzyl) aminocarbonyl group, (4-allylbenzyl) aminocarbonyl group, [4- (2-cyanoethyl) benzyl] aminocarbonyl group, [4- (2-acetoxyethyl) benzyl] aminocarbonyl group, and the like. 8-11 monoaralkylaminocarbonyl groups;

Anilinocarbonyl group, naphthylaminocarbonyl group, toluidinocarbonyl group, xylidinocarbonyl group, ethylanilinocarbonyl group, isopropylanilinocarbonyl group, methoxyanilinocarbonyl group, ethoxyanilinocarbonyl group, chloroani Rinocarbonyl group, acetylanilinocarbonyl group, methoxycarbonylanilinocarbonyl group, ethoxycarbonylanilinocarbonyl group, propoxycarbonylanilinocarbonyl group, 4-methylanilinocarbonyl group, 4-
A monoarylaminocarbonyl group having 7 to 11 carbon atoms such as an ethylanilinocarbonyl group;

A vinylaminocarbonyl group, an allylaminocarbonyl group, a butenylaminocarbonyl group, a pentenylaminocarbonyl group, a hexenylaminocarbonyl group, a cyclohexenylaminocarbonyl group, an octadienylaminocarbonyl group, an adamantenylaminocarbonyl group, etc. Examples thereof include monoalkenylaminocarbonyl groups having 3 to 11 carbon atoms.

Examples of the di-substituted aminocarbonyl group of R ^{1 to} R ¹⁶ include a di-substituted aminocarbonyl group which may have a substituent similar to the above-mentioned alkyl group, preferably dimethylaminocarbonyl. Group, diethylaminocarbonyl group, methylethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, di-n-hexylaminocarbonyl group, dicyclohexylaminocarbonyl group, dioctylaminocarbonyl group, pyrrolidinocarbonyl group, piperidino Carbonyl group, morpholino carbonyl group, bis (methoxyethyl)
Aminocarbonyl group, bis (ethoxyethyl) aminocarbonyl group, bis (propoxyethyl) aminocarbonyl group, bis (butoxyethyl) aminocarbonyl group, di (acetyloxyethyl) aminocarbonyl group, di (hydroxyethyl) aminocarbonyl group, N-ethyl-N
A dialkylaminocarbonyl group having 3 to 17 carbon atoms such as a-(2-cyanoethyl) aminocarbonyl group and a di (propionyloxyethyl) aminocarbonyl group;

Dibenzylaminocarbonyl group, diphenethylaminocarbonyl group, bis (4-ethylbenzyl)
A diaralkylaminocarbonyl group having 15 to 21 carbon atoms such as aminocarbonyl group and bis (4-isopropylbenzyl) aminocarbonyl group;

A diarylaminocarbonyl group having 13 to 15 carbon atoms such as a diphenylaminocarbonyl group, a ditolylaminocarbonyl group and an N-phenyl-N-tolylaminocarbonyl group;

Divinylaminocarbonyl group, diallylaminocarbonyl group, dibutenylaminocarbonyl group, dipentenylaminocarbonyl group, dihexenylaminocarbonyl group, N-vinyl-N-allylaminocarbonyl group and the like, having 5 to 13 carbon atoms. Alkenylaminocarbonyl group;

N-phenyl-N-allylaminocarbonyl group, N- (2-acetyloxyethyl) -N-ethylaminocarbonyl group, N-tolyl-N-methylaminocarbonyl group, N-vinyl-N-methylamino A di-substituted aminocarbonyl group having 4 to 11 carbon atoms having a substituent selected from a substituted or unsubstituted alkyl group such as carbonyl group, N-benzyl-N-allylaminocarbonyl group, aralkyl group, aryl group and alkenyl group; Can be mentioned.

Specific examples of the substituted or unsubstituted hydroxy group represented by R ^{1 to} R ¹⁶ include a hydroxyl group; an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom between carbon and carbon atoms There may be mentioned a substituted or unsubstituted hydrocarbon oxy group such as an alkoxy group, an aralkyloxy group, an aryloxy group, an alkenyloxy group which may be present.

Examples of the substituted or unsubstituted alkoxy group of R ^{1 to} R ¹⁶ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec. -Butoxy group, n-pentyloxy group, isopentyloxy group, t
ert-pentyloxy group, sec-pentyloxy group, cyclopentyloxy group, n-hexyloxy group,
1-methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group Base 2,
3-dimethylbutoxy group, 1,1,2-trimethylpropoxy group, 1,2,2-trimethylpropoxy group, 1-
Ethylbutoxy group, 2-ethylbutoxy group, 1-ethyl-2-methylpropoxy group, cyclohexyloxy group,
Methylcyclopentyloxy group, n-heptyloxy group, 1-methylhexyloxy group, 2-methylhexyloxy group, 3-methylhexyloxy group, 4-methylhexyloxy group, 5-methylhexyloxy group, 1,1
-Dimethylpentyloxy group, 1,2-dimethylpentyloxy group, 1,3-dimethylpentyloxy group, 1,
4-dimethylpentyloxy group, 2,2-dimethylpentyloxy group, 2,3-dimethylpentyloxy group,
2,4-dimethylpentyloxy group, 3,3-dimethylpentyloxy group, 3,4-dimethylpentyloxy group, 1-ethylpentyloxy group, 2-ethylpentyloxy group, 3-ethylpentyloxy group, 1, 1,2-
Trimethylbutoxy group, 1,1,3-trimethylbutoxy group, 1,2,3-trimethylbutoxy group, 1,2,2
-Trimethylbutoxy group, 1,3,3-trimethylbutoxy group, 2,3,3-trimethylbutoxy group, 1-ethyl-1-methylbutoxy group, 1-ethyl-2-methylbutoxy group, 1-ethyl-3 -Methylbutoxy group, 2-ethyl-1-methylbutoxy group, 2-ethyl-3-methylbutoxy group, 1-n-propylbutoxy group, 1-isopropylbutoxy group, 1-isopropyl-2-methylpropoxy group, methyl Cyclohexyloxy group, n-octyloxy group, 1-methylheptyloxy group, 2-methylheptyloxy group, 3-methylheptyloxy group, 4-
Methylheptyloxy group, 5-methylheptyloxy group, 6-methylheptyloxy group, 1,1-dimethylhexyloxy group, 1,2-dimethylhexyloxy group,
1,3-dimethylhexyloxy group, 1,4-dimethylhexyloxy group, 1,5-dimethylhexyloxy group, 2,2-dimethylhexyloxy group, 2,3-dimethylhexyloxy group, 2,4-dimethyl Hexyloxy group, 2,5-dimethylhexyloxy group, 3,3-dimethylhexyloxy group, 3,4-dimethylhexyloxy group, 3,5-dimethylhexyloxy group, 4,4-
Dimethylhexyloxy group, 4,5-dimethylhexyloxy group, 1-ethylhexyloxy group, 2-ethylhexyloxy group, 3-ethylhexyloxy group, 4-ethylhexyloxy group, 1-n-propylpentyloxy group, 2-n -Propylpentyloxy group, 1-isopropylpentyloxy group, 2-isopropylpentyloxy group, 1-ethyl-1-methylpentyloxy group, 1
-Ethyl-2-methylpentyloxy group, 1-ethyl-
3-methylpentyloxy group, 1-ethyl-4-methylpentyloxy group, 2-ethyl-1-methylpentyloxy group, 2-ethyl-2-methylpentyloxy group, 2
-Ethyl-3-methylpentyloxy group, 2-ethyl-
4-methylpentyloxy group, 3-ethyl-1-methylpentyloxy group, 3-ethyl-2-methylpentyloxy group, 3-ethyl-3-methylpentyloxy group, 3
-Ethyl-4-methylpentyloxy group, 1,1,2-
Trimethylpentyloxy group, 1,1,3-trimethylpentyloxy group, 1,1,4-trimethylpentyloxy group, 1,2,2-trimethylpentyloxy group,
1,2,3-trimethylpentyloxy group, 1,2,4
-Trimethylpentyloxy group, 1,3,4-trimethylpentyloxy group, 2,2,3-trimethylpentyloxy group, 2,2,4-trimethylpentyloxy group,
2,3,4-trimethylpentyloxy group, 1,3,3
-Trimethylpentyloxy group, 2,3,3-trimethylpentyloxy group, 3,3,4-trimethylpentyloxy group, 1,4,4-trimethylpentyloxy group,
2,4,4-trimethylpentyloxy group, 3,4,4
-Trimethylpentyloxy group, 1-n-butylbutoxy group, 1-isobutylbutoxy group, 1-sec-butylbutoxy group, 1-tert-butylbutoxy group, 2-t
ert-butylbutoxy group, 1-n-propyl-1-methylbutoxy group, 1-n-propyl-2-methylbutoxy group, 1-n-propyl-3-methylbutoxy group, 1-
Isopropyl-1-methylbutoxy group, 1-isopropyl-2-methylbutoxy group, 1-isopropyl-3-methylbutoxy group, 1,1-diethylbutoxy group, 1,2
-Diethylbutoxy group, 1-ethyl-1,2-dimethylbutoxy group, 1-ethyl-1,3-dimethylbutoxy group, 1-ethyl-2,3-dimethylbutoxy group, 2-ethyl-1,1-dimethyl Butoxy group, 2-ethyl-1,
2-dimethylbutoxy group, 2-ethyl-1,3-dimethylbutoxy group, 2-ethyl-2,3-dimethylbutoxy group, 1,1,3,3-tetramethylbutoxy group, 1,2
-Dimethylcyclohexyloxy group, 1,3-dimethylcyclohexyloxy group, 1,4-dimethylcyclohexyloxy group, ethylcyclohexyloxy group, n-nonyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n
-Dodecyloxy group, 1-adamantyloxy group, n-
A linear, branched or cyclic unsubstituted alkoxy group having 1 to 15 carbon atoms such as a pentadecyloxy group;

Methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, n-propoxyethoxy group,
Isopropoxyethoxy group, n-butoxyethoxy group,
Isobutoxyethoxy group, tert-butoxyethoxy group, sec-butoxyethoxy group, n-pentyloxyethoxy group, isopentyloxyethoxy group, tert
-Pentyloxyethoxy group, sec-pentyloxyethoxy group, cyclopentyloxyethoxy group, n-hexyloxyethoxy group, ethylcyclohexyloxyethoxy group, n-nonyloxyethoxy group, (3,5,5
5-trimethylhexyloxy) ethoxy group, (3,
5,5-trimethylhexyloxy) butoxy group, n-
Decyloxyethoxy group, n-undecyloxyethoxy group, n-dodecyloxyethoxy group, 3-methoxypropoxy group, 3-ethoxypropoxy group, 3- (n-propoxy) propoxy group, 2-isopropoxypropoxy group, 2 -Methoxybutoxy group, 2-ethoxybutoxy group, 2- (n-propoxy) butoxy group, 4-isopropoxybutoxy group, decalyloxyethoxy group, adamantyloxyethoxy group and the like, having 2 carbon atoms substituted with an alkoxy group. ~ 15 alkoxy groups;

Methoxymethoxymethoxy group, ethoxymethoxymethoxy group, propoxymethoxymethoxy group, butoxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxymethoxy group, propoxyethoxymethoxy group, butoxyethoxymethoxy group, methoxypropoxymethoxy group, ethoxypropoxy. Methoxy group,
Propoxypropoxymethoxy group, butoxypropoxymethoxy group, methoxybutoxymethoxy group, ethoxybutoxymethoxy group, propoxybutoxymethoxy group, butoxybutoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, propoxymethoxyethoxy group, butoxymethoxyethoxy group, Methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propoxyethoxyethoxy group, butoxyethoxyethoxy group, methoxypropoxyethoxy group, ethoxypropoxyethoxy group, propoxypropoxyethoxy group, butoxypropoxyethoxy group, methoxybutoxyethoxy group, ethoxybutoxyethoxy group, Propoxy butoxy ethoxy group, butoxy butoxy ethoxy group, methoxy methoxy propoxy , Ethoxy methoxypropoxy group,
Propoxymethoxypropoxy group, butoxymethoxypropoxy group, methoxyethoxypropoxy group, ethoxyethoxypropoxy group, propoxyethoxypropoxy group, butoxyethoxypropoxy group, methoxypropoxypropoxy group, ethoxypropoxypropoxy group, propoxypropoxypropoxy group, butoxypropoxypropoxy group, Methoxybutoxypropoxy group, ethoxybutoxypropoxy group, propoxybutoxypropoxy group, butoxybutoxypropoxy group, methoxymethoxybutoxy group, ethoxymethoxybutoxy group, propoxymethoxybutoxy group, butoxymethoxybutoxy group,
Methoxyethoxy butoxy group, ethoxy ethoxy butoxy group, propoxy ethoxy butoxy group, butoxy ethoxy butoxy go, methoxy propoxy butoxy group, ethoxy propoxy butoxy group, propoxy propoxy butoxy group, butoxy propoxy butoxy group, methoxy butoxy butoxy group, ethoxy butoxy butoxy group , Propoxybutoxybutoxy group, butoxybutoxybutoxy group, (4-ethylcyclohexyloxy) ethoxyethoxy group, (2-ethyl-1-hexyloxy) ethoxypropoxy group, [4- (3,5,5-trimethylhexyloxy) Butoxy] ethoxy group or the like, which is substituted with an alkoxyalkoxy group, and has a linear, branched, or cyclic carbon number 3
~ 15 alkoxy groups;

Methoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, n-propoxycarbonylmethoxy group, isopropoxycarbonylmethoxy group, (4 '
3 to 1 carbon atoms substituted with an alkoxycarbonyl group such as -ethylcyclohexyloxy) carbonylmethoxy group
An alkoxy group of 0;

An alkoxy group having 3 to 10 carbon atoms, which is substituted with an acyl group such as an acetylmethoxy group, an ethylcarbonylmethoxy group, an octylcarbonylmethoxy group and a phenacyloxy group;

An alkoxy group having 3 to 10 carbon atoms, which is substituted with an acyloxy group such as an acetyloxymethoxy group, an acetyloxyethoxy group, an acetyloxyhexyloxy group and a butanoyloxycyclohexyloxy group;

Methylaminomethoxy group, 2-methylaminoethoxy group, 2- (2-methylaminoethoxy) ethoxy group, 4-methylaminobutoxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropoxy group. Group, 2-methylamino-2-methylpropoxy group,
2-ethylaminoethoxy group, 2- (2-ethylaminoethoxy) ethoxy group, 3-ethylaminopropoxy group, 1-ethylaminopropoxy group, 2-isopropylaminoethoxy group, 2- (n-butylamino) ethoxy group , 3- (n-hexylamino) propoxy group, 4-
An alkoxy group having 2 to 10 carbon atoms substituted with an alkylamino group such as (cyclohexylamino) butyloxy group;

Methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropoxy group, ethylaminoethoxypropoxy group, 4-
3 to 1 carbon atoms substituted with an alkylaminoalkoxy group such as (2′-isobutylaminopropoxy) butoxy group
An alkoxy group of 0;

Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoethoxy)
Ethoxy group, 4-dimethylaminobutoxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropoxy group, 2-dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group, 2-
(2-diethylaminoethoxy) ethoxy group, 3-diethylaminopropoxy group, 1-diethylaminopropoxy group, 2-diisopropylaminoethoxy group, 2- (di-
an alkoxy group having 3 to 15 carbon atoms, which is substituted with a dialkylamino group such as (n-butylamino) ethoxy group, 2-piperidylethoxy group, and 3- (di-n-hexylamino) propoxy group;

Number of carbon atoms substituted with a dialkylaminoalkoxy group such as a dimethylaminomethoxymethoxy group, a dimethylaminoethoxyethoxy group, a dimethylaminoethoxypropoxy group, a diethylaminoethoxypropoxy group and a 4- (2'-diisobutylaminopropoxy) butoxy group. 4 to 15 alkoxy groups;

Methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group,
A 2-n-butylthioethoxy group, a 2-isobutylthioethoxy group, a (3,5,5-trimethylhexylthio) hexyloxy group, or another alkoxy group having 2 to 15 carbon atoms, which is substituted with an alkylthio group;

And the like, preferably a methoxy group,
Ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso
-Pentoxy group, neopentoxy group, 2-methylbutoxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, decalyloxy group, methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group Carbon number 1
The alkoxy groups of 10 to 10 are mentioned.

Examples of the substituted or unsubstituted aralkyloxy group for R ^{1 to} R ¹⁶ are aralkyloxy groups which may have the same substituents as the above-mentioned alkyl groups,
Preferably, benzyloxy group, nitrobenzyloxy group, cyanobenzyloxy group, hydroxybenzyloxy group, methylbenzyloxy group, trifluoromethylbenzyloxy group, naphthylmethoxy group, nitronaphthylmethoxy group, cyanonaphthylmethoxy group, hydroxynaphthyl Examples thereof include an aralkyloxy group having 7 to 15 carbon atoms such as a methoxy group, a methylnaphthylmethoxy group, a trifluoromethylnaphthylmethoxy group, and a fluoren-9-ylethoxy group.

Examples of the substituted or unsubstituted aryloxy group represented by R ^{1 to} R ¹⁶ include aryloxy groups which may have the same substituents as the above-mentioned alkyl groups, preferably a phenylthio group. A 2-methylphenylthio group,
4-methylphenylthio group, 4-t-butylphenylthio group, 2-methoxyphenylthio group, 4-iso-propylphenylthio group, tolyloxy group, naphthoxy group,
C6-18 aryl such as ferrocenyloxy group, cobaltcenyloxy group, nickelocenyloxy group, octamethylferrocenyloxy group, octamethylcobaltcenyloxy group, octamethylnickerocenyloxy group An oxy group is mentioned.

Further, the substituted or unsubstituted heteroaryl of R ^{1 to} R ¹⁶ which is an aryloxy group having an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom between carbon atoms. Examples of the oxy group include a heteroaryloxy group in which the above-mentioned heteroaryl group is bonded to an oxygen atom.

Examples of the substituted or unsubstituted alkenyloxy group of R ^{1 to} R ¹⁶ are alkenyloxy groups which may have the same substituents as the above-mentioned alkyl groups,
Preferably, a vinyloxy group, a propenyloxy group, 1
-Butenyloxy group, iso-butenyloxy group, 1-
Pentenyloxy group, 2-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-1-butenyloxy group, 2-methyl-2-butenyloxy group, cyclopentadienyloxy group, 2,2-dicyanovinyl group An oxy group, a 2-cyano-2-methylcarboxyl vinyloxy group, a 2-cyano-2-methylsulfone vinyloxy group, a styryloxy group, a 4-phenyl-2-butenyloxy group, a cinnamylalkoxy group and the like having 2 to 2 carbon atoms. 10
Alkenyloxy groups of

Further, examples of the substituted hydrocarbon oxy group represented by R ^{1 to} R ¹⁶ include a hydrocarbon oxy group in which a carbon atom directly bonded to an oxygen atom directly bonded to the azaannulene ring is substituted with an oxo group. Specific examples include a substituted or unsubstituted acyloxy group; an alkoxycarbonyloxy group,
Substituted or unsubstituted hydrocarbon oxycarbonyloxy group such as aralkyloxycarbonyloxy group, aryloxycarbonyloxy group, alkenyloxycarbonyloxy group; substituted or unsubstituted monosubstituted aminocarbonyloxy group, disubstituted aminocarbonyloxy group, etc. And a hydrocarbon aminocarbonyloxy group thereof.

Examples of the substituted or unsubstituted acyloxy group of R ^{1 to} R ¹⁶ include an acyloxy group which may have a substituent similar to the above-mentioned alkyl group, preferably a formyloxy group, Methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group Group, n-pentylcarbonyloxy group, iso-pentylcarbonyloxy group, neopentylcarbonyloxy group, 2-methylbutylcarbonyloxy group, benzoyloxy group, methylbenzoyloxy group, ethylbenzoyloxy group, tolylcarbonyloxy group, propyl Ben Yloxy group, 4-t-butylbenzoyloxy group, nitrobenzylcarbonyloxy group, 3-butoxy-2-naphthoyloxy group, cinnamoyloxy group, ferrocenecarbonyloxy group, 1-methylferrocene-1′-carbonyloxy group And an acyloxy group having 1 to 15 carbon atoms.

Examples of the substituted or unsubstituted alkoxycarbonyloxy group for R ^{1 to} R ¹⁶ are alkoxycarbonyloxy groups which may have the same substituents as the above-mentioned alkyl groups, and are preferably methoxy. Carbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group, n-butoxycarbonyloxy group, iso-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, t-butoxycarbonyloxy group , N-pentoxycarbonyloxy group, iso-pentoxycarbonyloxy group, neopentoxycarbonyloxy group,
2-pentoxycarbonyloxy group, 2-ethylhexyloxycarbonyloxy group, 3,5,5-trimethylhexyloxycarbonyloxy group, decalyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, chloroethoxycarbonyloxy group, hydroxymethoxy A C2-C11 alkoxycarbonyloxy group such as a carbonyloxy group or a hydroxyethoxycarbonyloxy group;

Methoxymethoxycarbonyloxy group, methoxyethoxycarbonyloxy group, ethoxyethoxycarbonyloxy group, propoxyethoxycarbonyloxy group, butoxyethoxycarbonyloxy group, pentoxyethoxycarbonyloxy group, hexyloxyethoxycarbonyloxy group, butoxybutoxycarbonyl. Oxy group, hexyloxybutoxycarbonyloxy group, hydroxymethoxymethoxycarbonyloxy group,
An alkoxycarbonyloxy group having 3 to 11 carbon atoms, which is substituted with an alkoxy group such as a hydroxyethoxyethoxycarbonyloxy group;

A methoxymethoxymethoxycarbonyloxy group, a methoxyethoxyethoxycarbonyloxy group,
4-11 carbon atoms substituted with an alkoxyalkoxy group such as ethoxyethoxyethoxycarbonyloxy group, propoxyethoxyethoxycarbonyloxy group, butoxyethoxyethoxycarbonylcarbonyl group, pentoxyethoxyethoxycarbonyloxy group, hexyloxyethoxyethoxycarbonyloxy group An alkoxycarbonyloxy group of

Ferrocenylmethoxycarbonyloxy group, ferrocenylethoxycarbonyloxy group, ferrocenylpropoxycarbonyloxy group, ferrocenylbutoxycarbonyloxy group, ferrocenylpentyloxycarbonyloxy group, ferrocenylhexyloxycarbonyloxy group Group, ferrocenylheptyloxycarbonyloxy group, ferrocenyloctyloxycarbonyloxy group, ferrocenylnonyloxycarbonyloxy group, ferrocenyldecyloxycarbonyloxy group,

Cobalt cenyl methoxycarbonyloxy group, cobalt cenyl ethoxycarbonyloxy group, cobalt cenyl propoxycarbonyloxy group, cobalt cenyl butoxycarbonyloxy group, cobalt cenyl pentyloxycarbonyloxy group, cobalt cenylhexyloxycarbonyloxy group. Group, cobalt cenylheptyloxycarbonyloxy group, cobalt cenyloctyloxycarbonyloxy group, cobalt cenyl nonyloxycarbonyloxy group, cobalt cenyldecyloxycarbonyloxy group,

Nickerocenylmethoxycarbonyloxy group, nickelocenylethoxycarbonyloxy group, nickelocenylpropoxycarbonyloxy group, nickelocenylbutoxycarbonyloxy group, nickelocenylpentyloxycarbonyloxy group, nickelocenylhexyloxycarbonyl group. Oxy group, nickelocenylheptyloxycarbonyloxy group, nickelocenyloctyloxycarbonyloxy group, nickelocenylnonyloxycarbonyloxy group, nickelocenyldecyloxycarbonyloxy group,

Dichlorotitanocenyl methoxycarbonyloxy group, trichlorotitanium cyclopentadienyl methoxycarbonyloxy group, bis (trifluoromethanesulfonato) titanocene methoxycarbonyloxy group, dichlorozirconocenyl methoxycarbonyloxy group, dimethylzirconocenyl methoxy group Carbonyloxy group, diethoxyzirconocenyl methoxycarbonyloxy group,
Bis (cyclopentadienyl) chromium methoxycarbonyloxy group, bis (cyclopentadienyl) dichlorohafnium methoxycarbonyloxy group, bis (cyclopentadienyl) dichloroniobium methoxycarbonyloxy group, bis (cyclopentadienyl) ruthenium methoxy group Carbonyloxy group, bis (cyclopentadienyl)
An alkoxycarbonyloxy group having 11 to 20 carbon atoms substituted with a metallocenyl group such as a vanadium methoxycarbonyloxy group, a bis (cyclopentadienyl) dichlorovanadium methoxycarbonyloxy group, a bis (cyclopentadienyl) osmium methoxycarbonyloxy group; Etc.

