KR20070021019A - Novel oxonol compound and process for producing the compound - Google Patents

Abstract

A compound represented by formula (I) as defined herein, a compound represented by formula (II) as defined herein, and a compound represented by formula (III) as defined herein, and represented by formula (IV) as defined herein A process for preparing a compound represented by formula (I), comprising the step of reacting a losing compound.

Description

New oxonol compound and its manufacturing method {NOVEL OXONOL COMPOUND AND PROCESS FOR PRODUCING THE COMPOUND}

The present invention relates to compounds useful as intermediates for oxonol dyes and methods of preparing such compounds. More specifically, the present invention is useful as an intermediate for an oxanol dye used in a heat mode type information recording medium on which information is recorded with visible laser light, represented by a recordable digital multifunction disk (DVD-R). It relates to a compound and a method for preparing the compound.

BACKGROUND ART An information recording medium (optical disk) capable of recording information only once by laser light is known. Such an information recording medium called a recordable CD (referred to as CD-R) has an advantage that a small amount of the CD can be quickly provided at a reasonable price, compared to the production of a conventional CD. The demand for such CDs is increasing due to the recent spread of personal computers. A typical structure of a CD-R type information recording medium is obtained by laminating a transparent disk substrate and a protective layer made of a recording layer containing an organic dye, a reflective layer containing a metal such as gold, and a resin in this order.

The information recorded on such an optical disk is achieved by irradiating the disk locally with laser light in the near infrared region (generally, laser light having a wavelength around 780 nm) and locally heating the film, and deforming the recording layer. On the other hand, in general, information reading (reproducing) is performed by irradiating a disk with a laser light having the same wavelength as the laser light used for recording, between an area (recording area) of a thermally deformed recording layer and an undeformed area (unrecorded area). This is done by detecting the difference in reflectance.

In recent years, an information recording medium having a high recording density has been demanded. In order to increase the recording density, it is effective to reduce the diameter of the laser beam that irradiates the recording medium. The shorter the wavelength of the laser light, the narrower the laser beam is, so it is theoretically known that laser light having a short wavelength is advantageous for increasing the density. Thus, an optical disc capable of recording / reproducing with laser light having a wavelength of less than 780 nm, which has been conventionally used, has been developed. For example, optical discs called recordable digital video discs (called DVD-Rs) are commercially available. The optical disc has a pregrove with a track pitch of 0.8 μm narrower than 1.6 μm for CD-R, and forms a recording layer containing dye on a transparent disc substrate having a diameter of 120 mm or 80 mm, and generally A reflective layer and a protective layer are further formed on the recording layer, and the same disk as the obtained disk or a disk-shaped protective substrate of the same size as the disk is adhered with an adhesive with the recording layer inward. In the DVD-R, recording and reproducing are performed by irradiation with visible laser light (generally, laser light having a wavelength in the range of 600 to 700 nm), which enables higher density recording than a CD-R type optical disk.

JP-A-63-209995 discloses a CD-R type information recording medium in which a recording layer containing an oxonol dye is formed on a substrate. The use of the dye compound has been described an effect that can stably maintain the recording / playback characteristics over a long period of time. The oxonol dye compounds have ammonium in the form of salts incorporated into the molecule. On the other hand, JP-A-2000-52658 describes an oxonol dye compound which exhibits high light resistance and durability, and provides an optical information recording medium having satisfactory recording characteristics.

Typical oxonol dye moieties can be synthesized by the condensation reaction of a methine source (a compound used to combine one or more methine groups in methine dye synthesis) with a corresponding active methylene compound. Such dyes are JP-B-39-22069, JP-B-43-3504, JP-B-52-38056, JP-B-54-38129, JP-B-55-10059, JP- B-58-35544, JP-A-49-99620, JP-A-52-92716, JP-A-59-16834, JP-A-63-316853 (US Pat. No. 4,920,031), JP-A-64-40827, British Patent 1,133,986, US Patent 3,247,127, US Patent 4,042,397, US Patent 4,181,225, US Patent 5,213,956, US Patent 5,260,179, International Publication No. 02 / 080161, JP-A-63-209995 and JP-A-2-62279.

