TWI399411B - Spiro-indanes type cyanine dye and its use - Google Patents

Description

Spiroindoline cyanine dye and its use

The present invention relates to a material which can be used as an optical disk recording medium, and more particularly to a novel cyanine dye which can be used in a high-speed DVD-R optical disk medium, a preparation method thereof and an optical recording medium formed using the same in an optical disk recording layer.

Cyanine dyes are an important organic dye that has a wide range of applications in textiles, photographic science, lasers, fluorescent probes and optical disc recording media. The first cyanine dye was first synthesized by Greviln Williams in 1856 and was originally used as a textile dye. In 1875, Vogel discovered that cyanine dyes have special photosensitivity and are therefore used in photographic materials. Later, Law et al. first proposed the application of cyanine dyes to optical discs as a recording medium (K. Y. Law, P. S. Vincett, and G. E. Johnson, Appl. Phys. Lett., 39, 18 (1981)). Since the cyanine dye has a large molar extinction coefficient, even a small energy (about 0.5 nJ/bit) can ablate a small pit, and a higher signal-to-noise ratio can be obtained, and the n value is relatively large, and k Appropriate values (see US 5,976,658; US 5,773,193), which can be made into high-quality recordable compact discs (CD-R and DVD-R), CD-R international standard (Orange Book) was originally formulated according to the type of cyanine dye Most CD-R disc burners are also designed with reference to its characteristics. Later, phthalocyanine and azo dyes were successively developed as CD-R recording media. Basically, the use of organic dyes as a storage material is mainly because it can coat the recording material on the substrate by a relatively simple spin coating method, and the vacuum evaporation coating method can reduce the production process and reduce the production. Cost, therefore, the stability of the organic dye and its solubility characteristics to organic solvents are quite important.

With the advent of information and multimedia generations, the circulation of a large amount of information requires storage media with high density, miniaturization and low production cost, and high-density optical storage media is the research and development goal. CD-R has the advantages of low price, fast programming speed, easy portability and high compatibility with personal computers. For optical information storage media, among them, those who have successfully developed their process technologies include shortening the read and write laser source. The wavelength, for example, changing the laser source from infrared laser to red laser can also be started by increasing the numerical aperture of the lens, which is the current DVD-R high storage density disc, recording and reading of DVD-R disc. At 650nm, its recording capacity is 7 times that of CD-R discs.

The DVD-R dye has an appropriate amount of absorption at 650 nm, the dye has good solubility in an organic solvent, especially an alcohol solvent, the dye must have a sufficiently high reflectance after film formation, and the dye has sufficient stability to satisfy the long Time to save data requirements. In addition to the absorption wavelength, another problem encountered in the DVD-R is the programming speed. The DVD-R gradually shifts from a low-speed (1X~8X) recording medium to a high-speed (12~16X). However, when recording high-speed recordable discs, the characteristics of the recording layer are more important. An effective method is to research and develop novel recording materials. When performing high-speed optical recording, it is necessary to use a time shorter than the normal writing time. Burning, on the other hand, due to the need for high-power laser irradiation, the margins required for burning and reading will become narrower, especially the jitter characteristics are poor, and the laser power is increased. And so on. It is necessary to improve the characteristics of the dye by changing the structural properties of the dye, to improve the thermal decomposition characteristics and to improve the burning speed of the DVD-R disc. The dye molecules of optical disc media generally have the basic structural characteristics of conjugated dyes, that is, the skeleton determines the range of their main absorption bands. The development of new dyes can be calculated by semi-empirical molecular orbital calculation methods, mainly EHMO, PPP, CNDO. MNDO, etc., in which the PPP method (Pariser-Parr-Pople) is considered to be the best method for calculating the absorption wavelength of dye molecules. Since the relationship between the molecular structure of the dye and its function (especially thermal properties) has not been thoroughly studied, the choice of dye depends to a large extent on the experiment, and a suitable recording material is screened.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and to provide a recording layer dye for use in a high-speed recordable optical disc with a significant improvement in characteristics for thermal decomposition and burn-in recording. The inventors have carefully studied the results of the above problems and found that a spiroindoline-type cyanine dye has an improved thermal decomposition property and thus has an effect of increasing the burning speed when used in a disc medium.