Examples of the substituted or unsubstituted aralkyloxycarbonyloxy group for R ^{1 to} R ¹⁶ are aralkyloxycarbonyloxy groups which may have the same substituents as the above-mentioned alkyl groups, and are preferable. Is a benzyloxycarbonyloxy group, a nitrobenzyloxycarbonyloxy group, a cyanobenzyloxycarbonyloxy group, a hydroxybenzyloxycarbonyloxy group, a methylbenzyloxycarbonyloxy group, a trifluoromethylbenzyloxycarbonyloxy group, a naphthylmethoxycarbonyloxy group. , Nitronaphthylmethoxycarbonyloxy group, cyanonaphthylmethoxycarbonyloxy group, hydroxynaphthylmethoxycarbonyloxy group, methylnaphthylmethoxycarbonyloxy group, trifluoromethyl Luna border Le methoxycarbonyloxy group, fluoren-9-yl ethoxycarbonyloxy group, aralkyloxycarbonyl group having 8 to 16 carbon atoms such as, and the like.

Examples of the substituted or unsubstituted aryloxycarbonyloxy group represented by R ^{1 to} R ¹⁶ include aryloxycarbonyloxy groups which may have the same substituents as the above-mentioned aryl groups, and are preferable. Is a phenoxycarbonyloxy group, a 2-methylphenoxycarbonyloxy group, a 4-methylphenoxycarbonyloxy group,
4-t-butylphenoxycarbonyloxy group, 2-methoxyphenoxycarbonyloxy group, 4-iso-propylphenoxycarbonyloxy group, naphthoxycarbonyloxy group, ferrocenyloxycarbonyloxy group, cobaltcenyloxycarbonyloxy group, Nickelocenyloxycarbonyloxy group, zirconocenyloxycarbonyloxy group, octamethylferrocenyloxycarbonyloxy group, octamethylcobaltcenyloxycarbonyloxy group, octamethylnickerocenyloxycarbonyloxy group, octamethylzirconose 7 to 11 carbon atoms such as a nyloxycarbonyloxy group
And the aryloxycarbonyloxy group.

Examples of the substituted or unsubstituted alkenyloxycarbonyloxy group for R ^{1 to} R ¹⁶ are alkenyloxycarbonyloxy groups which may have the same substituents as the above-mentioned alkyl groups, and are preferable. Is a vinyloxycarbonyloxy group, a propenyloxycarbonyloxy group, a 1-butenyloxycarbonyloxy group,
iso-butenyloxycarbonyloxy group, 1-pentenyloxycarbonyloxy group, 2-pentenyloxycarbonyloxy group, cyclopentadienyloxycarbonyloxy group, 2-methyl-1-butenyloxycarbonyloxy group, 3-methyl -1-butenyloxycarbonyloxy group, 2-methyl-2-butenyloxycarbonyloxy group, 2,2-dicyanovinyloxycarbonyloxy group, 2-cyano-2-methylcarboxylvinyloxycarbonyloxy group, 2- Examples thereof include an alkenyloxycarbonyloxy group having 3 to 11 carbon atoms such as a cyano-2-methylsulfone vinyloxycarbonyloxy group, a styryloxycarbonyloxy group and a 4-phenyl-2-butenyloxycarbonyloxy group.

Examples of the mono-substituted aminocarbonyloxy group represented by R ^{1 to} R ¹⁶ include mono-substituted aminocarbonyloxy groups which may have the same substituents as the above-mentioned alkyl groups, preferably methyl. Aminocarbonyloxy group, ethylaminocarbonyloxy group, propylaminocarbonyloxy group, butylaminocarbonyloxy group, pentylaminocarbonyloxy group, hexylaminocarbonyloxy group, heptylaminocarbonyloxy group, octylaminocarbonyloxy group, (2- 2 to 1 carbon atoms such as ethylhexyl) aminocarbonyloxy group, cyclohexylaminocarbonyloxy group, (3,5,5-trimethylhexyl) aminocarbonyloxy group, nonylaminocarbonyloxy group and decylaminocarbonyloxy group Mono alkylaminocarbonyloxy group;

Benzylaminocarbonyloxy group, phenethylaminocarbonyloxy group, (3-phenylpropylaminocarbonyloxy group, (4-ethylbenzyl) aminocarbonyloxy group, (4-isopropylbenzyl) aminocarbonyloxy group, (4- Methylbenzyl) aminocarbonyloxy group, (4-ethylbenzyl) aminocarbonyloxy group, (4-allylbenzyl) aminocarbonyloxy group, [4- (2-cyanoethyl) benzyl] aminocarbonyloxy group, [4-
A monoaralkylaminocarbonyloxy group having 8 to 11 carbon atoms such as (2-acetoxyethyl) benzyl] aminocarbonyloxy group;

Anilinocarbonyloxy group, naphthylaminocarbonyloxy group, toluidinocarbonyloxy group, xylidinocarbonyloxy group, ethylanilinocarbonyloxy group, isopropylanilinocarbonyloxy group, methoxyanilinocarbonyloxy group, ethoxy Anilinocarbonyloxy group, chloroanilinocarbonyloxy group, acetylanilinocarbonyloxy group,
Methoxycarbonylanilinocarbonyloxy group, ethoxycarbonylanilinocarbonyloxy group, propoxycarbonylanilinocarbonyloxy group, 4-methylanilinocarbonyloxy group, 4-ethylanilinocarbonyloxy group, and the like having 7 to 11 carbon atoms. Monoarylaminocarbonyloxy group;

Vinylaminocarbonyloxy group, allylaminocarbonyloxy group, butenylaminocarbonyloxy group, pentenylaminocarbonyloxy group, hexenylaminocarbonyloxy group, cyclohexenylaminocarbonyloxy group, octadienylaminocarbonyloxy group, adaman Examples thereof include monoalkenylaminocarbonyloxy groups having 3 to 11 carbon atoms such as a tenylaminocarbonyloxy group.

Examples of the di-substituted aminocarbonyloxy group represented by R ^{1 to} R ¹⁶ include a di-substituted aminocarbonyloxy group which may have the same substituents as the above-mentioned alkyl groups, preferably dimethyl. Aminocarbonyloxy group, diethylaminocarbonyloxy group, methylethylaminocarbonyloxy group, dipropylaminocarbonyloxy group, dibutylaminocarbonyloxy group, di-
n-hexylaminocarbonyloxy group, dicyclohexylaminocarbonyloxy group, dioctylaminocarbonyloxy group, pyrrolidinocarbonyloxy group, piperidinocarbonyloxy group, morpholinocarbonyloxy group, bis (methoxyethyl) aminocarbonyloxy group, bis ( Ethoxyethyl) aminocarbonyloxy group, bis (propoxyethyl) aminocarbonyloxy group, bis (butoxyethyl) aminocarbonyloxy group, di (acetyloxyethyl) aminocarbonyloxy group, di (hydroxyethyl) aminocarbonyloxy group, N -Ethyl-N- (2-cyanoethyl) aminocarbonyloxy group, di (propionyloxyethyl) aminocarbonyloxy group and like dialkylaminocarbonyloxy groups having 3 to 17 carbon atoms Shi group;

Diaralkyl having 15 to 21 carbon atoms such as dibenzylaminocarbonyloxy group, diphenethylaminocarbonyloxy group, bis (4-ethylbenzyl) aminocarbonyloxy group and bis (4-isopropylbenzyl) aminocarbonyloxy group. Aminocarbonyloxy group;

Diphenylaminocarbonyloxy group, ditolylaminocarbonyloxy group, N-phenyl-N-
13 to 1 carbon atoms such as tolylaminocarbonyloxy group
A diarylaminocarbonyloxy group of 5;

Carbon such as divinylaminocarbonyloxy group, diallylaminocarbonyloxy group, dibutenylaminocarbonyloxy group, dipentenylaminocarbonyloxy group, dihexenylaminocarbonyloxy group, N-vinyl-N-allylaminocarbonyloxy group A dialkenylaminocarbonyloxy group of the number 5 to 13;

N-phenyl-N-allylaminocarbonyloxy group, N- (2-acetyloxyethyl) -N-
Substituted or unsubstituted alkyl such as ethylaminocarbonyloxy group, N-tolyl-N-methylaminocarbonyloxy group, N-vinyl-N-methylaminocarbonyloxy group, N-benzyl-N-allylaminocarbonyloxy group, etc. And a di-substituted aminocarbonyloxy group having 4 to 11 carbon atoms having a substituent selected from a group, an aralkyl group, an aryl group and an alkenyl group.

Specific examples of the substituted or unsubstituted mercapto group represented by R ^{1 to} R ¹⁶ include an unsubstituted mercapto group; an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted carbon atom between carbon and carbon atoms. Alternatively, a substituted or unsubstituted hydrocarbon thio group such as an alkylthio group which may have an unsubstituted nitrogen atom, an aralkylthio group, an arylthio group and an alkenylthio group may be mentioned.

Examples of the substituted or unsubstituted alkylthio group represented by R ^{1 to} R ¹⁶ include alkylthio groups which may have the same substituents as the above-mentioned alkyl groups, preferably methylthio group and ethylthio group. Group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, sec-butylthio group, n-pentylthio group, isopentylthio group, te
rt-pentylthio group, sec-pentylthio group, cyclopentylthio group, n-hexylthio group, 1-methylpentylthio group, 2-methylpentylthio group, 3-methylpentylthio group, 4-methylpentylthio group, 1,1 −
Dimethylbutylthio group, 1,2-dimethylbutylthio group, 1,3-dimethylbutylthio group, 2,3-dimethylbutylthio group, 1,1,2-trimethylpropylthio group, 1,2,2-trimethyl Propylthio group, 1-ethylbutylthio group, 2-ethylbutylthio group, 1-ethyl-2-methylpropylthio group, cyclohexylthio group,
Methylcyclopentylthio group, n-heptylthio group, 1
-Methylhexylthio group, 2-methylhexylthio group,
3-methylhexylthio group, 4-methylhexylthio group, 5-methylhexylthio group, 1,1-dimethylpentylthio group, 1,2-dimethylpentylthio group, 1,3
-Dimethylpentylthio group, 1,4-dimethylpentylthio group, 2,2-dimethylpentylthio group, 2,3-dimethylpentylthio group, 2,4-dimethylpentylthio group, 3,3-dimethylpentylthio group , 3,4-dimethylpentylthio group, 1-ethylpentylthio group, 2-ethylpentylthio group, 3-ethylpentylthio group, 1,
1,2-trimethylbutylthio group, 1,1,3-trimethylbutylthio group, 1,2,3-trimethylbutylthio group, 1,2,2-trimethylbutylthio group, 1,3,3
-Trimethylbutylthio group, 2,3,3-trimethylbutylthio group, 1-ethyl-1-methylbutylthio group, 1
-Ethyl-2-methylbutylthio group, 1-ethyl-3-
Methylbutylthio group, 2-ethyl-1-methylbutylthio group, 2-ethyl-3-methylbutylthio group, 1-n-
Propylbutylthio group, 1-isopropylbutylthio group, 1-isopropyl-2-methylpropylthio group, methylcyclohexylthio group, n-octylthio group, 1-
Methylheptylthio group, 2-methylheptylthio group, 3
-Methylheptylthio group, 4-methylheptylthio group,
5-methylheptylthio group, 6-methylheptylthio group, 1,1-dimethylhexylthio group, 1,2-dimethylhexylthio group, 1,3-dimethylhexylthio group,
1,4-dimethylhexylthio group, 1,5-dimethylhexylthio group, 2,2-dimethylhexylthio group, 2,
3-dimethylhexylthio group, 2,4-dimethylhexylthio group, 2,5-dimethylhexylthio group, 3,3-
Dimethylhexylthio group, 3,4-dimethylhexylthio group, 3,5-dimethylhexylthio group, 4,4-dimethylhexylthio group, 4,5-dimethylhexylthio group, 1-ethylhexylthio group, 2-ethylhexyl Thio group, 3-ethylhexylthio group, 4-ethylhexylthio group, 1-n-propylpentylthio group, 2-n-propylpentylthio group, 1-isopropylpentylthio group, 2-isopropylpentylthio group, 1-ethyl -1
-Methylpentylthio group, 1-ethyl-2-methylpentylthio group, 1-ethyl-3-methylpentylthio group,
1-ethyl-4-methylpentylthio group, 2-ethyl-
1-methylpentylthio group, 2-ethyl-2-methylpentylthio group, 2-ethyl-3-methylpentylthio group, 2-ethyl-4-methylpentylthio group, 3-ethyl-1-methylpentylthio group , 3-ethyl-2-methylpentylthio group, 3-ethyl-3-methylpentylthio group, 3-ethyl-4-methylpentylthio group, 1,
1,2-trimethylpentylthio group, 1,1,3-trimethylpentylthio group, 1,1,4-trimethylpentylthio group, 1,2,2-trimethylpentylthio group,
1,2,3-trimethylpentylthio group, 1,2,4-
Trimethylpentylthio group, 1,3,4-trimethylpentylthio group, 2,2,3-trimethylpentylthio group, 2,2,4-trimethylpentylthio group, 2,3
4-trimethylpentylthio group, 1,3,3-trimethylpentylthio group, 2,3,3-trimethylpentylthio group, 3,3,4-trimethylpentylthio group, 1,
4,4-trimethylpentylthio group, 2,4,4-trimethylpentylthio group, 3,4,4-trimethylpentylthio group, 1-n-butylbutylthio group, 1-isobutylbutylthio group, 1-sec -Butylbutylthio group, 1
-Tert-butylbutylthio group, 2-tert-butylbutylthio group, 1-n-propyl-1-methylbutylthio group, 1-n-propyl-2-methylbutylthio group,
1-n-propyl-3-methylbutylthio group, 1-isopropyl-1-methylbutylthio group, 1-isopropyl-2-methylbutylthio group, 1-isopropyl-3-methylbutylthio group, 1,1- Diethylbutylthio group,
1,2-diethylbutylthio group, 1-ethyl-1,2-
Dimethylbutylthio group, 1-ethyl-1,3-dimethylbutylthio group, 1-ethyl-2,3-dimethylbutylthio group, 2-ethyl-1,1-dimethylbutylthio group, 2
-Ethyl-1,2-dimethylbutylthio group, 2-ethyl-1,3-dimethylbutylthio group, 2-ethyl-2,3
-Dimethylbutylthio group, 1,1,3,3-tetramethylbutylthio group, 1,2-dimethylcyclohexylthio group, 1,3-dimethylcyclohexylthio group, 1,4-
Dimethylcyclohexylthio group, ethylcyclohexylthio group, n-nonylthio group, 3,5,5-trimethylhexylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, 1-adamantylthio group, n
A straight-chain, branched or cyclic unsubstituted alkylthio group having 1 to 15 carbon atoms such as pentadecylthio group;

Methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, n-propoxyethylthio group, isopropoxyethylthio group, n-butoxyethylthio group, isobutoxyethylthio group, tert-butoxyethylthio group, sec-butoxyethylthio group, n
-Pentyloxyethylthio group, isopentyloxyethylthio group, tert-pentyloxyethylthio group,
sec-pentyloxyethylthio group, cyclopentyloxyethylthio group, n-hexyloxyethylthio group, ethylcyclohexyloxyethylthio group, n-nonyloxyethylthio group, (3,5,5-trimethylhexyloxy) ethylthio group , (3,5,5-trimethylhexyloxy) butylthio group, n-decyloxyethylthio group, n-undecyloxyethylthio group, n-
Dodecyloxyethylthio group, 3-methoxypropylthio group, 3-ethoxypropylthio group, 3- (n-propoxy) propylthio group, 2-isopropoxypropylthio group, 2-methoxybutylthio group, 2-ethoxybutylthio group Group, 2- (n-propoxy) butylthio group, 4-isopropoxybutylthio group, decalyloxyethylthio group, adamantyloxyethylthio group, and the like, an alkylthio group having 2 to 15 carbon atoms substituted with an alkoxy group;

Methoxymethoxymethylthio group, ethoxymethoxymethylthio group, propoxymethoxymethylthio group, butoxymethoxymethylthio group, methoxyethoxymethylthio group, ethoxyethoxymethylthio group, propoxyethoxymethylthio group, butoxyethoxymethylthio group, methoxypropoxymethylthio group, ethoxypropoxy. Methylthio group, propoxypropoxymethylthio group, butoxypropoxymethylthio group, methoxybutoxymethylthio group, ethoxybutoxymethylthio group, propoxybutoxymethylthio group, butoxybutoxymethylthio group, methoxymethoxyethylthio group, ethoxymethoxyethylthio group, propoxymethoxyethylthio group ,
Butoxymethoxyethylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, propoxyethoxyethylthio group, butoxyethoxyethylthio group, methoxypropoxyethylthio group, ethoxypropoxyethylthio group, propoxypropoxyethylthio group, butoxypropoxy Ethylthio group, methoxybutoxyethylthio group, ethoxybutoxyethylthio group, propoxybutoxyethylthio group, butoxybutoxyethylthio group, methoxymethoxypropylthio group, ethoxymethoxypropylthio group, propoxymethoxypropylthio group, butoxymethoxypropylthio group Group, methoxyethoxypropylthio group, ethoxyethoxypropylthio group, propoxyethoxypropylthio group, butoxyethoxypropylthio group, Xypropoxypropylthio group, ethoxypropoxypropylthio group, propoxypropoxypropylthio group, butoxypropoxypropylthio group, methoxybutoxypropylthio group, ethoxybutoxypropylthio group, propoxybutoxypropylthio group, butoxybutoxypropylthio group, methoxymethoxy Butylthio group, ethoxymethoxybutylthio group, propoxymethoxybutylthio group, butoxymethoxybutylthio group, methoxyethoxybutylthio group, ethoxyethoxybutylthio group, propoxyshiethoxybutylthio group, butoxyethoxybutoxy-go, methoxypropoxybutylthio group Group, ethoxypropoxybutylthio group, propoxypropoxybutylthio group, butoxypropoxybutylthio group, methoxybutoxybutylthio group , Ethoxy butoxy butyl thio group, propoxy butoxy butyl thio group, butoxy butoxy butyl thio group, (4 Echirushikuro hexyloxy) ethoxyethyl thio group, (2-ethyl-1-hexyloxy) ethoxy propyl thio group,
A linear, branched or cyclic C3-15 alkylthio group substituted with an alkoxyalkoxy group such as [4- (3,5,5-trimethylhexyloxy) butoxy] ethylthio group;

C3-C3 substituted with an alkoxycarbonyl group such as methoxycarbonylmethylthio group, ethoxycarbonylmethylthio group, n-propoxycarbonylmethylthio group, isopropoxycarbonylmethylthio group and (4'-ethylcyclohexyloxy) carbonylmethylthio group. 10 alkylthio groups;

C3-10 substituted with an acyl group such as acetylmethylthio group, ethylcarbonylmethylthio group, octylcarbonylmethylthio group, phenacylthio group.
An alkylthio group of

An alkylthio group having 3 to 10 carbon atoms substituted with an acylthio group such as acetyloxymethylthio group, acetyloxyethylthio group, acetyloxyhexylthio group, butanoyloxycyclohexylthio group;

Methylaminomethylthio group, 2-methylaminoethylthio group, 2- (2-methylaminoethoxy) ethylthio group, 4-methylaminobutylthio group, 1-methylaminopropan-2-ylthio group, 3-methyl Aminopropylthio group, 2-methylamino-2-methylpropylthio group, 2-ethylaminoethylthio group, 2- (2-
Ethylaminoethoxy) ethylthio group, 3-ethylaminopropylthio group, 1-ethylaminopropylthio group,
2-isopropylaminoethylthio group, 2- (n-butylamino) ethylthio group, 3- (n-hexylamino)
2 to 1 carbon atoms substituted with an alkylamino group such as propylthio group and 4- (cyclohexylamino) butylthio group
An alkylthio group of 0;

Substituted with an alkylaminoalkylthio group such as methylaminomethoxymethylthio group, methylaminoethoxyethylthio group, methylaminoethoxypropylthio group, ethylaminoethoxypropylthio group, 4- (2'-isobutylaminopropoxy) butylthio group. An alkylthio group having 3 to 10 carbon atoms;

Dimethylaminomethylthio group, 2-dimethylaminoethylthio group, 2- (2-dimethylaminoethoxy) ethylthio group, 4-dimethylaminobutylthio group, 1-dimethylaminopropan-2-ylthio group, 3
-Dimethylaminopropylthio group, 2-dimethylamino-2-methylpropylthio group, 2-diethylaminoethylthio group, 2- (2-diethylaminoethoxy) ethylthio group, 3-diethylaminopropylthio group, 1-diethylaminopropylthio group , 2-diisopropylaminoethylthio group, 2- (di-n-butylamino) ethylthio group, 2-piperidylethylthio group, 3- (di-n-hexylamino) propylthio group and the like. An alkylthio group having 3 to 15 carbon atoms;

Substitution with an alkylthio group of dialkylami such as dimethylaminomethoxymethylthio group, dimethylaminoethoxyethylthio group, dimethylaminoethoxypropylthio group, diethylaminoethoxypropylthio group, 4- (2'-diisobutylaminopropoxy) butylthio group. An alkylthio group having 4 to 15 carbon atoms;

Methylthiomethylthio group, 2-methylthioethylthio group, 2-ethylthioethylthio group, 2-n-
An alkylthio group such as propylthioethylthio group, 2-isopropylthioethylthio group, 2-n-butylthioethylthio group, 2-isobutylthioethylthio group, (3,5,5-trimethylhexylthio) hexylthio group A substituted alkylthio group having 2 to 15 carbon atoms;

And the like, preferably, methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group. Group, iso-pentylthio group, neopentylthio group, 2-methylbutylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, 3,5,5-trimethylhexylthio group , A decalylthio group, a methoxyethylthio group, an ethoxyethylthio group, a methoxyethoxyethylthio group, an ethoxyethoxyethylthio group, an n-decylthio group and the like, and an alkylthio group having 1 to 10 carbon atoms.