Although compounds with specific structures are described in "Collection of Czechoslovak Chemical Communications, 1911-1938, 65, 12, 2000", this prior art is not relevant to the present invention.

The present inventors studied the method of synthesizing an oxonol dye compound. As a result, it was found that the compounds of the present invention are useful intermediates for the oxonol dyes, which are preferred dyes for use in DVD-R. The present invention is accomplished based on this finding. The compounds of the present invention are particularly useful for synthesizing oxonol dyes obtained by dimerization, in which two chromophores are bonded to linkers by covalent bonds.

SUMMARY OF THE INVENTION An object of the present invention is to provide a compound capable of synthesizing an oxonol dye that maintains sufficient recording characteristics and realizes high reflectivity and high modulus even at high recording speeds of four times or more. The dye has a complex refractive index with a large real part n, with an imaginary part k being almost equal to or less than this. In addition, the osonol dye derived from the compound of the present invention achieves sufficiently low jitter at a wide range of recording speeds of 1 to 16 times the speed.

The object of the present invention can be advantageously achieved with the following configuration.

(1) A compound represented by the following general formula (1).

R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; R ³ , R ⁴ , R ^6, and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; R ⁵ has a hydrogen atom, a halogen atom, or 1 to 10 carbon atoms A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 10 carbon atoms, or a substitution having 1 to 6 carbon atoms or Unsubstituted heterocyclic group; R ⁸ represents a hydrogen atom or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ^12, and R ¹³ each independently represent hydrogen. An atom or a substituent; And substituents R ¹ and R ² may be bonded to each other to form a ring (preferably a 6-membered ring such as cyclohexane).

(2) A compound represented by the following general formula (II).

R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; R ⁵ Is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted group having 2 to 10 carbon atoms An acylamino group of R 1, a substituted or unsubstituted hetero ring having 1 to 6 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ^12, and R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, and a cyano group , Nitro group, carboxyl group, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, substituted or unsubstituted having 2 to 10 carbon atoms Substituted acylamino group, 2-10 bullets Substituted or unsubstituted aminocarbonylamino group having an atom, substituted or unsubstituted alkoxycarbonylamino group having 2 to 10 carbon atoms, substituted or unsubstituted aryloxycarbonylamino group having 6 to 10 carbon atoms, Substituted or unsubstituted sulfamoyl group having 0 to 10 carbon atoms, Substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, Substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms , Substituted or unsubstituted acyl group having 2 to 10 carbon atoms, substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, Or a substituted or unsubstituted carbamoyl group having 1 to 10 carbon atoms, provided that substituents R ¹ and R ² are bonded to each other to form a ring (preferably a 6 membered ring such as cyclohexane) May be formed.)

(3) A process for producing a compound represented by the following general formula (I), comprising the step of reacting a compound represented by the following general formula (III) with a compound represented by the following general formula (IV).

R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; R ³ , R ⁴ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; R ⁵ represents a hydrogen atom, a halogen atom or 1 to 10 carbon atoms. Substituted or unsubstituted alkyl group having 6 to 10 carbon atoms, substituted or unsubstituted aryl group having 2 to 10 carbon atoms, substituted or unsubstituted acylamino group having 1 to 6 carbon atoms, or Unsubstituted heterocycle R ⁸ represents a hydrogen atom or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or Substituents, provided that substituents R ¹ and R ² may be bonded to each other to form a ring (preferably a six-membered ring such as cyclohexane).

The compounds of the present invention are completely new compounds, and when used for DVD-R, an oxonoline compound which exhibits excellent performance can be easily synthesized from the compound with satisfactory efficiency. Since the raw materials used are readily available and inexpensive, the compound of the present invention is a preferred intermediate from the viewpoint of industrial production.