SUMMARY OF THE INVENTION An object of the present invention is to provide a spiroindoline-type cyanine dye which can be used as a material for a high-speed recordable optical recording medium, which is represented by the following general formula (I):

Wherein Z ₁ and Z ₂ independently represent a condensed naphthalene ring or a fused benzene ring which may be substituted to form a benzofluorene ring or an anthracene ring together with the nitrogen-containing ring to which they are bonded; Y ₁ and Y ₂ may be the same or different and each represents an organic group having 1 to 18 carbon atoms; X ^- represents a counter ion; and R ₁ and R ₂ may be the same or different and each is substituted or unsubstituted. a hydrocarbon group of ₁ to 12 carbon atoms; or R ₁ and R ₂ are bonded to each other to form a 3-6 membered carbocyclic ring, which in turn may be fused to a benzene ring; R ₃ , R ₄ , R ₅ , R ₆ may be the same or Different substituents, each representing a hydrogen atom, may be a straight or branched alkyl group having 1 to 6 carbon atoms, may be a linear or branched alkenyl group having 2 to 6 carbon atoms, may be contained a cycloalkyl group of 3 to 6 carbon atoms, which may be a cycloalkenyl group having 5 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkane having 1 to 7 carbon atoms A mercapto group, which may be an alkoxycarbonyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amine group, may be an alkylamine group having 1 to 6 carbon atoms, may be 1 a dialkylamino group of 6 to 6 carbon atoms, which may be an alkoxycarbonyl group having 3 to 7 carbon atoms An alkyl group, which may be an alkylthio group having 1 to 6 carbon atoms, may be an alkanesulfonyl group having 1 to 6 carbon atoms, may be an aryl group having 6 to 16 carbon atoms or may be 7- An arylcarbonyl group of 17 carbon atoms; R ₃ and R ₄ , R ₄ and R ₅ , or R ₅ and R ₆ may together with the carbon to which they are bonded form a 5-6 membered cycloalkyl group.

In the spiroindoline-type cyanine dye represented by the above formula (I) of the present invention, the fused naphthalene ring or benzene ring represented by Z ₁ and Z ₂ may be substituted by one or more substituents, and the like The group includes, for example, a C _1-6 aliphatic hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, tert-butyl, pentyl, isopentyl, Neopentyl and tert-pentyl; alkoxy such as methoxy, trifluoromethoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentyloxy An aryloxy group such as a phenoxy group; and an aralkyl group such as a benzyl group; an alkoxycarbonyl group such as a methoxycarbonyl group, a trifluoromethoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group; a decyloxy group such as an ethoxy group; , trifluoroacetoxy; and aralkyloxy such as benzyloxy; alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl , butylsulfonyl, tris-butylsulfonyl and pentylsulfonyl; alkylamine sulfonyl such as methylsulfonyl, dimethylamine sulfonyl, ethylamine sulfonyl, diethyl Aminesulfonyl, propylsulfonyl, dipropylaminesulfonyl, butylsulfonyl, dibutyl Sulfo acyl, sulfo acyl pentylamine, dipentylamine, and sulfo acyl; halogen such as fluorine, chlorine, bromine and iodine; a nitro group and a cyano group.

Further, the benzofluorene ring formed by Z ₁ and Z ₂ and the hydrazine respectively may be 1H-benzo[e]pyrene or 3H-benzo[g]fluorene.