Examples of the substituted or unsubstituted aralkylthio group represented by R ^{1 to} R ¹⁶ include an aralkylthio group which may have the same substituent as the above-mentioned alkyl group, and preferably a benzylthio group. , Nitrobenzylthio group, cyanobenzylthio group, hydroxybenzylthio group, methylbenzylthio group, trifluoromethylbenzylthio group,
Naphthylmethylthio group, nitronaphthylmethylthio group,
Examples thereof include aralkylthio groups having 7 to 15 carbon atoms such as cyanonaphthylmethylthio group, hydroxynaphthylmethylthio group, methylnaphthylmethylthio group, trifluoromethylnaphthylmethylthio group, and fluoren-9-ylethylthio group.

Examples of the substituted or unsubstituted arylthio group represented by R ^{1 to} R ¹⁶ include arylthio groups which may have the same substituents as the above-mentioned alkyl groups, preferably a phenylthio group and 2 -Methylphenylthio group, 4-
Methylphenylthio group, 4-t-butylphenylthio group, 2-methoxyphenylthio group, 4-iso-propylphenylthio group, tolylthio group, naphthylthio group, ferrocenylthio group, cobaltcenylthio group, nickelocenylthio group, An arylthio group having 6 to 18 carbon atoms such as an octamethylferrocenylthio group, an octamethylcobaltcenylthio group and an octamethylnickerocenylthio group can be mentioned.

Further, the substituted or unsubstituted heteroarylthio of R ^{1 to} R ¹⁶ which is an arylthio group having an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom between carbon atoms. Examples of the group include a heteroarylthio group in which the heteroaryl group described above is bonded to an oxygen atom.

Examples of the substituted or unsubstituted alkenylthio group for R ^{1 to} R ¹⁶ are alkenylthio groups which may have the same substituents as the above-mentioned alkyl groups, and preferably a vinylthio group. , Propenylthio group, 1-butenylthio group, iso-butenylthio group, 1-pentenylthio group, 2-pentenylthio group, 2-methyl-1-butenylthio group, 3-methyl-1-butenylthio group, 2-methyl-2 -Butenylthio group, cyclopentadienylthio group, 2,2-dicyanovinylthio group, 2-cyano-2-
Examples thereof include alkenylthio groups having 2 to 10 carbon atoms such as methylcarboxylvinylthio group, 2-cyano-2-methylsulfone vinylthio group, styrylthio group, 4-phenyl-2-butenylthio group and cinnamylalkoxy group.

Examples of the substituted hydrocarbon thio group represented by R ^{1 to} R ¹⁶ include a hydrocarbon thio group in which a carbon atom directly bonded to a sulfur atom directly bonded to an azaannulene ring is substituted with an oxo group. Specific examples thereof include substituted or unsubstituted acylthio groups; substituted or unsubstituted hydrocarbon oxycarbonylthio groups such as alkoxycarbonylthio groups, aralkyloxycarbonylthio groups, aryloxycarbonylthio groups, alkenyloxycarbonylthio groups; mono; Substituted or unsubstituted hydrocarbon aminocarbonylthio groups such as a substituted aminocarbonylthio group and a disubstituted aminocarbonylthio group may be mentioned.

Examples of the substituted or unsubstituted acylthio groups represented by R ^{1 to} R ¹⁶ include acylthio groups which may have the same substituents as the above-mentioned alkyl groups, and preferably,
Formylthio group, methylcarbonylthio group, ethylcarbonylthio group, n-propylcarbonylthio group, iso
-Propylcarbonylthio group, n-butylcarbonylthio group, iso-butylcarbonylthio group, sec-butylcarbonylthio group, t-butylcarbonylthio group, n
-Pentylcarbonylthio group, iso-pentylcarbonylthio group, neopentylcarbonylthio group, 2-methylbutylcarbonylthio group, benzoylthio group, methylbenzoylthio group, ethylbenzoylthio group, tolylcarbonylthio group, propylbenzoylthio group , 4-t-
1 to 1 carbon atoms such as butylbenzoylthio group, nitrobenzylcarbonylthio group, 3-butoxy-2-naphthoylthio group, cinnamoylthio group, ferrocenecarbonylthio group, 1-methylferrocene-1′-carbonylthio group
There may be mentioned 15 acylthio groups.

Examples of the substituted or unsubstituted alkoxycarbonylthio group for R ^{1 to} R ¹⁶ are alkoxycarbonylthio groups which may have the same substituents as the above-mentioned alkyl groups, and are preferably methoxy. Carbonylthio group, ethoxycarbonylthio group, n-propoxycarbonylthio group, iso-propoxycarbonylthio group, n
-Butoxycarbonylthio group, iso-butoxycarbonylthio group, sec-butoxycarbonylthio group, t-
Butoxycarbonylthio group, n-pentoxycarbonylthio group, iso-pentoxycarbonylthio group, neopentoxycarbonylthio group, 2-pentoxycarbonylthio group, 2-ethylhexyloxycarbonylthio group,
Carbon number 2-11 such as 3,5,5-trimethylhexyloxycarbonylthio group, decalyloxycarbonylthio group, cyclohexyloxycarbonylthio group, chloroethoxycarbonylthio group, hydroxymethoxycarbonylthio group, hydroxyethoxycarbonylthio group An alkoxycarbonylthio group of:

Methoxymethoxycarbonylthio group, methoxyethoxycarbonylthio group, ethoxyethoxycarbonylthio group, propoxyethoxycarbonylthio group,
Alkylthio such as butoxyethoxycarbonylthio group, pentoxyethoxycarbonylthio group, hexyloxyethoxycarbonylthio group, butoxybutoxycarbonylthio group, hexyloxybutoxycarbonylthio group, hydroxymethoxymethoxycarbonylthio group, hydroxyethoxyethoxycarbonylthio group, etc. An alkoxycarbonylthio group having 3 to 11 carbon atoms in which a group is substituted;

Methoxymethoxymethoxycarbonylthio group, methoxyethoxyethoxycarbonylthio group, ethoxyethoxyethoxycarbonylthio group, propoxyethoxyethoxycarbonylthio group, butoxyethoxyethoxycarbonylthio group, pentoxyethoxyethoxycarbonylthio group, hexyloxyethoxyethoxy. A carbonylthio group, or an alkoxycarbonylthio group having 4 to 11 carbon atoms substituted with an alkoxyalkoxy group;

A ferrocenylmethoxycarbonylthio group,
Ferrocenylethoxycarbonylthio group, ferrocenylpropoxycarbonylthio group, ferrocenylbutoxycarbonylthio group, ferrocenylpentyloxycarbonylthio group, ferrocenylhexyloxycarbonylthio group, ferrocenylheptyloxycarbonylthio group, Ferrocenyloctyloxycarbonylthio group, ferrocenylnonyloxycarbonylthio group, ferrocenyldecyloxycarbonylthio group,

Cobalt cenyl methoxycarbonylthio group, cobalt cenyl ethoxycarbonylthio group, cobalt cenyl propoxycarbonylthio group, cobalt cenyl butoxycarbonylthio group, cobalt cenyl pentyloxycarbonylthio group, cobalt cenylhexyloxycarbonylthio group. Group, cobaltcenylheptyloxycarbonylthio group, cobaltcenyloctyloxycarbonylthio group, cobaltcenylnonyloxycarbonylthio group, cobaltcenyldecyloxycarbonylthio group,

Nickelocenylmethoxycarbonylthio group, nickelocenylethoxycarbonylthio group, nickelocenylpropoxycarbonylthio group, nickelocenylbutoxycarbonylthio group, nickelocenylpentyloxycarbonylthio group, nickelocenylhexyloxycarbonyl group. Thio group, nickelocenylheptyloxycarbonylthio group, nickelocenyloctyloxycarbonylthio group, nickelocenylnonyloxycarbonylthio group, nickelocenyldecyloxycarbonylthio group,

Dichlorotitanocenylmethoxycarbonylthio group, trichlorotitanium cyclopentadienylmethoxycarbonylthio group, bis (trifluoromethanesulfonato) titanocene methoxycarbonylthio group, dichlorozirconocenylmethoxycarbonylthio group, dimethylzirconocenylmethoxy group Carbonylthio group, diethoxyzirconocenylmethoxycarbonylthio group, bis (cyclopentadienyl) chromium methoxycarbonylthio group, bis (cyclopentadienyl) dichlorohafnium methoxycarbonylthio group, bis (cyclopentadienyl) dichloroniobium Methoxycarbonylthio group, bis (cyclopentadienyl) ruthenium methoxycarbonylthio group, bis (cyclopentadienyl) vanadium methoxycarbonylthio group, Scan (cyclopentadienyl) dichloro vanadium methoxycarbonyl-thio group, bis alkoxycarbonyl thio group (cyclopentadienyl) carbon atoms substituted with metallocenyl group such as osmium methoxycarbonyl thio 11-20; and the like.

Examples of the substituted or unsubstituted aralkyloxycarbonylthio group represented by R ^{1 to} R ¹⁶ are aralkyloxycarbonylthio groups which may have the same substituents as the above-mentioned alkyl groups, and are preferable. Is a benzyloxycarbonylthio group, a nitrobenzyloxycarbonylthio group, a cyanobenzyloxycarbonylthio group, a hydroxybenzyloxycarbonylthio group, a methylbenzyloxycarbonylthio group, a trifluoromethylbenzyloxycarbonylthio group, a naphthylmethoxycarbonylthio group. , Nitronaphthylmethoxycarbonylthio group, cyanonaphthylmethoxycarbonylthio group, hydroxynaphthylmethoxycarbonylthio group, methylnaphthylmethoxycarbonylthio group, trifluoromethylnaphthylmethoxycarbo group Thio group, or the like aralkyloxycarbonyl thio group having 8 to 16 carbon atoms such as fluoren-9-yl ethoxycarbonyl thio group.

Examples of the substituted or unsubstituted aryloxycarbonylthio group represented by R ^{1 to} R ¹⁶ include aryloxycarbonylthio groups which may have the same substituents as the above-mentioned aryl groups, and are preferable. Is a phenoxycarbonylthio group, a 2-methylphenoxycarbonylthio group, a 4-methylphenoxycarbonylthio group, a 4-t-
Butylphenoxycarbonylthio group, 2-methoxyphenoxycarbonylthio group, 4-iso-propylphenoxycarbonylthio group, naphthoxycarbonylthio group,
Ferrocenyloxycarbonylthio group, cobaltcenyloxycarbonylthio group, nickelocenyloxycarbonylthio group, zirconocenyloxycarbonylthio group,
Aryloxycarbonyl having 7 to 11 carbon atoms such as octamethylferrocenyloxycarbonylthio group, octamethylcobaltcenyloxycarbonylthio group, octamethylnickerocenyloxycarbonylthio group, octamethylzirconocenyloxycarbonylthio group A thio group is mentioned.

Examples of the substituted or unsubstituted alkenyloxycarbonylthio group for R ^{1 to} R ¹⁶ are alkenyloxycarbonylthio groups which may have the same substituents as the above-mentioned alkyl groups, and are preferable. Is a vinyloxycarbonylthio group, propenyloxycarbonylthio group, 1-butenyloxycarbonylthio group, iso-butenyloxycarbonylthio group, 1-pentenyloxycarbonylthio group, 2-pentenyloxycarbonylthio group, cyclopenta A dienyloxycarbonylthio group,
2-methyl-1-butenyloxycarbonylthio group, 3
-Methyl-1-butenyloxycarbonylthio group, 2-
Methyl-2-butenyloxycarbonylthio group, 2,2
-Dicyanovinyloxycarbonylthio group, 2-cyano-2-methylcarboxylvinyloxycarbonylthio group, 2-cyano-2-methylsulfone vinyloxycarbonylthio group, styryloxycarbonylthio group, 4-
Examples thereof include alkenyloxycarbonylthio groups having 3 to 11 carbon atoms such as phenyl-2-butenyloxycarbonylthio group.

Examples of the mono-substituted aminocarbonylthio group represented by R ^{1 to} R ¹⁶ include mono-substituted aminocarbonylthio groups which may have the same substituents as the above-mentioned alkyl groups, preferably methyl. Aminocarbonylthio group, ethylaminocarbonylthio group, propylaminocarbonylthio group, butylaminocarbonylthio group, pentylaminocarbonylthio group, hexylaminocarbonylthio group, heptylaminocarbonylthio group, octylaminocarbonylthio group, (2- C2-C11 monoalkylamino such as ethylhexyl) aminocarbonylthio group, cyclohexylaminocarbonylthio group, (3,5,5-trimethylhexyl) aminocarbonylthio group, nonylaminocarbonylthio group, and decylaminocarbonylthio group. Carboni Thio;

Benzylaminocarbonylthio group, phenethylaminocarbonylthio group, (3-phenylpropylaminocarbonylthio group, (4-ethylbenzyl) aminocarbonylthio group, (4-isopropylbenzyl) aminocarbonylthio group, (4- Methylbenzyl) aminocarbonylthio group, (4-ethylbenzyl) aminocarbonylthio group, (4-allylbenzyl) aminocarbonylthio group, [4- (2-cyanoethyl) benzyl] aminocarbonylthio group, [4- (2 -Acetoxyethyl)
Benzyl] aminocarbonylthio group or the like having 8 to 1 carbon atoms
A monoaralkylaminocarbonylthio group of 1;

Anilinocarbonylthio group, naphthylaminocarbonylthio group, toluidinocarbonylthio group, xylidinocarbonylthio group, ethylanilinocarbonylthio group, isopropylanilinocarbonylthio group, methoxyanilinocarbonylthio group, ethoxy Anilinocarbonylthio group, chloroanilinocarbonylthio group, acetylanilinocarbonylthio group, methoxycarbonylanilinocarbonylthio group, ethoxycarbonylanilinocarbonylthio group, propoxycarbonylanilinocarbonylthio group, 4-methylanilinocarbonyl Thio group,
4-ethylanilinocarbonylthio group, etc., 7 carbon atoms
11 monoarylaminocarbonylthio groups;

Vinylaminocarbonylthio group, allylaminocarbonylthio group, butenylaminocarbonylthio group, pentenylaminocarbonylthio group, hexenylaminocarbonylthio group, cyclohexenylaminocarbonylthio group, octadienylaminocarbonylthio group,
3 carbon atoms such as adamantenyl aminocarbonylthio group
To 11 monoalkenylaminocarbonylthio groups and the like.

Examples of the di-substituted aminocarbonylthio group represented by R ^{1 to} R ¹⁶ include a di-substituted aminocarbonylthio group which may have the same substituents as the above-mentioned alkyl groups, preferably dimethyl. Aminocarbonylthio group, diethylaminocarbonylthio group, methylethylaminocarbonylthio group, dipropylaminocarbonylthio group,
Dibutylaminocarbonylthio group, di-n-hexylaminocarbonylthio group, dicyclohexylaminocarbonylthio group, dioctylaminocarbonylthio group, pyrrolidinocarbonylthio group, piperidinocarbonylthio group, morpholinocarbonylthio group, bis (methoxyethyl ) Aminocarbonylthio group, bis (ethoxyethyl)
Aminocarbonylthio group, bis (propoxyethyl) aminocarbonylthio group, bis (butoxyethyl) aminocarbonylthio group, di (acetyloxyethyl) aminocarbonylthio group, di (hydroxyethyl) aminocarbonylthio group, N-ethyl- N- (2-cyanoethyl)
A dialkylaminocarbonylthio group having 3 to 17 carbon atoms such as aminocarbonylthio group and di (propionyloxyethyl) aminocarbonylthio group;

1 carbon atom such as dibenzylaminocarbonylthio group, diphenethylaminocarbonylthio group, bis (4-ethylbenzyl) aminocarbonylthio group, bis (4-isopropylbenzyl) aminocarbonylthio group
5 to 21 diaralkylaminocarbonylthio groups;

A diarylaminocarbonylthio group having 13 to 15 carbon atoms such as a diphenylaminocarbonylthio group, a ditolylaminocarbonylthio group and an N-phenyl-N-tolylaminocarbonylthio group;

Carbon such as divinylaminocarbonylthio group, diallylaminocarbonylthio group, dibutenylaminocarbonylthio group, dipentenylaminocarbonylthio group, dihexenylaminocarbonylthio group and N-vinyl-N-allylaminocarbonylthio group. A dialkenylaminocarbonylthio group of the number 5 to 13;

N-phenyl-N-allylaminocarbonylthio group, N- (2-acetyloxyethyl) -N-ethylaminocarbonylthio group, N-tolyl-N-methylaminocarbonylthio group, N-vinyl-N A substituted or unsubstituted alkyl group such as -methylaminocarbonylthio group, N-benzyl-N-allylaminocarbonylthio group, or the like, an aralkyl group, an aryl group, or an alkenyl group, having 4 to 11 carbon atoms A di-substituted aminocarbonylthio group may be mentioned.

Specific examples of the substituted or unsubstituted amino group represented by R ^{1 to} R ¹⁶ include an unsubstituted amino group; carbon-
Between carbon atoms, it may have an oxygen atom, a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom,
Examples include mono-substituted amino groups and di-substituted amino groups.

Examples of the mono-substituted amino group represented by R ^{1 to} R ¹⁶ include mono-substituted amino groups which may have the same substituents as the above-mentioned alkyl groups, preferably a methylamino group and an ethyl group. Amino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, tert-butylamino group, sec-butylamino group, n-pentylamino group, isopentylamino group,
tert-pentylamino group, sec-pentylamino group, cyclopentylamino group, n-hexylamino group,
1-methylpentylamino group, 2-methylpentylamino group, 3-methylpentylamino group, 4-methylpentylamino group, 1,1-dimethylbutylamino group, 1,2
-Dimethylbutylamino group, 1,3-dimethylbutylamino group, 2,3-dimethylbutylamino group, 1,1,2
-Trimethylpropylamino group, 1,2,2-trimethylpropylamino group, 1-ethylbutylamino group, 2-
Ethylbutylamino group, 1-ethyl-2-methylpropylamino group, cyclohexylamino group, methylcyclopentylamino group, n-heptylamino group, 1-methylhexylamino group, 2-methylhexylamino group, 3-methylhexylamino group Group, 4-methylhexylamino group,
5-methylhexylamino group, 1,1-dimethylpentylamino group, 1,2-dimethylpentylamino group, 1,
3-dimethylpentylamino group, 1,4-dimethylpentylamino group, 2,2-dimethylpentylamino group,
2,3-dimethylpentylamino group, 2,4-dimethylpentylamino group, 3,3-dimethylpentylamino group, 3,4-dimethylpentylamino group, 1-ethylpentylamino group, 2-ethylpentylamino group, 3-ethylpentylamino group, 1,1,2-trimethylbutylamino group, 1,1,3-trimethylbutylamino group,
1,2,3-trimethylbutylamino group, 1,2,2-
Trimethylbutylamino group, 1,3,3-trimethylbutylamino group, 2,3,3-trimethylbutylamino group, 1-ethyl-1-methylbutylamino group, 1-ethyl-2-methylbutylamino group, 1 -Ethyl-3-methylbutylamino group, 2-ethyl-1-methylbutylamino group, 2-ethyl-3-methylbutylamino group, 1-n
-Propylbutylamino group, 1-isopropylbutylamino group, 1-isopropyl-2-methylpropylamino group, methylcyclohexylamino group, n-octylamino group, 1-methylheptylamino group, 2-methylheptylamino group, 3 -Methylheptylamino group, 4-methylheptylamino group, 5-methylheptylamino group, 6-
Methylheptylamino group, 1,1-dimethylhexylamino group, 1,2-dimethylhexylamino group, 1,3-
Dimethylhexylamino group, 1,4-dimethylhexylamino group, 1,5-dimethylhexylamino group, 2,2
-Dimethylhexylamino group, 2,3-dimethylhexylamino group, 2,4-dimethylhexylamino group, 2,
5-dimethylhexylamino group, 3,3-dimethylhexylamino group, 3,4-dimethylhexylamino group,
3,5-dimethylhexylamino group, 4,4-dimethylhexylamino group, 4,5-dimethylhexylamino group, 1-ethylhexylamino group, 2-ethylhexylamino group, 3-ethylhexylamino group, 4-ethylhexylamino group , 1-n-propylpentylamino group,
2-n-propylpentylamino group, 1-isopropylpentylamino group, 2-isopropylpentylamino group, 1-ethyl-1-methylpentylamino group, 1-ethyl-2-methylpentylamino group, 1-ethyl-3 −
Methylpentylamino group, 1-ethyl-4-methylpentylamino group, 2-ethyl-1-methylpentylamino group, 2-ethyl-2-methylpentylamino group, 2-ethyl-3-methylpentylamino group, 2 -Ethyl-4-
Methylpentylamino group, 3-ethyl-1-methylpentylamino group, 3-ethyl-2-methylpentylamino group, 3-ethyl-3-methylpentylamino group, 3-ethyl-4-methylpentylamino group, 1 , 1,2-Trimethylpentylamino group, 1,1,3-trimethylpentylamino group, 1,1,4-trimethylpentylamino group, 1,2,2-trimethylpentylamino group, 1,
2,3-trimethylpentylamino group, 1,2,4-trimethylpentylamino group, 1,3,4-trimethylpentylamino group, 2,2,3-trimethylpentylamino group, 2,2,4-trimethylpentyl group Amino group, 2,
3,4-trimethylpentylamino group, 1,3,3-trimethylpentylamino group, 2,3,3-trimethylpentylamino group, 3,3,4-trimethylpentylamino group, 1,4,4-trimethylpentyl group Amino group, 2,
4,4-trimethylpentylamino group, 3,4,4-trimethylpentylamino group, 1-n-butylbutylamino group, 1-isobutylbutylamino group, 1-sec-butylbutylamino group, 1-tert-butyl Butylamino group, 2-tert-butylbutylamino group, 1-n-
Propyl-1-methylbutylamino group, 1-n-propyl-2-methylbutylamino group, 1-n-propyl-3
-Methylbutylamino group, 1-isopropyl-1-methylbutylamino group, 1-isopropyl-2-methylbutylamino group, 1-isopropyl-3-methylbutylamino group, 1,1-diethylbutylamino group, 1, 2-diethylbutylamino group, 1-ethyl-1,2-dimethylbutylamino group, 1-ethyl-1,3-dimethylbutylamino group, 1-ethyl-2,3-dimethylbutylamino group, 2-ethyl- 1,1-dimethylbutylamino group, 2
-Ethyl-1,2-dimethylbutylamino group, 2-ethyl-1,3-dimethylbutylamino group, 2-ethyl-
2,3-dimethylbutylamino group, 1,1,3,3-tetramethylbutylamino group, 1,2-dimethylcyclohexylamino group, 1,3-dimethylcyclohexylamino group, 1,4-dimethylcyclohexylamino group, Ethylcyclohexylamino group, n-nonylamino group, 3,
A straight chain having 1 to 15 carbon atoms such as 5,5-trimethylhexylamino group, n-decylamino group, n-undecylamino group, n-dodecylamino group, 1-adamantylamino group, and n-pentadecylamino group, A branched or cyclic unsubstituted monoalkylamino group;