Hereinafter, the present invention will be described in detail.

In the general formula, R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. . The substituents R ¹ and R ² may be bonded to each other to form a ring (preferably a 5 or 6 membered ring such as cyclohexane).

When R ¹ or R ² is substituted with one or more substituents, examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkoxy Neyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic-oxy group, acyloxy group, carbamoyloxy group, alkoxycarbo Nyloxy group, aryloxycarbonyloxy group, amino group (including anilino), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto, Alkylthio group, arylthio group, heterocyclic-thio group, sulfamoyl group, sulfo, alkyl- and arylsulfinyl group, alkyl- and arylsulfonyl group, acyl group, aryloxycarbonyl number, alkoxyka Beam group, a carbamoyl group, an aryl- include an azo group, an imide group, phosphino group, a phosphine group P, Phosphinicosuccinic group, amino group and silyl phosphinylmethyl - and heterocyclic.

More specifically, the substituents are halogen atoms (e.g. chlorine, bromine and iodine atoms), alkyl groups [i.e. alkyl groups (preferably alkyl groups having 1 to 10 carbon atoms, e.g. methyl, ethyl, n-propyl, Isopropyl, t-butyl, n-octyl, ecosyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl), cycloalkyl groups (preferably substituted or unsubstituted with 3 to 30 carbon atoms) Cycloalkyl groups such as cyclohexyl, cyclopentyl and 4-n-dodecylcyclohexyl), bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms, ie 5 to Monovalent groups formed by removing one hydrogen atom from a bicycloalkane having 30 carbon atoms; examples thereof include bicyclo [1.2.2] hept-2-yl and bicyclo [2.2.2] oct-3- Alkyl groups consisting of a plurality of rings such as Straight chain, branched, or substituted or unsubstituted alkyl group substituted on the ring that come; In addition, the alkyl group in the substituent described below (for example, the alkyl group in the alkylthio group) is an alkyl group having the same concept as above], an alkenyl group (that is, an alkenyl group (preferably having 2 to 30 carbon atoms or Unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl and oleyl), cycloalkenyl groups (preferably substituted or unsubstituted cycloalkenyl groups having 3 to 30 carbon atoms, ie, 3 to 3) Monovalent groups formed by removing one hydrogen atom from a cycloalkene having 30 carbon atoms; examples thereof include 2-cyclopenten-1-yl and 2-cyclohexen-1-yl) and bicycloalkenyl groups (A hydrogen atom is substituted from a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a bicycloalkene having one double bond. Removed Monovalent groups formed as examples of: straight chains comprising bicyclo [2.2.1] hept-2-en-1-yl and bicyclo [2.2.2] oct-2-en-4-yl), Branched or cyclic substituted or unsubstituted alkenyl groups], alkynyl groups (preferably substituted or unsubstituted alkynyl groups having 2 to 30 carbon atoms, such as ethynyl, propargyl and trimethylsilylethynyl) , Aryl groups (preferably substituted or unsubstituted aryl groups having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl and o-hexadecanoylaminophenyl), heterocycles Groups (preferably monovalent groups formed by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or nonaromatic heterocyclic compound, more preferably 5 having 3 to 30 carbon atoms Or a 6-membered aromatic heterocyclic group, examples of which include 2-furyl, 2-thienyl, 2-pyrimidinyl 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, e Oxy, isopropoxy, t-butoxy, n-octyloxy and 2-methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as , Phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy and 2-tetradecanoylaminophenoxy), silyloxy groups (preferably having from 3 to 20 carbon atoms Silyloxy groups such as trimethylsilyloxy and t-butyldimethylsilyloxy), heterocyclic-oxy groups (preferably substituted or unsubstituted heterocyclic-oxy groups having 2 to 30 carbon atoms, such as 1- Phenyltetrazolyl-5-oxy and 2-tetrahydropyranyloxy), acyloxy groups (preferably formyloxy, and 2 Substituted or unsubstituted alkylcarbonyloxy group having ˜30 carbon atoms and substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms such as acetyloxy, pivaloyloxy, stearyloxy , Benzoyloxy and p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms, such as N, N-dimethylcarba Moyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy and Nn-octylcarbamoyloxy), alkoxycarbonyloxy groups ( Preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy and n-octylcarbonyloxy ), An aryloxycarbonyloxy group (preferably having 7 to 30 carbon atoms Is a substituted or