In the formula (I), Y ₁ and Y ₂ may be the same or different and each represents an organic group having 1 to 18 carbon atoms, more preferably an organic group of 1 to 10 carbon atoms, such as a methyl group. Ethyl, propyl, isopropyl, 2-propenyl, ethynyl, 2-propynyl, isopropenyl, butyl, isobutyl, t-butyl, tert-butyl, 2-butene Base, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, 2-penten-4-ynyl, hexyl , isohexyl, 5-methylhexyl, heptyl, and octyl; aryl such as phenyl, o-tolyl, m-tolyl, p-tolyl, 2,4-dimethylphenyl, 2, 6-Dimethylphenyl, 2,4,6-trimethylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, and biphenyl groups. Such aliphatic hydrocarbon groups may carry one or more substituents, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, tert-butyl, Amyl, isopentyl, neopentyl and tert-pentyl; aryl such as phenyl; alkyl aryl such as o-tolyl, m-tolyl, p-tolyl, xylyl, 2, 4 , 6-trimethylphenyl, o-anisyl, m-anisyl, p-anisyl; and biphenyl; alkoxy such as methoxy, trifluoromethoxy, ethoxy, propoxy , isopropoxy, butoxy, tert-butoxy, pentyloxy, phenoxy; and aralkyloxy such as benzyloxy; alkoxycarbonyl such as methoxycarbonyl, trifluoromethoxycarbonyl, B Oxycarbonyl, propoxycarbonyl; alkoxy such as ethoxycarbonyl, trifluoroacetoxy; and aralkyloxy such as benzyloxy; and halogen such as fluorine, chlorine, bromine, and iodine.

X ^- in the formula (I) represents a counter ion. The counter ion is not limited and may be appropriately selected depending on the solubility and/or heat resistance in TFP (tetrafluoropropanol) depending on the application. Examples of the counter ion may be inorganic acid ions such as phosphate ions, perchloric acid ions, periodic acid ions, hexafluorophosphate ions, hexafluoroantimonate ions, hexafluorostannate ions, and tetrafluoroborate ions; organic acid ions such as Thiocyanate ion, benzenesulfonic acid ion, naphthalenesulfonic acid ion, p-toluenesulfonic acid ion, alkylsulfonate ion, phenyl carbonate ion, alkyl carbonate ion, halogenated alkyl carbonate ion, alkylsulfonate ion, Halogenated alkylsulfonate ions; and organometallic complex anions such as azo, bisphenyldithio, thiocatechol chelate, thiobisphenorate chelate. From the viewpoints of stability such as explosiveness and ease of handling, more desirable are anions including fluorine and a metal element selected from the group consisting of phosphorus, cerium and lanthanum; hexafluorophosphate ions and hexafluoroantimonate ions. The cyanine dye of the present invention which carries such an anion as a counter ion has relatively high heat resistance, easy handleability, and solubility in an organic solvent such as TFP.

The alkyl group having 1 to 4 carbon atoms represented by R ₁ and R ₂ in the formula (I) may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a second butyl group. a third butyl group, an isobutyl group or the like, a cycloalkyl group of a 3-6 membered ring formed by linking R ₁ and R _{2 to} each other, for example, a cyclopropane-1,1-diyl group, a cyclobutene-1,1-di group. Base, 2,4-dimethylcyclobutane-1,1-diyl, 3,3-dimethylcyclobutane-1,1-diyl, cyclopenta-1,1-diyl, cyclohexyl-1 ,1-diyl, tetrahydrofuran-4,4-diyl, thiopyran-4,4-diyl, hexahydropyridine-4,4-diyl, N-substituted hexahydropyridine-4,4-di Base, morpholine-2,2-diyl, morpholine-3,3-diyl, N-substituted morpholine-2,2-diyl and N-substituted morpholine-3,3-diyl and the like.