Methoxymethylamino group, methoxyethylamino group, ethoxyethylamino group, n-propoxyethylamino group, isopropoxyethylamino group, n-butoxyethylamino group, isobutoxyethylamino group,
tert-butoxyethylamino group, sec-butoxyethylamino group, n-pentyloxyethylamino group,
Isopentyloxyethylamino group, tert-pentyloxyethylamino group, sec-pentyloxyethylamino group, cyclopentyloxyethylamino group, n
-Hexyloxyethylamino group, ethylcyclohexyloxyethylamino group, n-nonyloxyethylamino group, (3,5,5-trimethylhexyloxy) ethylamino group, (3,5,5-trimethylhexyloxy) butylamino Group, n-decyloxyethylamino group, n-undecyloxyethylamino group, n-dodecyloxyethylamino group, 3-methoxypropylamino group, 3-ethoxypropylamino group, 3- (n-propoxy) propylamino Group, 2-isopropoxypropylamino group, 2-methoxybutylamino group, 2-ethoxybutylamino group, 2- (n-propoxy) butylamino group, 4-isopropoxybutylamino group, decalyloxyethylamino group, With an alkoxy group such as adamantyloxyethylamino group Conversion mono-alkylamino group having from 2 to 15 carbon atoms;

Methoxymethoxymethylamino group, ethoxymethoxymethylamino group, propoxymethoxymethylamino group, butoxymethoxymethylamino group, methoxyethoxymethylamino group, ethoxyethoxymethylamino group, propoxyethoxymethylamino group, butoxyethoxymethylamino group. , Methoxypropoxymethylamino group, ethoxypropoxymethylamino group, propoxypropoxymethylamino group, butoxypropoxymethylamino group, methoxybutoxymethylamino group, ethoxybutoxymethylamino group, propoxybutoxymethylamino group, butoxybutoxymethylamino group, methoxy Methoxyethylamino group, ethoxymethoxyethylamino group, propoxymethoxyethylamino group, butoxymethoxyethylamino group , Methoxyethoxyethylamino group, ethoxyethoxyethylamino group, propoxyethoxyethylamino group, butoxyethoxyethylamino group, methoxypropoxyethylamino group, ethoxypropoxyethylamino group, propoxypropoxyethylamino group, butoxypropoxyethylamino group, methoxy Butoxyethylamino group, ethoxybutoxyethylamino group, propoxybutoxyethylamino group, butoxybutoxyethylamino group, methoxymethoxypropylamino group, ethoxymethoxypropylamino group, propoxymethoxypropylamino group, butoxymethoxypropylamino group, methoxyethoxypropyl Amino group, ethoxyethoxypropylamino group, propoxyethoxypropylamino group, butoxyethoxypropy Amino group, methoxypropoxypropylamino group, ethoxypropoxypropylamino group, propoxypropoxypropylamino group, butoxypropoxypropylamino group, methoxybutoxypropylamino group, ethoxybutoxypropylamino group, propoxybutoxypropylamino group, butoxybutoxypropylamino group , Methoxymethoxybutylamino group, ethoxymethoxybutylamino group, propoxymethoxybutylamino group, butoxymethoxybutylamino group, methoxyethoxybutylamino group, ethoxyethoxybutylamino group, propoxyoxyethoxybutylamino group, butoxyethoxybutoxy-go, methoxy Propoxybutylamino group, ethoxypropoxybutylamino group, propoxypropoxybutylamino group, butoxyp Ropoxybutylamino group, methoxybutoxybutylamino group, ethoxybutoxybutylamino group, propoxybutoxybutylamino group, butoxybutoxybutylamino group, (4-ethylcyclohexyloxy) ethoxyethylamino group, (2-ethyl-1-to Xyloxy)
A linear, branched or cyclic C3-C15 monoalkylamino substituted with an alkoxyalkoxy group such as an ethoxypropylamino group and a [4- (3,5,5-trimethylhexyloxy) butoxy] ethylamino group. Group;

Substituted with an alkoxycarbonyl group such as methoxycarbonylmethylamino group, ethoxycarbonylmethylamino group, n-propoxycarbonylmethylamino group, isopropoxycarbonylmethylamino group, (4′-ethylcyclohexyloxy) carbonylmethylamino group. A monoalkylamino group having 3 to 10 carbon atoms;

A monoalkylamino group having 3 to 10 carbon atoms substituted with an acyl group such as an acetylmethylamino group, an ethylcarbonylmethylamino group, an octylcarbonylmethylamino group and a phenacylamino group;

A monoalkylamino group having 3 to 10 carbon atoms substituted with an acylamino group such as an acetyloxymethylamino group, an acetyloxyethylamino group, an acetyloxyhexylamino group and a butanoyloxycyclohexylamino group;

Methylaminomethylamino group, 2-methylaminoethylamino group, 2- (2-methylaminoethoxy) ethylamino group, 4-methylaminobutylamino group, 1-methylaminopropan-2-ylamino group, 3
-Methylaminopropylamino group, 2-methylamino-
2-methylpropylamino group, 2-ethylaminoethylamino group, 2- (2-ethylaminoethoxy) ethylamino group, 3-ethylaminopropylamino group, 1-ethylaminopropylamino group, 2-isopropylaminoethylamino Group, 2- (n-butylamino) ethylamino group, 3- (n-hexylamino) propylamino group, 4
A monoalkylamino group having 2 to 10 carbon atoms substituted with a monoalkylamino group such as a-(cyclohexylamino) butylamino group;

Methylaminomethoxymethylamino group, methylaminoethoxyethylamino group, methylaminoethoxypropylamino group, ethylaminoethoxypropylamino group, 4- (2'-isobutylaminopropoxy)
A monoalkylamino group having 3 to 10 carbon atoms substituted with an alkylaminomonoalkylamino group such as a butylamino group;

Dimethylaminomethylamino group, 2-dimethylaminoethylamino group, 2- (2-dimethylaminoethoxy) ethylamino group, 4-dimethylaminobutylamino group, 1-dimethylaminopropan-2-ylamino group, 3 -Dimethylaminopropylamino group, 2-dimethylamino-2-methylpropylamino group, 2-diethylaminoethylamino group, 2- (2-diethylaminoethoxy) ethylamino group, 3-diethylaminopropylamino group, 1-diethylaminopropylamino group Base, 2-
Diisopropylaminoethylamino group, 2- (di-n-
A butylamino) ethylamino group, a 2-piperidylethylamino group, a 3- (di-n-hexylamino) propylamino group, or another dimonoalkylamino group-substituted monoalkylamino group having 3 to 15 carbon atoms;

A dimethylaminomethoxymethylamino group,
4 to 4 carbon atoms substituted with monoalkylamino group of dialkylami such as dimethylaminoethoxyethylamino group, dimethylaminoethoxypropylamino group, diethylaminoethoxypropylamino group, 4- (2'-diisobutylaminopropoxy) butylamino group 15 monoalkylamino groups;

Methylthiomethylamino group, 2-methylthioethylamino group, 2-ethylthioethylamino group, 2
-N-propylthioethylamino group, 2-isopropylthioethylamino group, 2-n-butylthioethylamino group, 2-isobutylthioethylamino group, (3, 5, 5
-Trimethylhexylthio) hexylamino group or other monoalkylamino group-substituted monoalkylamino group having 2 to 15 carbon atoms;

Monoalkylamino groups such as, more preferably, methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, n-butylamino group, iso-butylamino group, sec-butylamino group. Group, t-butylamino group, n-pentylamino group, is
o-pentylamino group, neopentylamino group, 2-methylbutylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group, 3,5,5-trimethylhexyl A monoalkylamino group having 1 to 10 carbon atoms such as an amino group, a decalylamino group, a methoxyethylamino group, an ethoxyethylamino group, a methoxyethoxyethylamino group, an ethoxyethoxyethylamino group, and an n-decylamino group;

Benzylamino group, phenethylamino group,
(3-Phenylpropyl) amino group, (4-ethylbenzyl) amino group, (4-isopropylbenzyl) amino group, (4-methylbenzyl) amino group, (4-ethylbenzyl) amino group, (4-allylbenzyl) ) An amino group,
[4- (2-cyanoethyl) benzyl] amino group, [4
A monoaralkylamino group having 7 to 10 carbon atoms such as-(2-acetoxyethyl) benzyl] amino group;

Anilino group, naphthylamino group, toluidino group, xylidino group, ethylanilino group, isopropylanilino group, methoxyanilino group, ethoxyanilino group, chloroanilino group, acetylanilino group, methoxycarbonylanilino group, ethoxycarbonyl. Anilino group, propoxycarbonylanilino group, 4-methylanilino group, 4-ethylanilino group, ferrocenylamino group, cobaltcenylamino group, nickelocenylamino group, zirconocenylamino group, octamethylferrocenylamino group Group, octamethylcobaltcenylamino group, octamethylnickerocenylamino group, octamethylzirconocenylamino group and the like, a monoarylamino group having 6 to 10 carbon atoms;

A carbon number of 2 to 10 such as vinylamino group, allylamino group, butenylamino group, pentenylamino group, hexenylamino group, cyclohexenylamino group, cyclopentadienylamino group, octadienylamino group and adamantenylamino group. A monoalkenylamino group of:

Formylamino group, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group,
n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t
-Butylcarbonylamino group, n-pentylcarbonylamino group, iso-pentylcarbonylamino group, neopentylcarbonylamino group, 2-methylbutylcarbonylamino group, benzoylamino group, methylbenzoylamino group, ethylbenzoylamino group, tolylcarbonyl Amino group, propylbenzoylamino group, 4-t-butylbenzoylamino group, nitrobenzylcarbonylamino group, 3-butoxy-2-naphthoylamino group, cinnamoylamino group, ferrocenecarbonylamino group, 1
And mono-substituted amino groups such as an acylamino group having 1 to 16 carbon atoms such as -methylferrocene-1'-carbonylamino group, cobaltocenecarbonylamino group and nickelocenecarbonylamino group.

Examples of the di-substituted amino group of R ^{1 to} R ¹⁶ are di-substituted amino groups which may have the same substituents as the above-mentioned alkyl groups, preferably dimethylamino group and diethylamino group. Group, di (n-propyl) amino group, di (isopropyl) amino group, di (n-butyl) amino group, di (isobutyl) amino group, di (tert-butyl) amino group, di (sec-butyl) amino group Group, di (n-pentyl) amino group, di (isopentyl) amino group, di (tert-pentyl) amino group, di (sec-
Pentyl) amino group, di (cyclopentyl) amino group,
Di (n-hexyl) amino group, di (1-methylpentyl) amino group, di (2-methylpentyl) amino group, di (3-methylpentyl) amino group, di (4-methylpentyl) amino group, di (1,1-dimethylbutyl) amino group, di (1,2-dimethylbutyl) amino group, di (1,
3-dimethylbutyl) amino group, di (2,3-dimethylbutyl) amino group, di (1,1,2-trimethylpropyl) amino group, di (1,2,2-trimethylpropyl)
Amino group, di (1-ethylbutyl) amino group, di (2-
Ethylbutyl) amino group, di (1-ethyl-2-methylpropyl) amino group, di (cyclohexyl) amino group,
Di (methylcyclopentyl) amino group, di (n-heptyl) amino group, di (1-methylhexyl) amino group, di (2-methylhexyl) amino group, di (3-methylhexyl) amino group, di ( 4-methylhexyl) amino group,
Di (5-methylhexyl) amino group, di (1,1-dimethylpentyl) amino group, di (1,2-dimethylpentyl) amino group, di (1,3-dimethylpentyl) amino group, di (1,1) 4-dimethylpentyl) amino group, di (2,2-dimethylpentyl) amino group, di (2,3-)
Dimethylpentyl) amino group, di (2,4-dimethylpentyl) amino group, di (3,3-dimethylpentyl) amino group, di (3,4-dimethylpentyl) amino group, di (1-ethylpentyl) amino group Group, di (2-ethylpentyl) amino group, di (3-ethylpentyl) amino group,
Di (1,1,2-trimethylbutyl) amino group, di (1,1,3-trimethylbutyl) amino group, di (1,
2,3-trimethylbutyl) amino group, di (1,2,2)
-Trimethylbutyl) amino group, di (1,3,3-trimethylbutyl) amino group, di (2,3,3-trimethylbutyl) amino group, di (1-ethyl-1-methylbutyl) amino group, di ( 1-ethyl-2-methylbutyl) amino group, di (1-ethyl-3-methylbutyl) amino group, di (2-ethyl-1-methylbutyl) amino group, di (2-ethyl-3-methylbutyl) amino group, Di (1-
n-propylbutyl) amino group, di (1-isopropylbutyl) amino group, di (1-isopropyl-2-methylpropyl) amino group, di (methylcyclohexyl) amino group, di (n-octyl) amino group, di (1-Methylheptyl) amino group, di (2-methylheptyl) amino group, di (3-methylheptyl) amino group, di (4-methylheptyl) amino group, di (5-methylheptyl) amino group, di (, 6-methylheptyl) amino group, di (1,
1-dimethylhexyl) amino group, di (1,2-dimethylhexyl) amino group, di (1,3-dimethylhexyl) amino group, di (1,4-dimethylhexyl) amino group, di (1,5- Dimethylhexyl) amino group, di (2,2-dimethylhexyl) amino group, di (2,3-)
Dimethylhexyl) amino group, di (2,4-dimethylhexyl) amino group, di (2,5-dimethylhexyl) amino group, di (3,3-dimethylhexyl) amino group, di (3,4-dimethylhexyl) ) Amino group, di (3,5-
Dimethylhexyl) amino group, di (4,5-dimethylhexyl) amino group, di (4,5-dimethylhexyl) amino group, di (1-ethylhexyl) amino group, di (2-
Ethylhexyl) amino group, di (3-ethylhexyl)
Amino group, di (4-ethylhexyl) amino group, di (1
-N-propylpentyl) amino group, di (2-n-propylpentyl) amino group, di (1-isopropylpentyl) amino group, di (2-isopropylpentyl) amino group, di (1-ethyl-1-methyl) Pentyl) amino group,
Di (1-ethyl-2-methylpentyl) amino group, di (1-ethyl-3-methylpentyl) amino group, di (1
-Ethyl-4-methylpentyl) amino group, di (2-ethyl-1-methylpentyl) amino group, di (2-ethyl-2-methylpentyl) amino group, di (2-ethyl-3)
-Methylpentyl) amino group, di (2-ethyl-4-methylpentyl) amino group, di (3-ethyl-1-methylpentyl) amino group, di (3-ethyl-2-methylpentyl) amino group, di (3-Ethyl-3-methylpentyl) amino group, di (3-ethyl-4-methylpentyl)
Amino group, di (1,1,2-trimethylpentyl) amino group, di (1,1,3-trimethylpentyl) amino group, di (1,1,4-trimethylpentyl) amino group,
Di (1,2,2-trimethylpentyl) amino group, di (1,2,3-trimethylpentyl) amino group, di (1,2,4-trimethylpentyl) amino group, di (1,3,4-) Trimethylpentyl) amino group, di (2,2,3-trimethylpentyl) amino group, di (2,2,4-trimethylpentyl) amino group, di (2,3,4-trimethylpentyl) amino group, di ( 1,3,3-Trimethylpentyl) amino group, di (2,3,3-trimethylpentyl) amino group, di (3,3,4-trimethylpentyl) amino group, di (1,4,4-trimethylpentyl) ) Amino group, di (2,4,4-trimethylpentyl) amino group, di (3,4,4-trimethylpentyl) amino group, di (1
-N-butylbutyl) amino group, di (1-isobutylbutyl) amino group, di (1-sec-butylbutyl) amino group, di (1-tert-butylbutyl) amino group, di (2-tert-butylbutyl) amino group , Di (1-n
-Propyl-1-methylbutyl) amino group, di (1-n
-Propyl-2-methylbutyl) amino group, di (1-n
-Propyl-3-methylbutyl) amino group, di (1-isopropyl-1-methylbutyl) amino group, di (1-isopropyl-2-methylbutyl) amino group, di (1-isopropyl-3-methylbutyl) amino group, di (1, 1
-Diethylbutyl) amino group, di (1,2-diethylbutyl) amino group, di (1-ethyl-1,2-dimethylbutyl) amino group, di (1-ethyl-1,3-dimethylbutyl) amino group , Di (1-ethyl-2,3-dimethylbutyl) amino group, di (2-ethyl-1,1-dimethylbutyl) amino group, di (2-ethyl-1,2-dimethylbutyl) amino group, di (2-Ethyl-1,3-dimethylbutyl) amino group, di (2-ethyl-2,3-dimethylbutyl) amino group, di (1,1,3,3-tetramethylbutyl) amino group, di ( 1,2-dimethylcyclohexyl) amino group, di (1,3-dimethylcyclohexyl)
Amino group, di (1,4-dimethylcyclohexyl) amino group, di (, ethylcyclohexyl) amino group, di (n
-Nonyl) amino group, di (3,5,5-trimethylhexyl) amino group, di (n-decyl) amino group, di (n-
Undecyl) amino group, di (n-dodecyl) amino group,
A linear, branched or cyclic unsubstituted dialkylamino group having 1 to 15 carbon atoms such as a di (1-adamantyl) amino group and a di (n-pentadecyl) amino group;

Di (methoxymethyl) amino group, di (methoxyethyl) amino group, di (ethoxyethyl) amino group, di (n-propoxyethyl) amino group, di (isopropoxyethyl) amino group, di (n-butoxyethyl) )
Amino group, di (isobutoxyethyl) amino group, di (t
ert-butoxyethyl) amino group, di (sec-butoxyethyl) amino group, di (n-pentyloxyethyl) amino group, di (isopentyloxyethyl) amino group, di (tert-pentyloxyethyl) amino group,
Di (sec-pentyloxyethyl) amino group, di (cyclopentyloxyethyl) amino group, di (n-hexyloxyethyl) amino group, di (ethylcyclohexyloxyethyl) amino group, di (n-nonyloxyethyl) amino Group, di [(3,5,5-trimethylhexyloxy) ethyl] amino group, di [(3,5,5-trimethylhexyloxy) butyl] amino group, di (n-decyloxyethyl) amino group, di (N-undecyloxyethyl) amino group, di (n-dodecyloxyethyl) amino group, di (3-methoxypropyl) amino group, di (3
-Ethoxypropyl) amino group, di [3- (n-propoxy) propyl] amino group, di (2-isopropoxypropyl) amino group, di (2-methoxybutyl) amino group, di (2-ethoxybutyl) amino group Group, di [2- (n
-Propoxy) butyl] amino group, di (4-isopropoxybutyl) amino group, di (decalyloxyethyl) amino group, di (adamantyloxyethyl) amino group, and the like, having 2 to 2 carbon atoms substituted with an alkoxy group. 15 dialkylamino groups;

(Methoxymethoxymethyl) amino group, di (ethoxymethoxymethyl) amino group, di (propoxymethoxymethyl) amino group, di (butoxymethoxymethyl) amino group, di (methoxyethoxymethyl) amino group, di (ethoxy) Ethoxymethyl) amino group, di (propoxyethoxymethyl) amino group, di (butoxyethoxymethyl) amino group, di (methoxypropoxymethyl)
Amino group, di (ethoxypropoxymethyl) amino group,
Di (propoxypropoxymethyl) amino group, di (butoxypropoxymethyl) amino group, di (methoxybutoxymethyl) amino group, di (ethoxybutoxymethyl) amino group, di (propoxybutoxymethyl) amino group, di (butoxybutoxymethyl) ) Amino group, di (methoxymethoxyethyl) amino group, di (ethoxymethoxyethyl) amino group, di (propoxymethoxyethyl) amino group, di (butoxymethoxyethyl) amino group, di (methoxyethoxyethyl) amino group, di (Ethoxyethoxyethyl) amino group, di (propoxyethoxyethyl) amino group, di (butoxyethoxyethyl) amino group, di (methoxypropoxyethyl) amino group, di (ethoxypropoxyethyl) amino group, di (propoxypropoxyethyl) Amino group, (Butoxy propoxy ethyl)
Amino group, di (methoxybutoxyethyl) amino group, di (ethoxybutoxyethyl) amino group, di (propoxybutoxyethyl) amino group, di (butoxybutoxyethyl) amino group, di (methoxymethoxypropyl) amino group, di ( Ethoxymethoxypropyl) amino group, di (propoxymethoxypropyl) amino group, di (butoxymethoxypropyl) amino group, di (methoxyethoxypropyl) amino group, di (ethoxyethoxypropyl) amino group, di (propoxyethoxypropyl) amino group Group, di (butoxyethoxypropyl) amino group, di (methoxypropoxypropyl) amino group, di (ethoxypropoxypropyl) amino group, di (propoxypropoxypropyl) amino group, di (butoxypropoxypropyl) amino group, di (meth) Sibutoxypropyl) amino group, di (ethoxybutoxypropyl) amino group, di (propoxybutoxypropyl) amino group, di (butoxybutoxypropyl) amino group, di (methoxymethoxybutyl) amino group, di (ethoxymethoxybutyl) amino Group, di (propoxymethoxybutyl) amino group, di (butoxymethoxybutyl) amino group, di (methoxyethoxybutyl) amino group, di (ethoxyethoxybutyl) amino group, di (propoxyethoxyethoxybutyl) amino group, di ( Butoxy ethoxy butoxy go, methoxy propoxy butyl) amino group, di (ethoxy propoxy butyl) amino group, di (propoxy propoxy butyl) amino group, di (butoxy propoxy butyl) amino group, di (methoxy butoxy butyl) amino group, di ( Ethoxy Tokishibuchiru) amino group, di (propoxy butoxy butyl) amino group, di (butoxy-butoxy-butyl) amino group, di [(4
-Ethylcyclohexyloxy) ethoxyethyl] amino group, di [(2-ethyl-1-hexyloxy) ethoxypropyl] amino group, di {[4- (3,5,5-trimethylhexyloxy) butoxy] ethyl} amino A linear, branched or cyclic C3-15 dialkylamino group substituted with an alkoxyalkoxy group, such as a group;

Di (methoxycarbonylmethyl) amino group, di (ethoxycarbonylmethyl) amino group, di (n
-C3 to C substituted with an alkoxycarbonyl group such as a propoxycarbonylmethyl) amino group, a di (isopropoxycarbonylmethyl) amino group and a di [(4'-ethylcyclohexyloxy) carbonylmethyl] amino group.
10 dialkylamino groups;