unsubstituted aryloxycarbonyloxy group such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy and pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably amino And substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms and substituted or unsubstituted arylamino groups having 6 to 30 carbon atoms such as methylamino, dimethylamino, anilino, N-methylanilino And diphenylamino), acylamino group (preferably substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms and substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as Formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino and 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (preferably 1 to 30) carbon Substituted or unsubstituted aminocarbonylamino groups having an atom such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino and morpholinocarbonylamino), alkoxy Carbonylamino groups (preferably substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octa Decyloxycarbonylamino and N-methylmethoxycarbonylamino), aryloxycarbonylamino groups (preferably substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms, such as phenoxycarbo Nylamino, p-chlorophenoxycarbonylamino and mn-octyloxyphenoxycarbonylamino), sulfamoylamino groups (preferably substituted or unsubstituted sulfas having 0 to 30 carbon atoms) Monoamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino and Nn-octylaminosulfonylamino), alkyl- and arylsulfonylamino groups (preferably substituted or unsubstituted with 1 to 30 carbon atoms) Substituted alkylsulfonylamino groups and substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichloro Phenylsulfonylamino and p-methylphenylsulfonylamino), mercapto, alkylthio groups (preferably substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as methylthio, ethylthio and n- Hexadecylthio), arylthio groups (preferably substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio and m-methoxyphenylthio), heterocycles -Thio groups (preferably 2-30 shots) Substituted or unsubstituted heterocyclic-thio groups having atoms, such as 2-benzothiazolylthio and 1-phenyltetrazol-5-ylthio, sulfamoyl groups (preferably having from 0 to 30 carbon atoms) Substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl and N- (N'-phenylcarbamoyl) sulfamoyl), sulfo, alkyl- and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms and 6 to 30 carbon atoms) Substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl and p-methylphenylsulfinyl), alkyl- and arylsulfonyl groups (preferably 1 to 30 carbon atoms) A substituted or unsubstituted alkylsulfonyl group having and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl and p-methylphenylsulfonyl), acyl groups (preferably formyl, and substituted or unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms, 7 to 7) A substituted or unsubstituted arylcarbonyl group having 30 carbon atoms, and a substituted or unsubstituted heterocyclic-carbonyl group having 4 to 30 carbon atoms, in which the heterocycle is bonded to a carbonyl group via a carbon atom, such as acetyl, pi Valoyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl and 2-furylcarbonyl), aryloxycarbonyl groups (preferably between 7 and 30 carbon atoms) Substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl and pt-butylphenoxycarbonyl), alkoxycarbonyl groups (preferably 2 to 30 carbons Substituted or unsubstituted alkoxycarbonyl groups having an atom such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl and n-octadecyloxycarbonyl), carbamoyl group (preferably 1 to 30) Or unsubstituted carbamoyl groups having 3 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl and N -(Methylsulfonyl) carbamoyl), aryl- and heterocyclo-azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms and substituted or unsubstituted having 3 to 30 carbon atoms) Heterocyclic-azo groups such as phenylazo, p-chlorophenylazo, and 5-ethylthio-1,3,4-thiadiazol-2-ylazo, and imide groups (preferably N-succinimido) And N-phthalimido), phosphino groups (preferably substituted or unsubstituted phosphino groups having 2 to 30 carbon atoms, for example, Dimethylphosphino, diphenylphosphino and methylphenoxyphosphino), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl) And diethoxyphosphinyl), phosphinyloxy groups (preferably substituted or unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy), Phosphinylamino groups (preferably substituted or unsubstituted phosphinylamino groups having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino and dimethylaminophosphinylamino) and silyl groups (preferably 3 to 30 carbons) Substituted or unsubstituted silyl groups having an atom such as trimethylsilyl, t-butyldimethylsilyl and phenyldimethylsilyl).