The C _1-6 linear or branched alkyl group which may have a substituent represented by R ₃ , R ₄ , R ₅ or R ₆ in the formula (I) may be, for example, a methyl group, an ethyl group or a n-propyl group. , isopropyl, n-butyl, tert-butyl, second-butyl, n-pentyl, n-hexyl, etc.; a C _3-6 cycloalkyl group which may have a substituent is, for example, a cyclopropyl group. a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or the like; a C _1-6 alkoxy group which may have a substituent is, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group. a third-butoxy group, a second-butoxy group, a n-pentyloxy group, a n-hexyloxy group or the like; and a C _1-7 alkano group may be, for example, a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, Butyl, isobutyl, pentylene, isoamyl, pivaloyl, hexyl, heptyl, etc.; C _2-6 straight or branched alkenyl which may contain a substituent For example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group or the like; a C _5-6 cycloalkenyl group which may have a substituent is, for example, a cyclopentenyl group, a cyclohexenyl group or the like; fluorine atom, chlorine atom, bromine atom; hydroxy C _1-6 alkyl, for example hydroxymethyl, hydroxyethyl, and the like; C _2-7 alkyl The carbonyl group is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, second-butoxycarbonyl, n-pentyloxycarbonyl, n- Hexyloxycarbonyl or the like; a C _1-6 alkylamino group may be, for example, a methylamino group, an ethylamino group, a n-propylamino group or a n-butylamino group; and a di-(C _1-6 alkyl)amino group is, for example, two Methylamino, diethylamino, di-n-propylamino, di-n-butylamino, etc.; C _3-7 alkoxycarbonylalkyl can be, for example, methoxycarbonylmethyl, ethoxycarbonylmethyl, positive -propoxycarbonylmethyl, isopropoxycarbonylethyl, etc.; _C1-6 alkylthio may be, for example, methylthio, ethylthio, n-propylthio, n-butylthio, tert-butyl sulfide a base, a second-butylthio group, a n-pentylthio group, a n-hexylthio group or the like; the C _1-6 alkanesulfonyl group may be, for example, a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, Isopropyl sulfonyl, n-butanesulfonyl, tris-butsulfonyl, s-butasulfonyl, n-pentanesulfonyl, n-hexylsulfonyl, etc.; C which may contain a substituent _{The 6-16} aryl group may be, for example, a phenyl group, a naphthyl group, a fluorenyl group or the like; and the C _7-17 arylcarbonyl group which may have a substituent is, for example, a benzylidene group or a naphthalene group. A fluorenyl group or the like; a 5-6 membered cycloalkyl group in which R ₃ and R ₄ , R ₄ and R ₅ , or R ₅ and R ₆ may form together with the carbon to which they are bonded may be, for example, a cyclopentyl group, a cyclohexyl group or the like. .

The substituents which the above substituents may contain are the same as those described above for Y ₁ and Y ₂ .

Preferred specific examples of the compound represented by the above formula (I) according to the present invention are shown in the following compounds No. 1-12.

Further, the present invention relates to an optical recording medium characterized in that the recording layer contains the spiroindoline-type cyanine compound represented by the formula (I) of the present invention. The optical recording medium can further be provided with an undercoat layer on the substrate as needed. The recording layer can be formed by vacuum evaporation, sputtering, doctor blade, cast, and rotation. A film forming method generally employed in a spin coat method or a dipping method, and a coating composition containing the spiroindoline-type cyanine compound represented by the formula (I) of the present invention is formed into a film on a substrate. For the consideration of mass production and cost, spin coating is preferred.

Further, an adhesive may be used in the coating composition as needed. The adhesive may be a polyvinyl alcohol, a polyvinyl pyrrolidone, a ketone resin, a nitrocellulose, a cellulose acetate, a polyvinyl butyral, a polycarbonate, or the like. . When it is formed by spin coating, the number of rotations is preferably 500-5000 rpm, and after spin coating, treatment such as heating or solvent evaporation may be employed as appropriate.

When the recording layer is formed by a doctor blade method, a casting method, a spin coating method, a dipping method, or a coating method such as a spin coating method, the coating solvent is not particularly limited as long as it does not intrude into the substrate. For example, a ketone alcohol solvent such as diacetone alcohol or 3-hydroxy-3-methyl-2-butanone, or a cellosolve solvent such as methyl cellosolve or ethyl cellosolve. - a hydrocarbon solvent such as hexane or n-heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, n-butylcyclohexane, and tert-butyl a cyclocarbonic solvent such as cyclohexane or cyclooctane; an ether solvent such as diisopropyl ether or dibutyl ether; a perfluoroalkanol solvent such as perfluoropropanol, perfluoropentanol or perfluorobutanol; A hydoxy ester such as methyl lactate or ethyl lactate is a solvent.