Dialkyl having 3 to 10 carbon atoms substituted with an acyl group such as di (acetylmethyl) amino group, di (ethylcarbonylmethyl) amino group, di (octylcarbonylmethyl) amino group, di (phenacyl) amino group. Amino group;

C3 substituted with an acylamino group such as di (acetyloxymethyl) amino group, di (acetyloxyethyl) amino group, di (acetyloxyhexyl) amino group, di (butanoyloxycyclohexyl) amino group A dialkylamino group of 10;

Di (methylaminomethyl) amino group, di (2-methylaminoethyl) amino group, di (2- (2-
Methylaminoethoxy) ethyl) amino group, di (4-methylaminobutyl) amino group, di (1-methylaminopropan-2-yl) amino group, di (3-methylaminopropyl) amino group, di (2- Methylamino-2-methylpropyl) amino group, di (2-ethylaminoethyl) amino group, di (2- (2-ethylaminoethoxy) ethyl) amino group, di (3-ethylaminopropyl) amino group, di (1-ethylaminopropyl) amino group, di (2
-Isopropylaminoethyl) amino group, di (2- (n
-Butylamino) ethyl) amino group, di (3- (n-hexylamino) propyl) amino group, di (4- (cyclohexylamino) butyl) amino group and the like, having 2 to 10 carbon atoms substituted with a dialkylamino group. A dialkylamino group of

Di (methylaminomethoxymethyl) amino group, di (methylaminoethoxyethyl) amino group, di (methylaminoethoxypropyl) amino group, di (ethylaminoethoxypropyl) amino group, di [4- (2 '
-Isobutylaminopropoxy) butyl] amino group-containing alkylaminodialkylamino group-substituted dialkylamino group having 3 to 10 carbon atoms;

Di (dimethylaminomethyl) amino group, di (2-dimethylaminoethyl) amino group, di [2- (2
-Dimethylaminoethoxy) ethyl] amino group, di (4
-Dimethylaminobutyl) amino group, di (1-dimethylaminopropan-2-yl) amino group, di (3-dimethylaminopropyl) amino group, di (2-dimethylamino-2-methylpropyl) amino group, di (2-diethylaminoethyl) amino group, di [2- (2-diethylaminoethoxy) ethyl] amino group, di (3-diethylaminopropyl) amino group, di (1-diethylaminopropyl) amino group, di (2-diisopropylamino) ethyl)
Amino group, di [2- (di-n-butylamino) ethyl]
3 to 15 carbon atoms substituted with a didialkylamino group such as amino group, di (2-piperidylethyl) amino group and di [3- (di-n-hexylamino) propyl] amino group
A dialkylamino group of

Di (dimethylaminomethoxymethyl) amino group, di (dimethylaminoethoxyethyl) amino group,
Di (dimethylaminoethoxypropyl) amino group, di (diethylaminoethoxypropyl) amino group, di (4
A dialkylamino group having 4 to 15 carbon atoms substituted with a dialkylamino group of dialkylami such as-(2'-diisobutylaminopropoxy) butyl) amino group;

Methylthiomethyl) amino group, di (2-methylthioethyl) amino group, di (2-ethylthioethyl) amino group, di (2-n-propylthioethyl) amino group, di (2-isopropylthioethyl) ) Amino group, di (2-n-butylthioethyl) amino group, di (2-isobutylthioethyl) amino group, di [(3,5,5-trimethylhexylthio) hexyl] amino group and other dialkylamino groups A C2-C15 dialkylamino group substituted with;

Dialkylamino groups such as, more preferably, dimethylamino group, diethylamino group, di (n-propyl) amino group, di (iso-propyl) amino group,
Di (n-butyl) amino group, di (iso-butyl) amino group, di (sec-butyl) amino group, di (t-butyl) amino group, di (n-pentyl) amino group, di (is
o-pentyl) amino group, di (neopentyl) amino group, di (2-methylbutyl) amino group, di (n-hexyl) amino group, di (n-heptyl) amino group, di (n-)
Octyl) amino group, di (2-ethylhexyl) amino group, di (3,5,5-trimethylhexyl) amino group,
Di (decalyl) amino group, di (methoxyethyl) amino group, di (ethoxyethyl) amino group, di (methoxyethoxyethyl) amino group, di (ethoxyethoxyethyl)
An amino group, a di (n-decyl) amino group, a dialkylamino group having 1 to 10 carbon atoms such as di;

Dibenzylamino group, diphenethylamino group, bis (4-ethylbenzyl) amino group, bis (4-
14 to 2 carbon atoms such as isopropylbenzyl) amino group
A diaralkylamino group of 0;

Diphenylamino group, ditolylamino group,
A diarylamino group having 12 to 14 carbon atoms such as a dixylylamino group, an N-phenyl-N-tolylamino group, an N-phenyl-N-xylylamino group and a dimesitylamino group;

Divinylamino group, diallylamino group, dibutenylamino group, dipentenylamino group, dihexenylamino group, bis (cyclopentadienyl) amino group,
4 to 12 carbon atoms such as N-vinyl-N-allylamino group
A dialkenylamino group of

Diformylamino group, di (methylcarbonyl) amino group, di (ethylcarbonyl) amino group, di (n-propylcarbonyl) amino group, di (iso-propylcarbonyl) amino group, di (n-butylcarbonyl) ) Amino group, di (iso-butylcarbonyl) amino group, di (sec-butylcarbonyl) amino group, di (t
-Butylcarbonyl) amino group, di (n-pentylcarbonyl) amino group, di (iso-pentylcarbonyl)
Amino group, di (neopentylcarbonyl) amino group, di (2-methylbutylcarbonyl) amino group, di (benzoyl) amino group, di (methylbenzoyl) amino group, di (ethylbenzoyl) amino group, di (tolylcarbonyl) ) Amino group, di (propylbenzoyl) amino group, di (4-t-butylbenzoyl) amino group, di (nitrobenzylcarbonyl) amino group, di (3-butoxy-2-)
Naphthoyl) amino group, di (cinnamoyl) amino group,
A diacylamino group having 2 to 30 carbon atoms such as a succinic acid nitrogen atom;

N-phenyl-N-allylamino group, N-
(2-acetyloxyethyl) -N-ethylamino group,
N-tolyl-N-methylamino group, N-vinyl-N-methylamino group, N-benzyl-N-allylamino group, N
-Methyl-ferrocenylamino group, N-ethyl-cobaltcenylamino group, N-butyl-nickelocenylamino group, N-hexyl-octamethylferrocenylamino group, N-methyl-octamethylcobaltcenyl group C3-C24 di-substituted amino group having a substituent selected from a substituted or unsubstituted alkyl group such as amino group and N-methyl-octamethyl nickelocenylamino group, aralkyl group, aryl group and alkenyl group. Is mentioned.

X in the azaannulene ring skeleton of the general formula (1)
Specific examples of the optionally substituted methine group represented by ^{1 to} X ⁸ include general formulas (5) to (12), respectively.

[0219]

[Chemical 6]

[In the formula, G ^{1 to} G ⁸ represent a hydrogen atom or an arbitrary substituent. ]

Examples include a methine group represented by: Examples of preferred substituents are a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aralkyl group; a substituted or unsubstituted Aryl group; substituted or unsubstituted alkenyl group; acyloxy group and the like.

Further, R ^{1 to} R ¹⁶ of the general formula (1) and the general formulas (5) to (12) which are the substituents on the methine group.
In G ^{1 to} G ⁸ , each of the substituents may be linked via a linking group, and specifically, a ring is formed by aliphatic condensation or aromatic condensation, or the linking group is a hetero atom, or Formation of a heterocycle containing a heteroatom such as a metal complex residue may be mentioned.

As the linking group when R ^{1 to} R ¹⁶ and G ^{1 to} G ⁸ are bonded together to form a ring through adjacent substituents and a linking group, an oxygen atom, a sulfur atom and a nitrogen atom can be used. A group formed by appropriately selecting and combining an atom, a phosphorus atom, a hetero atom such as a metal atom and a metalloid atom, and a carbon atom, and examples of preferable linking groups include -O-, -S-, -C.
(= O)-, or an optionally substituted methylene group,
Examples thereof include a methine group, an ethynylene group, a phenylene group, an amino group, an imino group, a metal atom and a metalloid atom, and a desired ring can be obtained by appropriately combining them to form a connecting chain. Examples of the ring formed by the connecting chain include a linear, planar, or three-dimensional ring. Suitable examples of the connecting chain when forming a ring by the connection and the resulting ring,
_{-CH 2 -CH 2 -CH 2 -CH 2} -, - CH 2 (NO 2) -
_{CH 2 -CH 2 -CH 2 -,} - CH (CH 3) -CH 2 -C
Alicyclic condensed ring with an aliphatic chain such as H ₂ —CH ₂ —, —CH (Cl) —CH ₂ —CH ₂ —;

-CH = CH-CH = CH-, -C (NO
_{2) = CH-CH = CH} -, - C (CH 3) = CH-CH
= CH -, - C (CH 3) = CH-CH = CH -, - C
_{(CH 3) = CH-CH} = C (CH 3) -, - C (OCH
_{3) = CH-CH = C} (OCH 3) -, - C (OCH 2 C
_{H 2 CH (CH 3) -} (OCH 3)) = C (Cl) -C
(Cl) = C (OCH ₂ CH ₂ CH (CH ₃ )-(OC
_{H 3)) -, - C} (OCH 2 CH 2 CH (CH 3) 2) = C
(Cl) -C (Cl) = C (OCH 2 CH 2 CH (C
_{H 3) 2) -, -} CH = C (CH 3) -C (CH 3) = CH
-, -C (Cl) = CH-CH = CH-, -C {OCH
[CH (CH _{3) 2] 2} = CH-CH = CH} -, - C
{OCH [CH (CH _{3) 2] 2} = C (Br) -CH} =
CH -, - C {OCH [CH (CH _{3) 2] 2}} = CH-
C (Br) = CH -, - C {OCH [CH (CH _{3) 2]
2} = CH-CH = C} (Br) -, - C (C 2 H 5) = C
H-CH = CH -, - C (C 2 H 5) = CH-CH = C
_{(C 2 H 5) -,} - CH = C (C 2 H 5) -C (C 2 H 5) =
An aromatic condensed ring with an aliphatic chain such as CH-, -C (Cl) = CH-CH = CH-;

[0225] _{-O-CH 2 -CH 2 -O -} , - O-CH
_{(CH 3) -CH (CH 3} ) -O -, - COO-CH 2 -
_{CH 2 -, - COO-CH} 2 -, - CONH-CH 2 -C
_{H 2 -, - CONH-CH} 2 -, - CON (CH 3) -C
_{H 2 -CH 2 -, - CON} (CH 3) -CH 2 -, - S-C
_{H 2 -CH 2 -S -, -} S-CH (CH 3) -CH (C
_{H 3) -S -, - N} = CH-CH = N -, - CH = NN
A heterocyclic ring formed by an aliphatic chain having a hetero atom in a carbon-carbon atom chain, such as = CH-, or

[0226]

[Chemical 7]

(M 'is Fe, Ru, Co, Ni, Os
Or M "R '₂(M "is Ti, Zr, Hf, Nb, Mo,
V ', R'is CO, F, Cl, Br, I,
R¹~ R ¹⁶An alkyl group having 1 to 10 carbon atoms having the same substituent as
Alkyl group, alkoxy group, aryl group, aryloxy
Group, aralkyl group and aralkyloxy group. ) Table
You ) And other metal complex residues;

And the like heterocycles and the like.

R ^{1 to} R ¹⁶ of the general formula ( ¹ ) and G ¹ of the general formula (5) to the general formula (12) which are substituents on the methine group.
To a substituted or unsubstituted hydrocarbon group represented by G ⁸ and / or a substituted hydroxyl group substituted with a hydrocarbon group, a substituted mercapto group, or a substituted or unsubstituted hydrocarbon group having a carbon-carbon atom in a substituted amino group. Specific examples of the sulfur atom include an unsubstituted sulfur atom such as thia group; a sulfur atom substituted with oxygen such as sulfonyl group and sulfinyl group; and the like.

In the substituted or unsubstituted hydrocarbon groups represented by R ^{1 to} R ¹⁶ of the general formula (1) and G ^{1 to} G ⁸ of the formulas (5) to (12) which are the substituents on the methine group. , And / or a substituted hydroxyl group substituted with a hydrocarbon group, a substituted mercapto group, or a substituted amino group having a carbon atom between carbon atoms in the substituted amino group, or an unsubstituted nitrogen atom such as -N = And a substituted nitrogen atom such as a nitrogen atom; a hydrogen atom or an imino group substituted with the above-mentioned hydrocarbon group;

A divalent to tetravalent metal atom represented by M or 3
~ As the tetravalent semi-metal atom, periodic table IIA to VIIA group, V
Examples thereof include Group III and Group IB to VIIB metal atoms and metalloid atoms.

Specific examples of the divalent metal atom which may have a ligand include Cu, Zn, Fe, Co and N.
i, Ru, Rh, Pd, Pt, Mn, Sn, Mg, P
b, Hg, Cd, Ba, Ti, Be, Ca, Re, Os
A heterocyclic compound such as a divalent non-substituted metal atom or a substituted or non-substituted 5-membered ring nitrogen-containing aromatic compound, a 6-membered ring nitrogen-containing aromatic compound, a condensed ring nitrogen-containing compound, etc.
Examples thereof include divalent metal atoms coordinated with carbon monoxide, alcohol and the like.

Examples of the substituted or unsubstituted 5-membered ring nitrogen-containing aromatic compound coordinated to a divalent metal atom include pyrrole, 1-methylpyrrole, 3-methylpyrrole, 2,
5-dimethylpyrrole, pyrazole, N-methylpyrazole, 3,5-dimethylpyrazole, imidazole, N
-Methylimidazole, 2-methylimidazole, 4-
Methyl imidazole, 1,2-dimethyl imidazole,
Oxazole, thiazole, 4-methylthiazole,
2,4-dimethylthiazole, 1,2,3-oxadiazole, 1,2,3-triazole, 1,2,4-triazole, 1,3,4-thiadiazole, 2,5-dimethyl-1,3 , 4-thiadiazole and the like.

Examples of the substituted or unsubstituted 6-membered ring nitrogen-containing aromatic compound coordinated with a divalent metal atom include pyridine, 2-methylpyridine, 3-methylpyridine and 4-methylpyridine.
Methylpyridine, 2,3-dimethylpyridine, 2,4-
Dimethylpyridine, 2,5-dimethylpyridine, 2,6
-Dimethylpyridine, 3,4-dimethylpyridine, 3,
5-dimethylpyridine, 2-chloropyridine, 3-chloropyridine, 2-methoxypyridine, pyridazine, 3-
Examples thereof include methylpyridazine, pyrimidine, 4-methylpyrimidine, 2-chloropyrimidine, pyrazine, 2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2-methoxypyrazine, and s-triazine.

Examples of the substituted or unsubstituted condensed ring-containing nitrogen compound coordinated with a divalent metal atom include indole and
N-methylindole, 2-methylindole, 3-methylindole, 5-methylindole, 1,2-dimethylindole, 2,3-dimethylindole, 4-chloroindole, 5-chloroindole, 6-chloroindole, 4 -Methoxyindole, 5-methoxyindole, 6-methoxyindole, benzimidazole, 2-methylbenzimidazole, 5-methylbenzimidazole, 5,6-dimethylbenzimidazole,
5-chlorobenzimidazole, benzothiazole, 2
-Methylbenzothiazole, 2,5-dimethylbenzothiazole, 2-chlorobenzothiazole, purine, quinoline, 2-methylquinoline, 3-methylquinoline, 4-
Methylquinoline, 6-methylquinoline, 7-methylquinoline, 8-methylquinoline, 2,4-dimethylquinoline, 2,6-dimethylquinoline, 2-chloroquinoline,
6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, isoquinoline, 1-methylquinoline, quinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline, carbazole, N-methylcarbazole, acridine, 9-methylacridine, Examples include phenothiazine.

Suitable specific examples of the divalent metal atom include Cu, Ni, Co, Rh, Zn, Fe, Cu (pyridine) ₂ , Zn (pyridine) ₂ , Co (pyridine) ₂ , and F.
Examples thereof include unsubstituted or dicoordinated divalent metal atoms such as e (N-methylimidazole) and Co (N-methylimidazole).

When n is 0, M in the general formula (1) represents a trivalent or tetravalent metal atom or semimetal atom having a substituent.

Examples of the trivalent metal atom or metalloid atom having a substituent represented by M include Sc, Ti, V, Cr,
Mn, Mo, Ag, U, Fe, Co, Ni, Cu, Y,
Nb, Ru, Rh, La, Ta, Ir, Au, In, T
l, Bi, Ce, Pr, Nd, Pm, Sm, Eu, G
d, Tb, Dy, Ho, Er, Tm, Yb, Lu, B,
An alkyl group which may have a halogen atom, a hydroxyl group or a substituent represented by the above R ^{1 to} R ¹⁶ as a substituent on a trivalent unsubstituted metal atom or an unsubstituted metalloid atom such as As or Sb; Aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, halogen group similar to amino group, hydroxyl group,
An alkyl group which may have a substituent, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group,
A heterovalent thio group, an amino group, or a trivalent metal atom or semimetal atom selected from and bonded to a silyloxy group substituted with an alkyl group or an aryl group, or a halogen atom or a substituent similar to the above-mentioned substituents as a substituent A trivalent group selected from an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, and an amino group, which may have a group. A heterocyclic compound such as a 5-membered ring nitrogen-containing aromatic compound, a 6-membered ring nitrogen-containing aromatic compound, a condensed ring nitrogen-containing compound, etc. , A trivalent metal atom coordinated with alcohol or the like.

Examples of the silyloxy group substituted with an alkyl group or an aryl group include trialkylsilyloxy groups such as trimethylsilyloxy group and triethylsilyl group, triarylsilyloxy groups such as triphenylsilyloxy group and dimethylphenylsilyloxy. Examples thereof include alkylarylsilyloxy groups and the like.

Suitable specific examples of the trivalent metal atom include Al-F, Al-Cl, Al-Br, Al-I and G.
a-F, Ga-Cl, Ga-Br, Ga-I, In-
F, In-Cl, In-Br, In-I, Ti-F, T
i-Cl, Ti-Br, Ti-I, Al-C 6 H 5, Al
_{-C 6 H 4 (CH 3)} , In-C 6 H 5, In-C 6 H 4 (C
_{H 3), Mn (OH)} , Mn (OC 6 H 5), Mn [OS
i (CH _{3) 3],} Fe-Cl, Fe-Cl ( bis (N-
And methyl-imidazole)), Fe- (imidazolyloxy), Ru-Cl, and other mono-substituted trivalent metal atoms.

Preferable specific examples of the trivalent metalloid atom include BF, B-OCH ₃ , B-C ₆ H ₅ and BC ₆ H.
₄ (CH ₃ ), B (OH), B (OC ₆ H ₅ ), B [OSi
(CH ₃ ) ₃ ] and other mono-substituted trivalent semimetal atoms.

The tetravalent metal atom or metalloid atom having a substituent represented by M is Ti, Cr, Sn or Z.
In the tetravalent unsubstituted metal atom or unsubstituted semimetal atom such as r, Ge, Mn, or Si, the above-mentioned R ^{1 to} R ¹⁶ are used as a substituent.
Represented by a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, The same halogen atom as the amino group, hydroxyl group, optionally substituted alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group Substituted or unsubstituted 5-membered nitrogen-containing nitrogen as a ligand to a tetravalent metal atom or metalloid atom selected from an oxygen group, an silyloxy group substituted with an amino group, an alkyl group or an aryl group, or an oxygen atom Compounds such as aromatic compounds, 6-membered ring nitrogen-containing aromatic compounds and condensed ring nitrogen-containing compounds Ring compound, carbon monoxide, alcohol and the like is coordinated may be tetravalent metal atom.

As preferred specific examples of the tetravalent metal atom,
Is TiF₂, TiCl₂, TiBr ₂, TiI₂, CrF
₂, CrCl₂, CrBr₂, CrI₂, SnF₂, SnC
l₂, SnBr₂, SnI₂, ZrF₂, ZrCl₂, Zr
Br₂, ZrI₂, GeF₂, GeCl₂, GeBr₂, G
eI₂, MnF₂, MnCl₂, MnBr₂, MnI₂, T
i (OH)₂, Cr (OH)₂, Sn (OH)₂, Zr
(OH)₂, Ge (OH)₂, Mn (OH)₂, TiA₂,
CrA₂, SnA₂, ZrA₂, GeA₂, MnA₂, Ti
(OA)₂, Cr (OA)₂, Sn (OA)₂, Zr (O
A)₂, Ge (OA) ₂, Mn (OA)₂, Ti (S
A)₂, Cr (SA)₂, Sn (SA)₂, Zr (S
A)₂, Ge (SA)₂, Mn (SA)₂, Ti (NH
A)₂, Cr (NHA)₂, Sn (NHA)₂, Zr (N
HA)₂, Ge (NHA)₂, Mn (NHA)₂, Ti
(NA₂)₂, Cr (NA₂)₂, Sn (NA₂)₂, Zr
(NA₂)₂, Ge (NA₂)₂, Mn (NA₂)₂[A is
R mentioned above¹~ R¹⁶An alkyl group represented by, an aryl group,
Substituted or unsubstituted alkyl similar to the heteroaryl group
A group, an aryl group and a heteroaryl group are shown. ], Etc.
Alternative tetravalent metal atoms are mentioned.

Preferred specific examples of the tetravalent semimetal atom include SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ and Si.
(OH) ₂ , SiA ₂ , Si (OA) ₂ , Si (SA) ₂ ,
Si (NHA) ₂ , Si (NA ₂ ) ₂ [A means the above-mentioned A. ] Disubstituted tetravalent semimetal atoms such as

Specific examples of the oxo metal atom, which is a tetravalent metal atom to which an oxygen atom is bonded, include VO, MnO, and
TiO etc. are mentioned.

M is preferably Cu, Ni or C.
o, Rh, Zn, Fe, MnCl, CoCl, FeC
l, Fe (N-methylimidazolyloxy), Fe-C
l (bis (N-methylimidazole)), Cu (pyridine) ₂ , Zn (pyridine) ₂ , Co (pyridine) ₂ , Fe
(N- methylimidazole), Co (N- _{methylimidazole) 2, VO, TiO, TiA} 2, SiA 2, Sn
A ₂ , RuA ₂ , RhA ₂ , GeA ₂ , Si (OA) ₂ , S
n (OA) ₂ , Ge (OA) ₂ , Si (SA) ₂ , Sn
(SA) ₂ , Ge (SA) ₂ [A means A described above. ] Is mentioned.

Furthermore, when n is 1, M represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom.