In the functional groups listed above, one having at least one hydrogen atom may be substituted with one of the groups listed. Examples of the functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specific examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl and benzoylaminosulfonyl.

Preferably, R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or represent a cyclohexane ring (substituents R ¹ and R ² are bonded to each other). More preferably, R ¹ and R ² are different and are each unsubstituted or have an alkoxycarbonyl group having 1 to 5 carbon atoms, having 1 to 5 carbon atoms Or an alkyl group having 1 to 5 carbon atoms substituted with an acyloxy group or an alkoxy group having 1 to 5 carbon atoms, or R ¹ and R ² form a cyclohexane ring.

R ³ , R ⁴ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. Preferably, R ³ , R ⁴ , R ⁶ and R ⁷ are each hydrogen atoms.

R ⁵ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted having 2 to 10 carbon atoms, or Unsubstituted acylamino group or a substituted or unsubstituted heterocyclic group having 1 to 6 carbon atoms. Preferably, R ⁵ is a hydrogen atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, or an unsubstituted aryl group having 6 to 10 carbon atoms. Most preferably R ⁵ is a hydrogen atom.

R ⁸ represents a hydrogen atom or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms. Preferably, R ⁸ is a hydrogen atom.

Examples of R ⁵ include the corresponding ones of the substituents listed above with respect to substituents for R ¹ and R ² .

R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent. Examples of such substituents include the substituents indicated above with respect to the substituents for R ¹ and R ² . Preferably, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, nitro, cyano, 2 to 10 carbon atoms A substituted or unsubstituted alkoxycarbonylamino group having an atom, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms. More preferably, R ⁹ to R ¹³ are each an hydrogen group, a halogen atom, a nitro or an alkyl group having 1 to 5 carbon atoms unsubstituted or substituted with one or more halogen atoms. Especially preferably, R <^9> -R <^13> is a hydrogen atom each.

It is preferable that the compound represented by general formula (I) has a structure represented by general formula (II). In formula (II), R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl having 6 to 10 carbon atoms. Group; R ⁵ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted having 2 to 10 carbon atoms, or Unsubstituted acylamino group or substituted or unsubstituted heterocyclic group having 1 to 6 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cyano group, a nitro group, a carboxyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, Substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, Substituted or unsubstituted acylamino group having 2 to 10 carbon atoms, Substituted or unsubstituted aminocarbonylamino group having 2 to 10 carbon atoms , Substituted or unsubstituted alkoxycarbonylamino group having 2 to 10 carbon atoms, substituted or unsubstituted aryloxycarbonylamino group having 6 to 10 carbon atoms, substituted or unsubstituted having 0 to 10 carbon atoms Sulfamoyl group, substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, substituted or unsubstituted having 2 to 10 carbon atoms Acyl group of substitution, 7-1 A substituted or unsubstituted aryloxycarbonyl group having 0 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted carbamoyl group having 1 to 10 carbon atoms.

It is preferable that the structure represented by general formula (II) is as follows. R ¹ and R ² are different and are each unsubstituted or substituted with an alkoxycarbonyl group having 1 to 5 carbon atoms, an acyloxy group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms Or an alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² represent a cyclohexane ring (substituted with R ¹ and R ² bonded to each other). R ⁵ is a hydrogen atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, or an unsubstituted aryl group having 6 to 10 carbon atoms, and a hydrogen atom is preferable. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a nitro, or an alkyl group having 1 to 5 carbon atoms which are unsubstituted or substituted with one or more halogen atoms. . One of R ¹⁰ , R ¹¹ and R ¹² is a hydrogen atom, an alkyl group, a halogen atom, a nitro, an alkoxy group, an acylamino group or a carbamoyl group, and R ⁹ and R ¹³ are each preferably a hydrogen atom. More preferably, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each hydrogen atoms.