As the trivalent metal atom used together with one hydrogen atom in M, there can be mentioned IIIA to VIIA, VIII of the periodic table.
And metal atoms of group IB to VIIB. Suitable examples include Sc, Ti, V, Cr, Mn, Mo, Ag,
U, Fe, Co, Ni, Cu, Y, Nb, Ru, Rh,
La, Ta, Ir, Au, In, Tl, Pb, Bi, C
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
Examples thereof include trivalent unsubstituted metal atoms such as y, Ho, Er, Tm, Yb and Lu. More preferably, Lu, Ce, S
m, Ru, Eu, Y, Rh and the like.

Examples of the tetravalent metal atom represented by M include metal atoms of Group IIIA to VIIA, Group VIII and Group IB to VIIB of the periodic table. Suitable examples include Ti, V, Cr,
Mn, Mo, Zr, Nb, Ru, Rh, Ta, Ir, P
b, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
Examples thereof include trivalent unsubstituted metal atoms such as b, Dy, Ho, Er, Tm, Yb and Lu. More preferably, Zr, L
u, Ce, Ru, Rh and the like can be mentioned.

Further, in the present invention, as the compound represented by the general formula (1), the compound further exemplified by the general formula (2) is mentioned as a preferable example.

[0251]

[Chemical 8]

[In the formula, R¹⁷~ R^{twenty four}Each independently, water
Elementary atom, halogen atom, nitro group, cyano group, substitution or
Is an unsubstituted hydrocarbon group, substituted or unsubstituted hydroxy
Group, substituted or unsubstituted mercapto group, substituted or unsubstituted
Represents an alternative amino group, R¹⁷~ R ^{twenty four}Each substituent of
Via each substituent and linking group on the Zaporphyrin ring,
Each of them may be bonded together to form an aliphatic ring.
In a substituted or unsubstituted hydrocarbon group and / or hydrocarbon water
Substituted hydroxyl group substituted with elementary group, Substituted mercapto
Group, between the carbon-carbon atoms in the substituted amino group, an oxygen atom,
Substituted or unsubstituted sulfur atom, substituted or unsubstituted nitrogen
It may have atoms. M¹Has a ligand
A good divalent metal atom, or substituent and / or
Trivalent or tetravalent metal atom or half-gold with a ligand
Represents a genus atom. ]

In the compound represented by the general formula (2) of the present invention, specific examples of R ^{17 to} R ²⁴ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group and the like can be mentioned.

Examples of the substituted or unsubstituted hydroxy group, the substituted or unsubstituted mercapto group and the substituted or unsubstituted amino group of R ^{17 to} R ²⁴ include the same substituted or unsubstituted hydroxy groups as those described above for R ^{1 to} R ^16. Examples thereof include a substituted hydroxyl group, a substituted or unsubstituted mercapto group, and a substituted or unsubstituted amino group.

As the linking group when R ^{17 to} R ²⁴ are bonded together via a linking group to form an aliphatic ring,
The same linking groups as those described above for R ^{1 to} R ¹⁶ can be mentioned.

Examples of the divalent metal atom which may have a ligand used for M ¹ or the trivalent or tetravalent metal atom or semimetal atom having a substituent and / or a ligand. Is the same metal atom as M described above.

Further, in the present invention, as the compound represented by the general formula (1), compounds further exemplified by the general formula (3) are mentioned as preferable examples.

[0258]

[Chemical 9]

[Wherein, R ^{25 to} R ⁴⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted amino group, the X ⁹ to X ^{1 6} each independently represents a nitrogen atom or a substituted or unsubstituted methine group,
Each of the substituents on R ^{25 to} R ⁴⁰ and the methine group may be bonded together via a linking group to form an aliphatic ring, which may be a substituted or unsubstituted hydrocarbon group, and / or A substituted hydroxy group substituted by a hydrocarbon group, a substituted mercapto group, or a substituted amino group may have an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom between carbon atoms. good. Further, n represents 0 or 1, and when n is 0, M ² is a divalent metal atom which may have a ligand, or a trivalent or tetravalent one having a substituent and / or a ligand. It represents a valent metal atom or a metalloid atom, and when n is 1, M ² represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ]

In the compound represented by the general formula (3) of the present invention, specific examples of R ^{25 to} R ⁴⁰ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group and the like can be mentioned.

Examples of the substituted or unsubstituted hydroxy group, the substituted or unsubstituted mercapto group, and the substituted or unsubstituted amino group of R ^{25 to} R ⁴⁰ include the same substituted or unsubstituted R ^{1 to} R ¹⁶ as described above. Examples thereof include a substituted hydroxyl group, a substituted or unsubstituted mercapto group, and a substituted or unsubstituted amino group.

As the linking group when R ^{25 to} R ⁴⁰ are bonded together through a linking group to form an aliphatic ring,
The same linking groups as those described above for R ^{1 to} R ¹⁶ can be mentioned.

In the metal atom or metalloid atom used in M ² , when n is 0, a divalent metal atom which may have a ligand, or a substituent and / or a ligand having 3 Examples of the valent or tetravalent metal atom or metalloid atom include the same metal atom as M described above. When n is 1, M ² is 1 with a trivalent metal atom.
Examples of hydrogen atoms or tetravalent metal atoms are:
The metal atom similar to the above M is mentioned.

Further, in the present invention, as the compound represented by the general formula (1), the compound further exemplified by the general formula (4) is mentioned as a preferable example.

[0265]

[Chemical 10]

[In the formula, R⁴¹~ R⁷²Each independently, water
Elementary atom, halogen atom, nitro group, cyano group, substitution or
Is an unsubstituted hydrocarbon group, substituted or unsubstituted hydroxy
Group, substituted or unsubstituted mercapto group, substituted or unsubstituted
Represents an alternative amino group, R⁴¹~ R ⁷²Each substituent of is phthalocyanine
Together with each substituent on the anine ring and the linking group,
A substituted or unsubstituted hydrocarbon group which may be bound by
And / or substituted hydroxy substituted with hydrocarbon groups
Carbon-carbon in Si group, substituted mercapto group, substituted amino group
Oxygen atom, substituted or unsubstituted sulfur atom,
It may have a substituted or unsubstituted nitrogen atom. n is 0
Or 1 and when n is 0, M³Has a ligand
Optional divalent metal atom or trivalent having a substituent
Alternatively, it represents a tetravalent metal atom or a metalloid atom, and n is 1.
When M³Is a trivalent metal atom and one hydrogen atom, or
Represents a tetravalent metal atom. ]

In the compound represented by the general formula (4) of the present invention, specific examples of R ^{41 to} R ⁷² include hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group A cyano group and the like can be mentioned.

Examples of the substituted or unsubstituted hydroxy group, the substituted or unsubstituted mercapto group, or the substituted or unsubstituted amino group of R ^{41 to} R ⁷² include the same substituted or unsubstituted hydroxy groups as those described above for R ^{1 to} R ^16. Examples thereof include a substituted hydroxyl group, a substituted or unsubstituted mercapto group, and a substituted or unsubstituted amino group.

Examples of the linking group when R ^{41 to} R ⁷² are bonded together via a linking group to form a ring include the same linking groups as those described above for R ^{1 to} R ¹⁶ .

When n is 0 in the metal atom or metalloid atom used in M ³ , a divalent metal atom which may have a ligand, or a substituent and / or a ligand having a ligand of 3 Examples of the valent or tetravalent metal atom or metalloid atom include the same metal atom as M described above. Further, when n is 1, M ³ is a trivalent metal atom and 1
Examples of hydrogen atoms or tetravalent metal atoms are:
The metal atom similar to the above M is mentioned.

Among the azaannulene compounds described in the present invention, the compound of the general formula (1) is an oscillation wavelength region of a blue-violet nitride semiconductor laser of 350 to 450 nm, and a red semiconductor laser wavelength of 600 to 650 nm used in DVD-R. , CD
-Infrared semiconductor laser wavelength used in -R 750-85
It is suitable for recording / reproducing / erasing at 0 nm. Here, the compound of the general formula (3) is more suitable for recording / reproducing / erasing at a red semiconductor laser wavelength of 600 to 650 nm used in DVD-R, and the compound of the general formula (4) is a CD. -Infrared semiconductor laser wavelength used in -R 7
It is more preferably used for recording / reproducing / erasing at 50 to 850 nm. In particular, for the compound of general formula (2),
Oscillation wavelength range of blue-violet nitride semiconductor laser 350-45
0 nm, red semiconductor laser used in DVD-R wavelengths of 600 to 650 nm.
It is suitable for erasing.

Compounds represented by the general formula (1) used in the present invention, in which n is 0, are not limited, but for example, tetraazaporphyrin (alias: porphyrazine) in which X ^{1 to} X ⁴ are all nitrogen. ) For compounds, see, for example, J. Gen. Chem. USSR vol.47, pp1954-1958.
(1977) and the like. Typically, it can be produced by the following reaction.

That is, using at least one compound represented by the following general formulas (13) to (16), pentanol,
Alcohols such as hexanol, benzene, toluene,
Acetylacetonato salt of a divalent to tetravalent metal atom in an aromatic solvent such as xylene, 1-chloronaphthalene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene,
Organic metal salts such as acetates and trifluoroacetates or hydrates thereof, halides of metal atoms, sulfates, nitrates, perchlorates, chlorates, inorganic metal salts such as hypochlorites or the like By heating reaction in the presence of a base such as 1,8-diazabicyclo [5.4.0] -7-undecene together with a hydrate and the like, n = 0, X ^{1 to} X ⁴ in the general formula (1) can be obtained. A phthalocyanine compound in which four of them are nitrogen or a tetraazaporphyrin compound of the general formula (2) can be obtained.

[0274]

[Chemical 11]

[In the formula, R ^{73 to} R ⁸⁰ are R ¹ to R in the formula (1)]
Each has the same meaning as R ⁸ . ]

In addition, the tetraazaporphyrin compound of the general formula (2) is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform, or a Grignard reagent such as methylmagnesium bromide is reacted, By subsequently treating with an acid such as hydrochloric acid or sulfuric acid, a metal-free tetraazaporphyrin compound can be obtained.

Further, the monoazaporphyrin compound in which n = 0 and ^one of X ^{1 to} X ⁴ is nitrogen is not particularly limited, but for example, Bull. Chem. Soc. Jpn., 61,
3539-3547 (1988), Inorg. Chem., 32, 291-296 (199
3), Tetrahedron Lett., 36 (10), 1567-1570 (1995), Li
ebigs Ann. Chem., 339-359 (1977), Inorganica Chimic
It can be produced according to the method described in aActa, 203, 107-114 (1993) and the like. Typically, for example, it can be manufactured by the following method.

That is, a dipyrromethane compound represented by the general formula (17) and a pyrrole compound represented by the general formula (18) and the general formula (19) are combined with a halogenated solvent such as methylene chloride,
The reaction is carried out in the presence of hydrobromic acid in a solvent such as an alcohol solvent such as ethanol to obtain the condensate of formula (20) or a hydrobromide salt thereof.

[0279]

[Chemical 12]

[In the formula, R ⁸¹ , R ⁸² , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ ,
R ⁸⁷ , R ⁸⁹ , and R ⁹⁰ have the same meanings as R ^{1 to} R ⁸ in formula (1), and R ⁸³ , R ⁸⁸ , and R ⁹¹ represent X ^{1 in} formula (1).
To X ⁴ each have the same meaning as the substituent on the methine group, and r represents a hydrogen atom or a carboxyl group. ]

[0281]

[Chemical 13]

[In the formula, R⁹², R⁹³, R⁹⁵, R⁹⁶, R⁹⁸,
R⁹⁹, R¹⁰¹, R¹⁰²Is R in the formula (1) ¹~ R⁸And each
Represents the same meaning, R⁹⁴, R⁹⁷, R¹⁰⁰Of the formula (1)
X¹~ X ^FourWhich have the same meaning as the substituents on the methine group, respectively.
Represents the taste. ]

Then, the condensate represented by the general formula (20) is treated with bromine, iodine, N 2 in an organic acid such as acetic acid, methylene chloride or trifluoroacetic acid, a halogenated solvent or a solvent such as an alcohol solvent such as ethanol. Halogenation with a halogenating agent such as -bromosuccinimide or N-iodosuccinimide gives a dihalogenated compound of the general formula (21).

[0284]

[Chemical 14]

[In the formula, R ^{92 to} R ¹⁰² are the same as those of the formula (20);
^{92 to} R ¹⁰² each represent the same group, and a represents a halogen atom. ]

Next, in an alcohol solvent such as methanol or ethanol, a halogenated solvent such as methylene chloride, or an amide solvent such as N, N-dimethylformamide,
Coordination properties that can coordinate to metals or metalloids such as inorganic salts such as sulfates, nitrates and halogenated salts of metals or metalloids, or organic metal salts such as acetates and acetylacetonates, and pyridines Compounds, ionic compounds such as sodium chloride and sodium borofluoride capable of metal coordination with anions, oxidizing agents such as air, neutralizing agents such as N-ethyldiisopropylamine and triethanolamine, benzo-18-crown-6- By reacting with an azide salt such as sodium azide in the presence or absence of a phase transfer catalyst such as ether, n = 0 in the general formula (1),
A monoazaporphyrin compound in which one of X ^{1 to} X ⁴ is nitrogen can be obtained.

Further, the metal-complexed monoazaporphyrin compound is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform or with a Grignard reagent such as methylmagnesium bromide, and then The metal-free monoazaporphyrin compound can be obtained by treating with an acid such as hydrochloric acid or sulfuric acid.

The diazaporphyrin compound in which n = 0 and two of X ^{1 to} X ⁴ are nitrogen is not particularly limited, but for example, J. Chem. Soc. (C), 22 -29 ( 199
6), J. Biochem., 121, 654-660 (1997), Z. Physiol. C
hem, 214, 145 (1933), Die Chemie des Pyrrols, Band
II, Halfte 2, pp. 411 -414, Akademische Verlagesell
It is produced according to the method described in schuft, Leipzig (1940) and the like. Typically, it can be produced by the following three-step reaction.

First, in the first step, the dipyrromethane compound represented by the general formula (22) or (23) is treated with bromine in a carboxylic acid solvent such as acetic acid or a halogenated hydrocarbon solvent such as methylene chloride. Halogenated with a halogenating agent such as iodine, iodine, N-bromosuccinimide, or N-iodosuccinimide to obtain the dipyrromethene compound represented by the general formula (24) or the general formula (25).

[0290]

[Chemical 15]

[In the formula, R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁶ , R ¹⁰⁷ , R
¹⁰⁸ , R ¹⁰⁹ , R ¹¹¹ , and R ¹¹² have the same meanings as R ^{1 to} R ⁸ of formula (1), and R ¹¹³ and R ¹¹⁸ respectively represent the substituent on the methine group of formula (1). They have the same meaning, and r represents a hydrogen atom or a carboxyl group. ]

[0292]

[Chemical 16]

[0293] wherein, R ¹⁰³ to R ¹¹² each represent the same group as R ¹⁰³ to R ¹¹² in formula (22) and Equation (23), a represents a halogen atom. ]

Then, in the second step, the dipyrromethene compound represented by the general formula (24) or the general formula (25) is treated with metal or metal in an organic solvent such as an alcohol solvent such as ethanol and / or an amide solvent such as dimethylformamide. Inorganic salts such as semi-metal sulfates, nitrates, halogenated salts,
Alternatively, a dipyrromethene represented by the general formula (26) is obtained by reacting a metal or metalloid compound such as an organic metal salt such as an acetate salt or an acetylacetonate salt in the presence or absence of an oxidizing agent such as air. A metal complex is obtained.

[0295]

[Chemical 17]

[Wherein R ^{113 to} R ¹²² and a are represented by the formula (2
4) and R ^{113 to} R ^{122 in} Formula (25) and the same group as a, and M ⁴ has the same meaning as M in Formula (1). ]

Then, in the third step, the dipyrromethene metal complex (26) is mixed with an alcohol solvent such as ethanol and /
Alternatively, by reacting with an azide salt such as sodium azide in an organic solvent such as an amide solvent such as dimethylformamide, n = 0 in the general formula (1), and a diamine in which two of X ^{1 to} X ⁴ are nitrogen. A Zaporphyrin compound can be obtained.

Here, the general formula (2
4) and the dipyrromethene compound of the general formula (25) in an organic solvent such as an alcohol solvent such as ethanol and / or an amide solvent such as dimethylformamide,
Inorganic salts such as sulfates, nitrates and halogenated salts of metals or metalloids, or organic metal salts such as acetates and acetylacetonates are used in the presence or absence of an oxidizing agent such as air and the like. The above diazaporphyrin compound can also be obtained by reacting with an azide salt such as sodium iodide.

The metal-complexed diazaporphyrin compound is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform or a Grignard reagent such as methylmagnesium bromide, and then A metal-free diazaazaporphyrin compound can be obtained by treating with an acid such as hydrochloric acid or sulfuric acid.

The triazaporphyrin compound in which n = 0 and three of X ^{1 to} X ⁴ are nitrogen is not particularly limited, but for example, Can. J. Chem. Vol. 71, 742-
It is manufactured according to the method described in 753 (1996) and the like. Typically, it can be produced by the following reaction.

That is, the above general formulas (13) to (16)
A compound represented by the formula (27), at least one of unsaturated ketone compounds of the general formula (28) is reacted with a metal halide and / or a metal derivative in the presence of a solvent or without a solvent. However, in the general formula (1), n = 0, X ¹
It is possible to obtain a triazaporphyrin compound in which 3 out of X ⁴ are nitrogen.

[0302]

[Chemical 18]

[Wherein R ¹²³ , R ¹²⁴ , R ¹²⁶ , and R ¹²⁷ are
R ^{1 to} R ⁸ of the formula (1) have the same meanings as R ^{1 to} R ⁸ ,
¹²⁵ and R ¹²⁸ each have the same meaning as the substituent on the methine group of formula (1), and r represents a hydrogen atom or a carboxyl group. ]

Alternatively, the above general formulas (13)-
By using at least one compound represented by the formula (16), a Grignard reagent represented by the following general formula (29) is allowed to act in the presence of a solvent such as ether, and heating is performed in the presence of an amine such as quinoline, the general formula N = 0 in (1), X ^{1 to} X ⁴
It is possible to obtain a triazaporphyrin magnesium complex compound having a substituted methine group, three of which are nitrogen.

[0305]

[Chemical 19]

[In the formula, R'represents the same meaning as the substituent substituting the methine group of the formula (1), and X'represents a halogen atom. ]

Further, the metal complexed triazaporphyrin compound is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform or with a Grignard reagent such as methylmagnesium bromide, and then By treating with an acid such as hydrochloric acid or sulfuric acid, a metal-free triazaazaporphyrin compound can be obtained.

The porphyrin compound in which n = 0 and X ^{1 to} X ⁴ are all substituted or unsubstituted methine groups is not particularly limited, but for example, J. Org. Chem. Vol.
It is produced according to the method described in 58 (25), 7245-7257 (1993) and the like. Typically, it can be produced by the following reaction.

That is, the following general formulas (30) to (33)
In the presence of an acid such as propionic acid, in a solvent or in the absence of a solvent, at least one kind of pyrrole compound represented by and at least one kind of aldehyde compound represented by the following general formulas (34) to (37) is used. By heating and reacting, a metal-free porphyrin compound of the general formula (1) in which n = 0 and X ^{1 to} X ⁴ are all substituted or unsubstituted methine groups can be obtained.

[0310]

[Chemical 20]

[In the formula, R¹²⁹~ R¹³⁶Is R in the formula (1)¹
~ R⁸And the same meaning as R, ¹³⁷~ R¹⁴⁰Is an expression
X in (1)¹~ X^FourIs the same as the substituent that substitutes for the methine group
Represents one meaning. ]

Alternatively, a dipyrromethanedialdehyde compound represented by the following formula (38) and a dipyrromethane compound represented by the following formula (39) are used in the presence of an acid such as propionic acid or the like in a solvent or without a solvent. It is also possible to obtain a metal-free porphyrin compound of the formula (1) in which n = 0 and X ^{1 to} X ⁴ are all substituted or unsubstituted methine groups by heating in the reaction.

[0313]

[Chemical 21]

[Wherein, R ¹⁴² , R ¹⁴³ , R ¹⁴⁵ , R ¹⁴⁶ , R
¹⁴⁸ , R ¹⁴⁹ , R ¹⁵¹ , and R ¹⁵² have the same meanings as R ^{1 to} R ⁸ in formula (1), and R ¹⁴¹ and R ¹⁴⁷ represent methine that is X ^{1 to} X ⁴ in formula (1). It has the same meaning as the substituents on the group. ]

In the azaporphyrin compound represented by the general formula (1) of the present invention, when n is 1, it is represented by the following general formulas (40) and (41) obtained by the above-mentioned production method and the like. Compounds or only compounds represented by the general formula (40) are used as alcohols such as pentanol and hexanol, benzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene, 1,2,2,2.
In an aromatic solvent such as 4-trichlorobenzene, an organic metal salt such as an acetylacetonato salt of trivalent or tetravalent metal atom, acetate, trifluoroacetate or the hydrate thereof, a halide of metal atom, a sulfate salt In some cases, it is heated with an inorganic metal salt such as nitrate, perchlorate, chlorate, and hypochlorite or a hydrate thereof, or a disubstituted amide salt such as dimethylamide salt and diethylamide salt. You can get it.

[0316]

[Chemical formula 22]

[0317] [wherein, R ¹ to R ^16, X ¹ to X ⁴ represents R ¹ to R ^16, X ¹ to X ⁴ each identical groups of the formula (1). ]

Alternatively, instead of the compound represented by the general formula (40), a compound represented by the following general formula (42) which is a lithium salt thereof, or a compound obtained by coordinating the compound with an oxygen-containing hydrocarbon compound such as dimethoxyethane, Further, in place of the formula (41), the lithium salt thereof is a compound of the following general formula (43), or a compound obtained by coordinating an oxygen-containing hydrocarbon compound such as dimethoxyethane with the compound is used. It can be obtained by reacting with.

[0319]

[Chemical formula 23]

[0320] [wherein, R ¹ to R ^16, X ¹ to X ⁸ represents R ¹ to R ^16, X ¹ to X ⁸ each identical groups of the formula (1). ]

The central metal which is the compound of the present invention is 3
A compound of the following general formula (44), which is a valent metal and a hydrogen atom, is reacted with an oxidizing agent such as dichlorodicyanobenzoquinone or chloranil in a halogenated solvent such as dichloromethane, chloroform, dichloroethane or trichloroethane, if necessary, by heating reaction. By doing so, the following general formula (45), in which the central metal that is the compound of the present invention is a tetravalent metal,
Can be obtained.

[0322]

[Chemical formula 24]

[In the formula, R ^{153 to} R ¹⁸⁴ are R ^{1 of the} formula (2).
To R ¹⁶ each represent the same group, M ⁵ represents a trivalent metal atom, M ⁸ represents a tetravalent metal atom, and X ^{9 to} X ²⁴ represent
It has the same meaning as X ^{1 to} X ^{8 in} formula (1). ]

Further, the compound of the following general formula (46) is
Using a silver compound such as silver trifluoroacetate as a reaction aid, in an aromatic solvent such as benzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, the above-mentioned general A compound of the following general formula (47), which is a compound of the present invention, can be obtained by heating reaction with the lithium compound of the formula (42) or the above general formula (43) as the case may be.

[0325]

[Chemical 25]

[In the formula, R ^{185 to} R ¹⁰⁸ are R ^{1 of the} formula (1).
To R ¹⁶ respectively represent the same group, M ⁷ and M ⁸ represent a tetravalent metal atom, Q ¹ and Q ² represent a fluorine atom, a chlorine atom,
Represents a halogen atom such as a bromine atom or an iodine atom, and X ⁹ ~
X ²⁴ has the same meaning as X ^{1 to} X ⁸ in formula (1). ]

Regarding R ^{1 to} R ¹⁶ in which any substituent is a hydrogen atom, for example, nitration, halogenation, formylation, amination, carboxylation, hydroxylation, acylation, elimination reaction A selected hydrogen atom is substituted with an arbitrary substituent by a conventional synthesis method such as, and further, a hydrogen atom is generally substituted by a conventional synthesis method such as reduction, oxidation, isomerization, and rearrangement, if necessary. It is also possible to obtain compounds of formula (1).

The notation of substituents and the like is shown according to the general formula (1), but the general formulas (2) to (4) are included in the general formula (1), The replacement of the corresponding substituents and the like is self-evident. The dye of the recording layer constituting the optical recording medium of the present invention is substantially composed of one or more azaannulene compounds, particularly compounds of the general formulas (1) to (4), and , It has an absorption maximum at a wavelength of 290 nm to 690 nm, if necessary,
You may mix with dye compounds other than the above which have a large refractive index in 300 nm-900 nm. Specifically, cyanine compounds, squarylium compounds, naphthoquinone compounds, anthraquinone compounds, tetrapyrporphyrazine compounds, indophenol compounds, pyrylium compounds, thiopyrylium compounds, azulenium compounds, triphenylmethane compounds , Xanthene compounds, induslen compounds, indigo compounds, thioindigo compounds, merocyanine compounds, thiazine compounds, acridine compounds, oxazine compounds, dipyrromethene compounds, oxazole compounds, etc.,
It may be a mixture of a plurality of compounds. The mixing ratio of these compounds is about 0.1% by mass to 30% by mass.

When forming the recording layer, a quencher, a compound thermal decomposition accelerator, an ultraviolet absorber, an adhesive, an endothermic or endothermic decomposable compound is added to the compound represented by the general formula (1), if necessary. To the extent that a compound or a compound such as a solubility improver is effective or does not impair the recording / reproducing / erasing operation,
It is also possible to introduce a compound having a molecular weight of less than 3000 into the compound represented by the general formula (1) as a substituent.

Specific examples of the quencher include acetylacetonate type, bisdithiol type such as bisdithio-α-diketone type and bisphenyldithiol type, thiocateconal type, salicylaldehyde oxime type and thiobisphenolate type. Metal complexes are preferred. Further, amine type is also suitable.

The compound thermal decomposition accelerator is not particularly limited as long as the thermal decomposition of the compound can be confirmed by thermal loss analysis (TG analysis) and the like, and examples thereof include metal anti-knocking agents and metallocene compounds. , And metal compounds such as acetylacetonato metal complexes. Examples of the metal anti-knocking agent include tetraethyl lead, other lead compounds, simantrene [Mn (C ₅ H ₅ ) (CO)
₃ ] and the like, and examples of metallocene compounds include iron biscyclopentadienyl complex (ferrocene), Ti, V, Mn, Cr, Co, Ni, M
o, Ru, Rh, Zr, Lu, Ta, W, Os, Ir,
There are biscyclopentadienyl complexes such as Sc and Y.
Among them, ferrocene, ruthenocene, osmocene, nickelocene, titanocene and their derivatives have a good thermal decomposition promoting effect.

In addition to the metallocenes, iron-based metal compounds such as iron formate, iron oxalate, iron laurate, iron naphthenate, iron stearate, iron acetate, and other organic acid iron compounds, acetylacetonato iron complexes, Phenanthroline iron complex, bispyridine iron complex, ethylenediamine iron complex,
Chelating iron complexes such as ethylenediaminetetraacetic acid iron complex, diethylenetriamine iron complex, diethylene glycol dimethyl ether iron complex, diphosphino iron complex, and dimethylglyoximate iron complex, carbonyl iron complex, cyano iron complex, ammine iron complex, and other iron complexes, first chloride Examples thereof include iron halides such as iron, ferric chloride, ferrous bromide and ferric bromide, inorganic iron salts such as iron nitrate and iron sulfate, and iron oxide. The thermal decomposition accelerator used here is preferably one which is soluble in an organic solvent and has good wet heat resistance and light resistance.

Examples of the endothermic or endothermic decomposable compounds include compounds described in JP-A No. 10-291366, compounds having a substituent described in the publication, and the like.

The above-mentioned various quenchers, compound thermal decomposition accelerators and endothermic or endothermic decomposable compounds may be used alone or in combination of two or more, if necessary.

Alternatively, a compound having a quencher ability, a compound thermal decomposition promoting ability, an ultraviolet absorbing ability, and an adhesive ability is introduced as a substituent of the azaannulene compound of the present invention, particularly the compound represented by the general formula (1). It is also possible.

That is, a compound residue having a quencher ability, a compound thermal decomposition accelerating ability, an ultraviolet absorbing ability, an adhesive ability, an endothermic ability or an endothermic resolution with respect to the azaannulene compound residue of the general formula (1) described in the present invention. May be chemically bonded to each other through at least one single bond, double bond or triple bond to form one molecule. Preferably, each substituent of the azaannulene ring of the general formula (1) is represented by the general formula (48)

[0337]

[Chemical formula 26]

[Wherein, L ⁿ is a bond to the azaannulene compound of the formula (1), that is, a single bond or an optionally substituted methylene group, methine group, amino group, imino group, oxygen atom or sulfur atom. Represents an atomic chain having 1 to 20 atoms selected by linking at least one kind, and J ⁿ is a quencher, a compound thermal decomposition accelerator, an ultraviolet absorber, an adhesive ability, an endothermic ability or an endothermic resolution R ¹ to It represents a compound residue corresponding to R ¹⁶ . ]

A substituent represented by: or the general formula (1)
In the general formula (49), each substituent of the azaannulene ring is linked to another substituent and bonded.

[0340]

[Chemical 27]

[Wherein, L ^m1 and L ^m2 are adjacent to each other, and are bonded to the azaporphyrin compound of the formula (2), that is, a single bond, or a methylene group, a methine group or an amino group which may be substituted. 1 to 20 atoms selected from at least one selected from an imino group, an oxygen atom and a sulfur atom
And J ^m represents a compound residue corresponding to R 1 to R 22 having a quencher, a compound thermal decomposition accelerator, an ultraviolet absorber, an adhesive ability, an endothermic ability or an endothermic resolution. ]

Examples include the substituents represented by:

Preferred examples of the atom chain of L ⁿ , L ^m1 and L ^m2 include a single bond, a methylene group, an imino group, a thia group and -C.
_{(= O) -OCH 2 -,} - C (= O) -OCH (CH 3)
_{-, - OCH 2 -, -} OCH (CH 3) -, - CH 2 OC
_{H 2 -, - CH 2 OCH} (CH 3) -, - CH (CH 3) O
_{CH (CH 3) -, -} O-C (= O) -, - CH = CH
-, -CH = N-, -C (= O)-, -CH = CH-C
(= O) O -, - C (C = O) CH 2 CH 2 C (= O) -
Examples thereof include O- and groups in which these groups are substituted with the above-described substituents.

Preferred examples of J ⁿ and J ^m include metallocene residues such as ferrocene residue, cobaltocene residue, nickelocene residue, ruthenocene residue, osmocene residue and titanocene residue.

Suitable examples of the skeleton of the general formula (48) include:
The following metal complex residues are mentioned.

[0346]

[Chemical 28]

(M 'is Fe, Ru, Co, Ni, Os
Or M "Z '₂(M "is Ti, Zr, Hf, Nb, Mo,
Represents V, Z'is CO, F, Cl, Br, I,
R¹~ R ¹⁶An alkyl group having 1 to 10 carbon atoms having the same substituent as
Alkyl group, alkoxy group, aryl group, aryloxy
Group, aralkyl group and aralkyloxy group are shown)
You )

Further, examples of preferable skeleton of the general formula (49) include the following metal complex residues.

[0349]

[Chemical 29]

(M 'is Fe, Ru, Co, Ni, Os
Or M "Z '₂(M "is Ti, Zr, Hf, Nb, Mo,
Represents V, Z'is CO, F, Cl, Br, I,
R¹~ R ¹⁶An alkyl group having 1 to 10 carbon atoms having the same substituent as
Alkyl group, alkoxy group, aryl group, aryloxy
Group, aralkyl group and aralkyloxy group are shown)
You )

In the above compound group, for example, the wavelength λ
It is possible to realize a refractive index n ≧ 1.9 in the vicinity of = 400 nm. Particularly, in the case of phthalocyanine type dyes, azaporphyrin type dyes, and porphyrin type dyes, it is usually 400 nm.
There is a Soret band in the following ultraviolet region, and there is an absorption band having a clear maximum value represented by the Q band and the like on the long wavelength side within 400 nm from this Soret band. The absorption coefficient k and the refractive index n at the foot of the Soret band are adjusted to satisfy the above conditions at the recording wavelength λ.

The core of the basic molecule of the organic dye thus selected may be modified with various substituents, thereby optimizing the light absorption spectrum and modifying the solubility of the dye. Sexual improvement is done. Usually, these materials can be formed into a film by dissolving or dispersing them in an appropriate solvent and applying and drying them by a spin coating method, a spui method or the like. Further, in order to perform higher density recording, between the guide grooves formed on the substrate or the light transmission layer (land portion),
For recording (land / groove recording) in both the groove (groove portion), a vacuum vapor deposition method or the like is applied because it is necessary to achieve uniform control of the dye film thickness in both the groove and the land. The recording layer thickness is preferably formed in the range of 20 to 200 nm. More preferably, it is 20 to 120 nm. In order to suppress thermal interference and increase the recording density, it is desirable to secure the high refractive index of the organic dye recording film and reduce the film thickness.

In the optical recording medium of the present invention, as shown in FIGS. 1 and 2, the reflective layer can be provided adjacent to the recording layer. The material of the reflective layer is gold, silver,
Examples include metals such as aluminum, platinum, and copper, and alloys containing these. When a blue-violet laser having a wavelength of 390 to 430 nm is used, silver, aluminum and alloys containing them are preferable in terms of cost and optical characteristics, and particularly, silver, which has high durability, and Ti, Pd, Cu, etc. Is preferred. The thickness of the reflective layer is usually 20 to 1
It is 20 nm, preferably 10 to 80 nm. Further, instead of the metal reflection film, a dielectric reflection film {low refractive index dielectric film / high refractive index dielectric film} may be alternately laminated. For example, in the case of setting a relatively low reflectance of a disc, a SiO ₂ (n = 1.46) quarter wave film and a Si ₃ N ₄ (n = 2.0) quarter wave film are used. A simple structure such as a layer laminated film can be used.
It is also possible to employ a film structure of a disk that does not use any metal thin film layer. As a method of forming the reflective layer, a vacuum vapor deposition method, a sputtering method, an ion beam sputtering method, or the like can be used.

In the structure shown in FIG. 1, an organic material such as an ultraviolet curable resin or a thermosetting resin is spin-coated on the reflective layer 3 to form the protective film 4. Further, as shown in FIG. 1, a dummy substrate may be bonded on the protective film as in the conventional DVD.

Also in the case of the structure shown in FIG. 3, the reflective layer 2 and the recording layer 3 are sequentially formed on the substrate 1 on which the guide groove and the like are formed, and the ultraviolet curable resin is applied on the recording layer 3. After that, it is irradiated with UV to be cured to form the light transmission layer 8. or,
It is also possible to separately form the light transmitting layer 8 into a film having a uniform thickness and to bond the light transmitting layer 8 through an adhesive layer such as an ultraviolet curable resin or a pressure sensitive adhesive.

By forming a transparent protective layer between the substrate and the recording layer, it is also effective to suppress deformation of the substrate due to heat generated during recording. In addition, as shown in FIG.
When it is formed on the recording layer 3 via an adhesive, the transparent protective layer 4 is provided between the organic dye and these layers in order to prevent the substrate from being deformed and to prevent the organic dye from being dissolved in the ultraviolet curable resin. It is also effective to form. The transparent protective layer 4 is made of metal (for example, Mg, Al, Ti, Zn, Ga,
Zr, In, Sn, Sb, Ba, Hf, Ta, Sc,
Y, a rare earth element) or a semimetal (Si, Ge) oxide, nitride, sulfide, fluoride or the like, or a mixture thereof can be used. As a method for forming these transparent protective films, a vacuum vapor deposition method, a sputtering method, an ion beam sputtering method or the like can be used. Further, in the optical recording medium having this structure, a sheet made of, for example, polycarbonate having guide grooves formed by stamper thermal transfer having a thickness of 10 to 177 μm by injection molding or casting is used as the light transmitting layer. A recording layer made of an organic dye and a reflective layer may be formed in this order on this, and a substrate may be further attached.

Further, by forming the above-mentioned transparent protective layers adjacent to both sides of the recording layer, it is possible to more completely suppress the deformation of the substrate, the reflective layer, the protective film and the light transmitting layer due to the heat generated during recording, It is possible to improve repetitive rewriting characteristics.

The thicknesses of the recording film, the reflective film, and the transparent protective film are appropriate at the recording laser wavelength in order to secure the initial reflectance and the signal modulation degree conforming to the respective standards of CD, DVD, DVR and the like. Each can be optimized by calculating the reflectance of the multi-layered thin film structure in consideration of the effect of optical multiple reflection using a recording film, a reflective film, and a transparent protective film material having different optical constants.

Since the optical recording medium according to the present invention has a form in which one or more kinds of thin films are laminated as described above, the fact that multiple interference of light occurs is positively utilized, and according to each standard. It is important to set the film thickness of each layer so that the initial reflectance falls within the range specified by the standard and the modulation degree of the information signal to be detected is maximized. Therefore, regarding the multiple interference effect of this light, the method of calculating the reflectance: the effective Fresnel coefficient method will be described.

[0360] r _1, medium n ₀ and the medium n ₁ of FIG. 4 the r _2, medium n ₁
And Fresnel coefficient in medium n ₂ , the amplitude reflectance of the single-layer film is

[0361]

[Equation 1] Given in. here,

[0362]

[Equation 2]

Then, the phase difference between adjacent reflected and transmitted waves is 2
δ ₁ . According to Stokes' theorem, the traveling direction of light is calculated from the forward Fresnel coefficient and the backward Fresnel coefficient (represented by dashes).

[0364]

[Equation 3] The relationship is established. Therefore,

[0365]

[Equation 4] Is expressed as

In order to obtain the reflectance of the multilayer film, the Fresnel coefficients at the two front and rear boundaries of the final layer L are used to calculate the multiple interference as described above, and it is regarded as one virtual boundary. Sequential calculation is performed toward the upper layer with _RL as an effective Fresnel coefficient. That is,

[0367]

[Equation 5]

The complex reflectance in the final layer is
By the above calculation method with the final layer as a single layer film,

[0369]

[Equation 6]

[0370] Similarly, for j layer,

[0371]

[Equation 7]

Since it can be expressed as follows, the reflectance in the multilayer film can be calculated by sequentially calculating from the final layer to the first layer.

For example, the polycarbonate substrate 1 shown in FIG. 3, the silver reflection film 2 having a film thickness of 15 nm, (n, k) = (1.
(95, 0.15) organic dye recording film 3 (thickness is a variable parameter), a SiO ₂ protective film 4 having a film thickness of 30 nm, and a light transmission layer 8 of polycarbonate are sequentially formed on the light transmission layer side. FIG. 5 shows an example of calculating the reflectance in the case of recording and reproducing from. For example, the film thickness of the organic dye recording film 3 is 80
In the case of nm, the initial reflectance before recording is 15%, and when the refractive index n of the organic dye film after recording is 1.7, the reflectance is 8%.
Therefore, the modulation factor = (initial reflectance-reflectance after recording) / initial reflectance = 47%, the organic dye film thickness of the low reflectance type medium structure suitable for high-to-low recording is determined. It In the case of the high reflectance type, the structure is such that the thickness of the silver reflective film is thicker, and when performing low-to-high recording, the film structure is different, but optimization is possible by the same calculation method.

Although the present invention is shown as a rewritable type,
As long as the erasing operation is not performed, the recording / reproducing method and the form of the recording medium are not different from the conventional write-once type optical recording medium and are effective as a write-once type optical recording medium for recording only once. Therefore, it is possible to ensure high compatibility with the conventional one.

[0375]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1

This example is an example of a DVD using a blue laser having a wavelength λ = 405 nm.

A polycarbonate substrate having a thickness of 0.6 mm and an outer diameter of 120 mm was manufactured by injection molding from a stamper master having a groove shape having a pitch of 0.6 μm, a groove depth of 50 nm and a groove width of 0.28 μm. The film structure in this example is as shown in FIG. A tetraazaporphyrin dye "Tetra-t-butyl-5,10,15,20-tetraazaporphyrinoxovanadium (IV)" represented by the general formula (A) is formed on the substrate as a recording layer 2 by a vacuum deposition method. Then, a film having a thickness of 60 nm was formed on the groove. The refractive index and the absorption coefficient of the recording layer 2 were n = 1.8 and k = 0.05 at 405 nm. Then, a 100 nm thick silver reflective layer 3 is formed on the recording layer by a sputtering method, and then a UV curable resin "SD17" (manufactured by Dainippon Ink and Chemicals) is spin-coated on the reflective layer 3. A film having a thickness of about 3 μm is formed as a protective film 4, and U is formed thereon.
A V-adhesive was applied, and a dummy substrate (made of polycarbonate) having a thickness of 0.6 mm was attached thereto to manufacture an optical recording medium having the same outer shape as the DVD. At this time, the initial reflectance of the disc is 2
It was 3%.

This recording medium was measured by an optical disk evaluation apparatus equipped with a blue-violet laser manufactured by Pulstec Industrial Co., Ltd., and a simple repeated signal corresponding to a groove with a pit length of 0.5 μm was transmitted through a polycarbonate substrate at a wavelength of 405 nm and NA = 0.
65, linear velocity = 3.5 m / s, recording power = 8.5 mW
It was recorded under the conditions. Playback power of the recording unit = 0.5 mW
When regenerated by C., C / N = 59 dB was obtained. Figure 6
Is the RF signal output of this recording pattern.

After recording, the track is erased with a power of 3.7.
When erased with mW continuous (DC) light, the amount of unerased signal was C / N = 43 dB, and an erase ratio of 15 dB was obtained. FIG. 7 shows the RF signal output at this time. Some erasure can be seen. Further, when re-recording was performed on the same track under the same conditions as the above-mentioned recording, C / N = 56 dB was obtained. FIG. 8 shows the RF signal output at this time. This recording / erasing was repeated 20 times on the same track and the rewriting characteristics were evaluated. As a result, almost the same C / N value was obtained.

[0380]

[Chemical 30]

Example 2

This example is also an example of a DVD using a blue laser having a wavelength λ = 405 nm.

The same substrate as in Example 1, organic dye recording film,
A silver reflective film and a protective film were used. The film structure in this example is shown in FIG. The difference from Example 1 is that SiO ₂ having a film thickness of 30 nm is formed between the substrate 1 and the recording film 3 and between the recording film 3 and the reflective film 5 by a sputtering method, respectively.
That is, it is formed as. The initial reflectance of the disk was 12%, which almost coincided with the calculated value.

A simple repetitive signal corresponding to a pit length of 0.5 μm was recorded under the same conditions as in Example 1.

When the recording portion was reproduced at reproduction power = 0.5 mW, a CN ratio = 52 dB was confirmed. FIG. 9 shows the RF signal output for this recording pattern.

After recording, the track is erased with a power of 3.7.
When erased with mW continuous (DC) light, the amount of unerased signal was C / N = 19 dB, and an erase ratio of 32 dB was obtained. FIG. 10 shows the RF signal output at this time, and it can be seen that the RF signal is almost completely erased. Further, when re-recording was performed on the same track under the same conditions as the above-mentioned recording, C / N = 5
1 dB was obtained. FIG. 11 shows the RF for this recording pattern.
It is a signal output. This recording / erasing can be done on the same track
When the rewriting characteristic was evaluated repeatedly, the signal deterioration hardly occurred and the C / N was secured at 51 dB.
As can be seen from FIG. 12, almost no signal deterioration is observed. Both sides of the recording film have a hard dielectric (Si in this example is Si).
It is considered that the inclusion of O ₂ ) causes the deformation to occur only in the organic dye recording film, suppresses the influence on the substrate and the reflective film, and improves the rewriting performance repeatedly. 21A, 21B, and 21C show the deformation traces on the dye layer side when the peeling interface between the substrate-side SiO ₂ dielectric layer and the dye layer after recording, erasing, and re-recording is observed by SEM. Further, FIG. 21D shows an SEM observation image of the interface on the SiO ₂ dielectric layer side after recording. It should be noted that almost no deformation traces remained on the surface of the SiO ₂ dielectric layer adjacent to the dye layer, and dome-shaped void traces were recognized only in the recording area in the dye layer. Is. Moreover, it can be directly observed that the dome-shaped deformation mark is smoothed by the erasing operation by the laser. The surface of the substrate-side SiO ₂ dielectric layer did not change after erasing and re-recording.

Example 3

This example is an example of a DVR (optical disk for recording / reproducing through a light transmitting layer having a thickness of 10 to 177 μm) using a blue laser having a wavelength λ = 405 nm.

FIG. 3 shows a recording medium which can be satisfactorily recorded and reproduced by an optical system having a wavelength of 405 nm and NA = 0.85.
An example of the film configuration of is shown. Here, the polycarbonate substrate 1
A guide groove having a track pitch of 0.64 .mu.m is formed on the track, and its width is set to about 50% so that recording can be performed on both the land and the groove. That is, the actual track pitch is 0.32 μm. The groove depth is 40
nm. On top of this, a reflection film 2 of a silver alloy with a thickness of 12 nm
Of the diazaporphyrin dye represented by the following general formula (B) as the organic dye film 3
8,12,18-Tetraethyl-3,7,13,17-
Tetramethyl-5,15-diazaporphyrin copper (I
I) ”was used to form the film by a vacuum vapor deposition method.

[0391]

[Chemical 31]

The organic dye film 3 has a film thickness of 75 nm, and its optical constants are such that the refractive index n = 1.9 and k = 0.15.
Met. As the transparent protective layer 7, SiO having a thickness of 30 nm is used.
₂ was deposited by the sputtering method. The purpose of this film is to increase the hardness of the surface and to improve the repetitive recording characteristics, but it may be regarded here as a protection of the recording film. The light transmission layer has a thickness of 100 μm as described above.
This layer was formed by laminating a polycarbonate sheet using a pressure sensitive adhesive (PSA), and the total thickness of these layers was set to 100 μm.