The compound represented by general formula (I) of this invention is a new compound synthesize | combined for the first time by this inventor.

The manufacturing method (synthesis method) of the compound represented by general formula (I) is demonstrated below.

The compound represented by the general formula (I) is synthesized by reacting the compound represented by the following general formula (III) with the compound represented by the following general formula (IV).

In the general formula, R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. ; R ³ , R ⁴ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; R ⁵ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted having 2 to 10 carbon atoms, or Unsubstituted acylamino group or substituted or unsubstituted heterocyclic group having 1 to 6 carbon atoms; R ⁸ represents a hydrogen atom or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent.

Any solvent may be used for the reaction. Examples thereof include alcohols such as methanol, ethanol and isopropanol, amides such as dimethylformamide and dimethylacetamide, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform and methylene chloride. And dichloroethane) and hydrocarbons (eg, hexane and pentane).

The temperature may be selected in the range of -20 ~ 200 ℃. However, the temperature is preferably -10 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, and most preferably 10 ° C to 40 ° C.

The reaction time depends on the conditions including temperature. However, 5 minutes-10 hours are preferable.

It is preferable that a base coexists in the said reaction system. Examples of such bases include inorganic bases (eg sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide and potassium hydroxide) and organic bases (eg triethylamine, pyridine and diazabicycloundecene). The base is preferably an organic base.

The compound (III) and compound (IV) are preferably used in a ratio (molar ratio) selected from the range of 1:10 to 10: 1 in terms of equivalent ratio. Its ratio is more preferably 1: 3 to 3: 1, and most preferably 1: 1.5 to 1.5: 1.

Although the preferable example of a compound represented by general formula (I) of this invention is shown below, the compound of this invention is not limited to the following example.

The synthesis method of the compound of the present invention will be described. Compounds of the present invention can be synthesized with the following synthetic routes.

(Synthetic root)

In the general formula, R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. ; R ³ , R ⁴ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; R ⁵ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted having 2 to 10 carbon atoms, or Unsubstituted acylamino group or substituted or unsubstituted heterocyclic group having 1 to 6 carbon atoms; R ⁸ represents a hydrogen atom or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a substituent; However, substituents R ¹ and R ² may be bonded to each other to form a ring.

Example

The invention will be explained in more detail below with reference to examples.

Example 1

Synthesis of Compound 15

Synthesis Example 1

(Synthesis of Compound 15)

(Step 1)

Malonic acid (5.2 g, 0.05 mol) and concentrated sulfuric acid (0.5 mL) were added to acetic anhydride (10 mL). The mixture was stirred at room temperature to completely dissolve the raw compound. Subsequently, 4-ethylcyclohexanone (6.31 g, 0.05 mol) was added slowly and appropriately to the mixture while cooling on an ice bath. The resulting mixture was continuously stirred in the ice bath. As a result, as the reaction proceeded, colorless crystals precipitated. The crystals were taken by filtration, washed with distilled water and dried. Thus, intermediate 1 was obtained as colorless crystals in an amount of 9.0 g (yield 85.1%).

(Process 2)

The intermediate 1 (4.25 g, 0.02 mol) and intermediate 2 (5.70 g, 0.02 mol) were dissolved in methanol (50 mL), to which triethylamine (3.04 g, 0.03 mol) was added. The mixture was stirred continuously for 6 hours at room temperature. As a result, purple crystals precipitated. The crystals were taken by filtration and washed with methanol. Thus, compound 15 was obtained as purple crystals in an amount of 5.61 g (yield 76.3%).

(Reference example)

In DVD-R, the compound of the present invention is useful as a raw material for synthesizing an oxonol dye showing excellent performance, and is explained by the synthesis example.