The initial reflectance of the optical disc thus prepared was 14%, which is close to the calculated design value. The recording was performed with a linear velocity of 5.72 m / s, a reproducing light power of 0.3 mW, and a recording pattern of a single carrier having a mark length of 0.35 μm.
For recording a single mark, seven pulse trains of the same width were incident at a pulse / space ratio of 50%, the peak power was 6.0 mW, and the C / N was measured with a spectrum analyzer.
The characteristics of the media were evaluated by measuring the BW at 30 kHz. Mentioned above

In the case of an optical recording medium, a value of 45 dB was obtained as a result of the above recording / reproducing experiment. FIG. 13 shows the RF signal output for this recording pattern.

After recording, the track is erased with a power of 3.0.
When erased twice with mW continuous (DC) light, the amount of unerased signal was C / N = 10 dB, and an erase ratio of 32 dB was obtained. FIG. 14 shows the RF signal output at that time. Further, when re-recording was performed on the same track under the same conditions as the above-mentioned recording, a C / N value of 43 dB was obtained. FIG. 15 shows the RF signal output at that time. This recording / erasing was repeated 10 times on the same track to evaluate the rewriting characteristics, but it was possible to always secure a C / N of 43 dB.

The recording mark length of the disc is 0.17.
The C / N value in the single carrier wave recording of 3 μm was 42 dB, and the C / N value in the single carrier wave recording of the recording mark length of 0.173 μm was 51 dB. Furthermore, the shortest mark length is 0.38 μm
When a random pattern recording with the (1,7) code is performed, an eye pattern as shown in FIG. 16 is obtained.

Example 4

This example is also an example of a DVR (optical disk for recording / reproducing through a light transmission layer having a thickness of 10 to 177 μm) using a blue laser having a wavelength λ = 405 nm.

The same polycarbonate substrate as in Example 3 was used. The membrane configuration for this example is as shown in Figure 17:

Polycarbonate substrate (1) / dielectric film 1
(9) / dielectric film 2 (10) / organic dye recording film (3) / transparent protective layer (7) / light transmitting layer (8).

Si having a film thickness of 60 nm is formed on the substrate 1.₃N_Four(N
= 2.0), SiO with a film thickness of 60 nm ₂(N = 1.46)
Nitrogen gas and oxygen gas are sputtered with argon.
Mix a proper amount of gas with a silicon target
The layers were sequentially laminated by the reactive sputtering method used. these
The film protects the organic dye recording layer and the recording marks are deformed on the substrate side.
Recording layer, which will be described later, together with the function of not affecting
With the film structure including the transparent protective layer, the initial reflectance of the disk is
Complies with the standard (15% to 25 for DVR-Blue)
%).

Further, as a recording layer, a monoazaporphyrin dye represented by the following general formula (C) "2,3,7,8,1" is used.
3,17-hexaethyl-12,18-dimethyl-5-
"Azaporphyrin copper (II)" was formed into a film having a thickness of 50 nm by a vacuum evaporation method. The refractive index and absorption coefficient of the recording layer are n = 2.1 and k = 0.1 at 400 nm.
Met. Subsequently, a Si film having a thickness of 30 nm is formed on the recording layer.
An O ₂ transparent protective layer was formed by sputtering. The rest is the same as in the third embodiment.

[0403]

[Chemical 32]

In the optical disk thus produced, multiple reflection occurs without using a metal reflection film, and the reflectance at the light source of 405 nm has a value that matches the designed value of about 20%. .

Recording was performed with a linear velocity of 5.72 m / s, a reproducing light power of 0.3 mW, and a recording pattern of a single carrier having a mark length of 0.35 μm. Also, 7 is required for recording a single mark.
Pulse trains of the same width were made incident at a pulse / space ratio of 50%, peak power was set to 5.0 mW, and C / N was measured with a spectrum analyzer at RBW of 30 kHz to evaluate the characteristics of the medium. In the case of the optical recording medium described above, a value of 48 dB was obtained as a result of the above recording / reproducing experiment. After recording, erase the track with an erase power of 3.0
When erased with mW continuous (DC) light, the amount of unerased signal was C / N = 25 dB, and an erase ratio of 23 dB was obtained. Further, when re-recording was performed on the same track under the same conditions as the above-mentioned recording, a C / N value of 48 dB was obtained. This recording / erasing was repeated 10 times on the same track, and the rewriting characteristics were evaluated. A C / N value change of 1 dB or less was slightly observed up to the first 3 times, but finally the C / N value was 48 dB. We were able to secure N.

Example 5

The present example is an example of a DVD using a red laser having a wavelength λ = 658 nm.

The recording medium obtained in Example 1 was used. However, the recording film was formed by forming a tetraazaporphyrin dye on the substrate by a spin coating method using an ethylcyclohexane solution (20 g / l) so that the film thickness was 90 nm on the groove. The guide groove of the substrate has a track pitch of 0.74 μm, a width of 0.33 μm, and a groove depth of 150 nm. The refractive index and absorption coefficient of the recording layer were n = 2.1 and k = 0.05. Subsequently, a SiO ₂ transparent protective layer having a thickness of 30 nm is formed on the recording layer by a sputtering method, and a thickness of 100 nm is further formed.
nm reflective layer of silver is formed by sputtering method, and then UV curable resin "Product name SD17" is formed on the reflective layer.
(Dai Nippon Ink Co., Ltd.) is formed by spin coating to a thickness of about 3 μm as a protective film, and a UV adhesive is applied on it to form a dummy substrate (made of polycarbonate) with a thickness of 0.6 mm.
Were bonded together to produce an optical recording medium having the same outer shape as the DVD. At this time, the initial reflectance of the disc was 47%. An optical disk evaluation device equipped with a red laser manufactured by Pulstec Industrial Co., Ltd., a simple repetition signal corresponding to a pit length of 0.8 μm was formed on a groove through a polycarbonate substrate at wavelength 6
Recording was performed under the conditions of 58 nm, NA = 0.60, linear velocity = 3.5 m / s, and recording power = 9 mW. When the recording portion was reproduced with reproduction power = 0.5 mW, C / N = 58 dB
was gotten.

[0409] After recording, the track is erased with an erasing power of 4 mW.
After erasing with continuous (DC) light, the amount of unerased signal was C / N = 30 dB, and an erasing ratio of 28 dB was obtained. Further, when re-recording was performed on the same track under the same conditions as the above-mentioned recording, C / N = 55 dB was obtained. This recording / erasing was repeated 20 times on the same track to evaluate rewriting characteristics, but almost no signal deterioration was observed.

Example 6

This example is also an example of a CD using an infrared laser having a wavelength λ = 780 nm.

The guide groove has a track pitch of 0.74 μm, a width of 0.33 μm, and a groove depth of 170 nm, and a thickness of 30
nm SiO ₂ transparent protective layer by sputtering,
Then, a phthalocyanine dye was formed into a film having a thickness of 100 nm on the groove by a spin coating method using an ethylcyclohexane solution (20 g / l). The refractive index and absorption coefficient of the recording layer were n = 2.2 and k = 0.1. Further, a silver reflection layer having a thickness of 100 nm is formed by a sputtering method, and then a UV curable resin “SD17” (manufactured by Dainippon Ink and Chemicals, Inc.) is formed on the reflection layer by a spin coating method to a thickness of about 3 μm. It was used as a protective film. At this time, the initial reflectance of the disc was 68%. An optical disk evaluation device equipped with a near-red laser manufactured by Pulstec Industrial Co., Ltd., a simple repeating signal corresponding to a pit length of 1.2 μm in a groove through a polycarbonate substrate, with a wavelength of 781 nm and NA =
0.50, linear velocity = 2.4 m / s, recording power = 10.
It was recorded under the condition of 5 mW. Playback power of the recording unit = 0.
When reproduced at 7 mW, C / N = 57 dB was obtained. FIG. 18 shows the RF signal output at that time.

After recording, the track is erased with an erasing power of 3 mW.
When erased with continuous (DC) light, the amount of unerased signal was C / N = 33 dB, and an erase ratio of 24 dB was obtained. FIG. 19 shows the RF signal output at that time. Further, when re-recording was performed on the same track under the same conditions as the above-mentioned recording, C / N = 54 dB was obtained. FIG. 20 shows the RF signal output at that time. This recording / erasing was repeated 20 times on the same track to evaluate rewriting characteristics, but almost no signal deterioration was observed.

[0414]

As is apparent from the above description, according to the present invention, laser light of the same wavelength can be used in recording / reproducing / erasing operations, and one laser light source, particularly a small and lightweight laser diode is used. A rewritable optical information recording medium can be provided by a simple recording / reproducing apparatus equipped with the. In particular, the conventional CD-RW drive and DVD-RW drive can be used as they are as the recording / reproducing apparatus for the optical recording medium of the present invention. Furthermore, CD-R drive or DVD
-It can be used in the same way only by adding an erasing function to the R drive. No need for complicated signal detection such as polarization optics. Further, since recording / reproducing / erasing operations can be performed with different laser wavelengths, it can be applied to a mixed drive of CD and DVD.

In the optical recording medium of the present invention, the recording layer is composed of the thin organic dye thin film itself uniformly formed and is changed by laser irradiation, so that the noise level is sufficiently low and the high optical modulation degree (contrast) is obtained. That is, it has a high C / N value. Azaannulene compounds used in the optical recording medium of the present invention, in particular, phthalocyanine-based, naphthalocyanine-based, mono- or tetraazaporphyrin-based azaporphyrins and porphyrins and metal complexes thereof,
The optical absorption spectrum can be adjusted according to the laser wavelength used, and an optical recording medium suitable for a recording / reproducing apparatus using semiconductor lasers of various wavelengths can be provided. In particular, in order to increase the recording density, an optical recording medium adapted to a short wavelength laser such as an ultraviolet / blue-violet laser is possible.

By using optical multiple reflection in combination with a dielectric protection film and a reflection film, the reflectance before and after recording can be easily set, and the recording method can be freely selected. Both land / groove recording and in-groove recording can be performed by using a substrate having an appropriate guide groove. Further, both substrate reading and front surface reading are possible. Therefore, high reflectance type, low reflectance type, or High
Existing CDs, DVDs such as -to-Low and Low-to-High recording
And next-generation optical discs (so-called DVR-Blue, DV
It is possible to provide an optical recording medium completely compatible with D-Blue) and the like.

Further, it is possible to provide an inexpensive optical recording medium having a simple film structure, uniform characteristics and reproducibility, high light resistance and weather resistance, high reliability, and low manufacturing cost. .

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a basic configuration example of a CD-R or DVD-R optical information recording medium.

FIG. 2 is a schematic cross-sectional view showing another configuration example of the optical information recording medium according to the present invention.

FIG. 3 is a schematic cross-sectional view showing the basic configuration of an optical information recording medium for recording / reproducing via a light transmitting layer.

FIG. 4 is an explanatory diagram of a reflectance calculation method of an optical recording medium in consideration of optical multiple reflection of a multilayer thin film.

5 is an example of calculation of reflectance in the specific example of the configuration of FIG.

FIG. 6 is a waveform diagram showing a signal waveform (oscilloscope image) of initial recording in Example 1.

FIG. 7 is a waveform diagram showing a signal waveform (an oscilloscope image) after erasing in the first embodiment.

FIG. 8 is a waveform diagram showing a signal waveform (an oscilloscope image) at the time of re-recording in Example 1.

FIG. 9 is a waveform diagram showing a signal waveform (oscilloscope image) of initial recording in Example 2.

FIG. 10 is a waveform diagram showing a signal waveform (oscilloscope image) after erasing in the second embodiment.

FIG. 11 is a waveform diagram showing a signal waveform (an oscilloscope image) at the time of re-recording in the second embodiment.

FIG. 12 is a waveform diagram showing a signal waveform (an oscilloscope image) after recording and erasing 20 times repeatedly in Example 2.

FIG. 13 is a waveform diagram showing a signal waveform (oscilloscope image) of initial recording in Example 3;

FIG. 14 is a waveform diagram showing a signal waveform (an oscilloscope image) after erasing in the third embodiment.

FIG. 15 is a waveform diagram showing a signal waveform (an oscilloscope image) at the time of re-recording in Example 3.

FIG. 16 is a waveform diagram showing an initial recording eye pattern (an oscilloscope image) in Example 3.

FIG. 17 is a schematic sectional view of an optical information recording medium of Example 4.

FIG. 18 is a waveform diagram showing a signal waveform (oscilloscope image) of initial recording in Example 5.

FIG. 19 is a waveform diagram showing a signal waveform (an oscilloscope image) after erasing in the fifth embodiment.

FIG. 20 is a waveform diagram showing a signal waveform (an oscilloscope image) at the time of re-recording in Example 5.

FIG. 21 is a photograph showing a deformation trace on the dye layer side when SEM observation of the peeling interface between the substrate-side dielectric layer and the dye layer after recording A is performed. It is a photograph showing a deformation trace on the dye layer side when the peeling interface between the dielectric layer on the substrate side and the dye layer is observed by SEM after B erasing. 6 is a photograph showing a trace of deformation on the dye layer side when SEM observation of the peeling interface between the substrate-side dielectric layer and the dye layer after C re-recording. 6 is a photograph showing an SEM observation image of the surface of the dielectric layer when the peeling interface between the substrate-side dielectric layer and the dye layer is observed by SEM after D recording.

[Explanation of symbols]

1 substrate, 2 recording layer, 3 reflective layer, 4 protective film,
5, 6, 7 Transparent protective layer, 8 Light transmission layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G11B 7/24 G11B 7/24 534M B41M 5/26 7/0045 Z G11B 7/0045 C09B 47/00 // C09B 47/00 B41M 5/26 Y (72) Inventor Takashi Iwamura 6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo Inside Sony Corporation (72) Inventor Yuichi Sahi, 6-7 Kita-Shinagawa, Shinagawa-ku, Tokyo No. 35 Sony Corporation (72) Inventor Mitsuaki Oyamada 6-7 Kita-Shinagawa, Shinagawa-ku, Tokyo No. 35 Sony Corporation (72) Inventor Masanobu Yamamoto 6-7 Kita-Shinagawa, Shinagawa-ku, Tokyo No. 35 Sony Corporation (72) Inventor Masashi Koike 580-32 Nagaura Mitsui Chemical Co., Ltd., Sodegaura City, Chiba Prefecture In-company (72) Denmi Misawa 580-32 Nagaura Megumi Sodegaura City, Chiba Mitsui Chemical Co., Ltd. (72) Inventor Akira Ogiso Mitsui Chemicals Co., Ltd. 580-32 Nagaura, Sodegaura City, Chiba Prefecture (72) Inventor Ryosuke Nara 580-32 Nagaura, Sodegaura City, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Atsushi Tokuhiro 580-32 Nagaura, Sodegaura City, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor U Tsukahara 580-32 Nagaura, Sodegaura City, Chiba Mitsui Chemicals Co., Ltd. F-term (reference) 2H111 EA04 EA21 EA23 EA32 EA43 FA14 FA25 FA27 FA28 FB42 FB45 5D029 JA04 JB22 LA14 LA15 LA16 LB01 LB02 5D090 AA01 BB07 CC01 DD01 KK06

Claims (17)

[Claims] 1. A recording film having at least one light-absorbing organic compound film substantially consisting of at least one or more light-absorbing organic compounds (including those having a metal complex).
A rewritable optical information recording medium, wherein information is recorded and erased by a reversible physical change associated with laser light irradiation of the compound film alone. 2. The rewritable optical information recording medium according to claim 1, wherein the physical change is a shape change. 3. Data recording is performed by a local physical change caused by irradiation of a recording laser beam, and data reproduction is performed by detecting a change in return light intensity of a reproducing laser beam having a power smaller than that of the recording laser beam. Data erasing is performed by irradiating continuous light or pulsed light having a laser power larger than the power of the reproduction laser light and smaller than the power of the recording laser light at least once. 1. The rewritable optical information recording medium described in 1. 4. The light absorbing organic compound has a wavelength of 350 n.
The rewritable optical information recording medium according to claim 1, wherein the rewritable optical information recording medium is an organic dye compound that absorbs at least one kind of light having a wavelength selected from m to 850 nm. 5. The light-absorbing organic compound has a molecular weight of 300.
The rewritable optical information recording medium according to claim 1, wherein the rewritable optical information recording medium is an organic dye compound of less than 0. 6. The rewritable optical information recording medium according to claim 4, wherein the organic dye compound is selected from at least one kind of an azaannulene compound (including one having a metal complex). 7. The laser light used for recording / reproducing / erasing has a wavelength in the range of 350 nm to 450 nm, and the organic dye compound is an azaannulene compound represented by the following general formula (1). Item 6. A rewritable optical information recording medium according to item 6. [Chemical 1] [Wherein, R ^{1 to} R ¹⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group , A substituted or unsubstituted mercapto group, X ^{1 to} X ⁸ each independently represent a nitrogen atom or a substituted or unsubstituted methine group, and R ^{1 to} R ¹⁶ and each substituent on the methine group are linking groups. Carbon atoms in a substituted or unsubstituted hydrocarbon group, a hydrocarbon group-substituted hydroxyl group, a hydrocarbon group-substituted mercapto group, and / or a hydrocarbon group-substituted amino group, which may be bonded together. -A carbon atom may have an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom. Further, n represents 0 or 1, and when n is 0, M
Represents a divalent metal atom which may have a ligand, or a trivalent or tetravalent metal atom or a semimetal atom having a substituent and / or a ligand, and when n is 1,
M represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom. ] 8. A laser beam used for recording / reproducing / erasing
Is in the range of 350 nm to 450 nm,
The organic pigment compound is tetraaza represented by the following general formula (2).
The porphyrin compound according to claim 7, which is a porphyrin compound.
Rewritable optical information recording medium. [Chemical 2] [In the formula, R¹⁷~ R^{twenty four}Are each independently a hydrogen atom, halo
Gen atom, nitro group, cyano group, substituted or unsubstituted charcoal
Hydrogen group, substituted or unsubstituted hydroxy group, substituted or
Is an unsubstituted amino group, a substituted or unsubstituted mercapto group
Represents R¹⁷~ R ^{twenty four}Each substituent of is tetraazaporphyri
Linked together via each substituent on the ring and the linking group.
May combine to form an aliphatic ring, which may be substituted or absent
Substituted hydrocarbon group, Hydrocarbon group substituted hydroxyl group, charcoal
Hydrogen group substituted mercapto group and / or hydrocarbon group
Oxygen atom, sulfur between carbon-carbon atoms in the substituted amino group
May have an atom, a substituted or unsubstituted nitrogen atom
Yes. M¹Is a divalent metal atom which may have a ligand.
Ruvalent or trivalent with substituents and / or ligands
Represents a tetravalent metal atom or a metalloid atom. ] 9. The laser light used for recording / reproducing / erasing has a wavelength in the range of 600 nm to 700 nm, and the organic dye compound is an azaannulene compound represented by the following general formula (3). Item 6. A rewritable optical information recording medium according to item 6. [Chemical 3] [Wherein, R ^{25 to} R ⁴⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group represents a substituted or unsubstituted mercapto group, a X ⁹ to X ^{1 6} are each independently a substituted or unsubstituted methine group having any of the groups or atoms represented by nitrogen atom or or R ¹ to R ¹⁶ Represents R ^{25 to} R
⁴⁰ and each substituent on the methine group may be bonded together via a linking group to form an aliphatic ring,
In a substituted or unsubstituted hydrocarbon group, a hydrocarbon group-substituted hydroxyl group, a hydrocarbon group-substituted mercapto group, and / or a carbon group in a hydrocarbon group-substituted amino group,
It may have an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom. Further, n represents 0 or 1, and when n is 0, M ² is a trivalent or tetravalent metal atom having a divalent metal atom which may have a ligand or a substituent and / or a ligand. In the formula (1), M ² represents a trivalent metal atom and one hydrogen atom, or a tetravalent metal atom when n is 1. ] 10. A laser beam used for recording / reproducing / erasing has a wavelength in the range of 600 nm to 700 nm, and the organic dye compound is a tetraazaporphyrin compound represented by the general formula (2). The rewritable optical information recording medium according to claim 6. 11. A laser used for recording / reproducing / erasing.
The wavelength of light is in the range of 750 nm to 850 nm, and
The organic dye compound is phthalocyanine represented by the following general formula (4)
7. The writing according to claim 6, which is a nin compound.
Replaceable optical information recording medium. [Chemical 4] [In the formula, R⁴¹~ R⁷²Are each independently a hydrogen atom, halo
Gen atom, nitro group, cyano group, substituted or unsubstituted charcoal
Hydrogen group, substituted or unsubstituted hydroxy group, substituted or
Is an unsubstituted amino group, a substituted or unsubstituted mercapto group
Represents R⁴¹~ R ⁷²And each substituent on the methine group is linked
May be bonded together through a group,
Or a hydrocarbon group substituted with a hydrocarbon group in an unsubstituted hydrocarbon group
Sil group, hydrocarbon group-substituted mercapto group, and / or
Oxygen between carbon atoms in a hydrocarbon-substituted amino group
Having atoms, sulfur atoms, substituted or unsubstituted nitrogen atoms
You may stay. n represents 0 or 1, and when n is 0, M
³Is a divalent metal atom which may have a ligand, or
Trivalent or tetravalent having a substituent and / or a ligand
Represents a metal atom or a metalloid atom of n, and when n is 1, M³Is
Trivalent metal atom and one hydrogen atom, or tetravalent metal
Represents an atom. ] 12. The rewritable according to claim 1, further comprising a transparent protective layer between the light-absorbing organic compound recording film and the substrate or adjacent to one side or both sides of the light-absorbing organic compound recording film. Optical recording medium. 13. The rewritable optical information recording medium according to claim 12, wherein the transparent protective layer is made of at least one selected from inorganic sulfides, inorganic oxides, and inorganic nitrides. 14. A rewritable optical information recording medium having one or more layers of a light-absorbing organic compound film substantially consisting of at least one or more light-absorbing organic compound as a recording film is used, and the laser of the organic dye film alone is used. A recording / reproducing method characterized in that information is recorded and erased by a reversible physical change associated with light irradiation. 15. A rewritable optical information recording medium having one or more layers as a light-absorbing organic compound film consisting essentially of at least one light-absorbing organic compound, and irradiating a recording laser beam to the organic dye film. Data recording is performed by causing a local physical change in a single body, and data reproduction is performed by detecting a change in return light intensity of a reproduction laser beam having a power smaller than that of the recording laser beam, and
By irradiating continuous light or pulsed light having a laser power higher than the power of the reproduction laser light and lower than the power of the recording laser light at least once, the physical change is eliminated and data is erased. The recording / reproducing method according to claim 14. 16. The recording / reproducing method according to claim 14, wherein the physical change is a shape change. 17. A rewritable optical information recording medium having one or more layers of a light-absorbing organic compound film, which substantially consists of at least one or more light-absorbing organic compound, as a recording film. The recording / reproducing apparatus is characterized in that information is recorded and erased by a reversible physical change associated with the laser light irradiation.