[Synthesis of Intermediate 3]

 1,4-cyclohexadione (22.43 g, 0.2 mol) and malonic acid (41.62 g, 0.4 mol) were dissolved in acetic anhydride (85 mL), and concentrated sulfuric acid (7.0 mL, 0.12 mol) was added. The mixture was stirred on an ice bath. As the reaction proceeded, light brown crystals precipitated. These crystals were taken by filtration, washed with cold distilled water and dried. Thus, intermediate 3 was obtained as light brown crystals in an amount of 8.8 g (yield 15.5%).

(Process 3)

Compound 15 (4.40 g, 12.0 mmol) and Intermediate 3 (1.71 g, 6.0 mmol) shown in the Synthesis Example according to the present invention were dissolved in dimethylformamide (20 mL). Triethylamine (1.82 g, 18 mmol) was added dropwise to the solution and the reaction mixture was stirred at 50 ° C. for 4 hours. Subsequently, distilled water was added to the reaction mixture, and the obtained mixture was extracted with ethyl acetate. The organic layer obtained as an extract was purified by silica gel column chromatography (dichloromethane / methanol = 6/1). Thus, dye 1A was obtained as purple powder in the amount of 2.0 g (yield 39.5%).

(Process 4)

The dye 1A (1.24 g, 1.48 mmol) was dissolved in dimethylformamide used in the minimum necessary amount to dissolve the dye. Intermediate 4 was added to the solution as counter cation component and the resulting mixture was stirred continuously at room temperature. As a result, gold powder precipitated. The powder was taken by filtration. Thus, dye 1B was obtained as a metal powder in the amount of 0.95 g (yield 48.3%).

The structure of the dye 1B was confirmed by ¹ H NMR spectroscopy.

¹ H NMR (DMSO-d6): 0.84 (t, 6H), 1.20 (m, 10H), 1.62 (m, 8H), 1.96-2.14 (m, 12H), 7.11 (m, 4H), 7.24 (d, 2H), 7.34-7.77 (m, 18H), 7.90 (d, 2H), 9.00 (d, 4H), 9.65 (d, 4H), 10.71 (s, 2H)

Example 2

Synthesis of Compound 1

Synthesis Example 2

(Step 1)

Malonic acid (5.2 g, 50 mmol) and concentrated sulfuric acid (0.5 ml) were added to acetic anhydride (10 mL). The mixture was stirred at room temperature to completely dissolve the raw material. Subsequently, 2-pentanone (4.3 g, 50 mmol) was slowly added dropwise to the solution while cooling in an ice bath. The resulting mixture was stirred continuously at room temperature for 4 hours. The reaction mixture obtained was extracted with ethyl acetate, and the extract was washed twice with water, dehydrated and treated with an evaporator to distill off the solvent under reduced pressure. Thus, intermediate 5 was obtained as an oily substance in an amount of 7.15 g (yield 83%; 41.4 mmol).

(Process 2)

The intermediate 5 (3.44 g, 20 mmol) and intermediate 2 (5.7 g, 20 mmol) were dissolved in methanol (50 mL), to which triethylamine (3.04 g, 0.03 mol) was added. The mixture was stirred continuously at room temperature for 4 hours. As a result, purple crystals precipitated. The crystals were taken by filtration and washed with methanol. Thus, compound 1 was obtained as purple crystals in an amount of 5.3 g (yield 81.1%; 16.2 mmol).

In the same manner as in Example 1, Compound 1 according to the present invention was used to synthesize dye 2B. The structure of the dye was measured by NMR spectroscopy.

¹ H NMR (DMSO-d6): 0.90 (t, 6H), 1.39 (m, 4H), 1.45 (s, 6H), 1.77 (m, 4H), 1.98 (s, 8H), 7.10 (q, 4H) , 7.27 (d, 2H), 7.40-7.08 (m, 18H), 7.91 (s, 2H), 9.05 (d, 4H), 9.65 (d, 4H), 10.72 (s, 2H)

This application is based on Japanese Patent Application No. JP2004-158997 filed on May 28, 2004, all contents are hereby incorporated by reference and all have been described in detail.

Claims (10)

The compound represented by following General formula (1).

R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; R ³ , R ⁴ , R ^6, and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; R ⁵ has a hydrogen atom, a halogen atom, or 1 to 10 carbon atoms A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted acylamino group having 2 to 10 carbon atoms, or a substitution having 1 to 6 carbon atoms or Unsubstituted heterocyclic group; R ⁸ represents a hydrogen atom or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ^12, and R ¹³ each independently represent hydrogen. An atom or a substituent; , R ¹ and R ² may be bonded to each other to form a ring.) The compound of claim 1, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ^12, and R ¹³ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a nitro group, and a cyano group , Substituted or unsubstituted alkoxycarbonylamino group having 2 to 10 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or substituted or unsubstituted alkoxy having 2 to 10 carbon atoms A compound characterized by showing a carbonyl group. A compound according to claim 1, which is represented by the following general formula (II).

R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; R ⁵ Is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted group having 2 to 10 carbon atoms An acylamino group of R 1, a substituted or unsubstituted heterocyclic group having 1 to 6 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ^12, and R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, and a cyano group , Nitro group, carboxyl group, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, substituted or unsubstituted having 2 to 10 carbon atoms Substituted acylamino group, 2-10 Substituted or unsubstituted aminocarbonylamino group having a small atom, substituted or unsubstituted alkoxycarbonylamino group having 2 to 10 carbon atoms, substituted or unsubstituted aryloxycarbonylamino group having 6 to 10 carbon atoms , Substituted or unsubstituted sulfamoyl group having 0 to 10 carbon atoms, substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, substituted or unsubstituted arylsulfo having 6 to 10 carbon atoms Neyl group, substituted or unsubstituted acyl group having 2 to 10 carbon atoms, substituted or unsubstituted aryloxycarbonyl group having 7 to 10 carbon atoms, substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms Or a substituted or unsubstituted carbamoyl group having 1 to 10 carbon atoms, provided that substituents R ¹ and R ² may be bonded to each other to form a ring.) 4. A compound according to claim 3, wherein R ⁵ represents a hydrogen atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, or an unsubstituted aryl group having 6 to 10 carbon atoms. 4. A compound according to claim 3, wherein R ⁵ represents a hydrogen atom. 4. A compound according to claim 3, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ^12, and R ¹³ are each independently a hydrogen atom, a halogen atom, a nitro group, or an unsubstituted or substituted with one or more halogen atoms. An alkyl group having two carbon atoms. 4. A compound according to claim 3, wherein one of R ¹⁰ , R ¹¹ and R ¹² represents a hydrogen atom, an alkyl group, a halogen atom, a nitro group, an alkoxy group, an acylamino group or a carbamoyl group, and R ⁹ and R ¹³ each represent a hydrogen atom. A compound characterized by the above-mentioned. 4. A compound according to claim 3, wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each represent a hydrogen atom. A process for producing a compound represented by the following general formula (I), comprising the step of reacting a compound represented by the following general formula (III) with a compound represented by the following general formula (IV).

R ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; R ³ , R ⁴ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; R ⁵ represents a hydrogen atom, a halogen atom or 1 to 10 carbon atoms. Substituted or unsubstituted alkyl group having 6 to 10 carbon atoms, substituted or unsubstituted aryl group having 2 to 10 carbon atoms, substituted or unsubstituted acylamino group having 1 to 6 carbon atoms, or Unsubstituted heterocyclic group; R ⁸ represents a hydrogen atom or a substituted or unsubstituted acyl group having 2 to 10 carbon atoms; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or Represents a substituent, provided that R ¹ and R ² may be bonded to each other to form a ring.) The method of claim 9, wherein the reaction is performed at −20 ° C. to 200 ° C. for 5 minutes to 10 hours.