In the optical recording medium of the present invention, in addition to the recording layer and the undercoat layer, a reflective layer and a protective layer may be further included. The reflective layer is made of a metal such as gold, silver, aluminum, copper, platinum, or the like, and an alloy containing the metals; from the viewpoint of reflectivity and durability, gold, silver, aluminum, or the like is mainly used. The alloy of the ingredients is preferred. The thickness of the reflective layer is 40-200 nm, preferably 60-150 nm. The film formation method of the reflection layer may be, for example, a film formation on the substrate by a sputtering method, a vacuum deposition method, an ion plating method, or the like.

In addition, the protective layer is not particularly limited as long as it can protect the recording layer and the reflective layer, and for example, it can be formed of an ultraviolet curable resin, a lanthanide resin or the like. As the binder to be used in the bonding, an ultraviolet curable resin, a hot melt adhesive or the like can be used. In this case, a recording layer may be provided on the upper portion of the two substrates to be bonded, and the dummy substrate may be a single substrate without a recording layer.

The invention will now be described in more detail by the following examples in which the synthesis steps of the dyes of the invention are described to produce tests and results for optical recording media.

Preparation method:

The spiroindoline type cyanine dye of the present invention will be described by the compound represented by the above formula (I), and will be synthesized in accordance with the production method shown in the following reaction scheme.

Step 1: Synthesis of benzophthalocyanine dyes from the basic heterocyclic intermediate 2-methyl-3-dihydroindenylbenzopyrene and its derivatives. Most of the steps are based on Fischer synthesis (Fischer). First, the indoline is heated under acidic conditions to form the corresponding hydrazine, and then acid-catalyzed to form a ring to form an intermediate hydrazine derivative: Fischer 吲哚 synthesis, generally speaking In the ring closure of the aryl ring, it is preferably carried out in the presence of an acid catalyst. The acid catalyst used can be used as a catalyst as long as it can form a complex with an organic ligand. Commonly used catalysts are inorganic acids such as H ₂ SO ₄ , HCl, H ₃ PO ₄ ; organic acids such as HCOOH, TsOH; Lewis (Lewis) Acids such as ZnCl ₂ , TiCl _{4 ,} etc.; the reaction temperature is generally in the range of 40 to 120 °C. In the ring closure process, the reaction solvent can be either an aqueous solution, such as an aqueous solution of H ₂ SO ₄ as a solvent. In order to prevent the ruthenium from being oxidized in the air, it is preferred to pass N ₂ in the solution for protection; the solvent can use alcohol (MeOH). , EtOH) solvent; ether solvent such as dioxane, tetrahydrofuran (THF), etc., or a mixture of two or more solvents mixed in different ratios. Step 2: The intermediate hydrazine derivative is then reacted with a salt forming agent (also referred to as an alkylating agent) represented by Y ₁ -E to obtain an N-alkylated hydrazine derivative. In the formula Y ₁ -E, Y ₁ is as defined above, more specifically an alkyl group of 1 to 8 carbon atoms, and E is a leaving group, more specifically a halogen (e.g., iodine, bromine, chlorine). The reaction temperature of this reaction is usually in the range of 0 to 110 ° C, and the reaction time is usually from 1 to 48 hours.

Step 3: The N-alkylated anthracene derivative obtained in the step 2 is subjected to a condensation reaction with a 2-anilinovinylindoium salt, and finally the corresponding anion (X ^- ) is substituted. Cyanine dye. In this step, the 2-anilinovinylguanidinium salt is reacted with aniline and trimethyl orthoformate under acidic conditions to form N,N-dipheyl-formamidine. Then, the obtained N,N-diphenylformamidine is reacted with an indolenium derivative (indolenium) to form.

The following examples are intended to further illustrate the technical contents of the present invention, and the objects and effects thereof, but are not intended to limit the present invention, and all such variations and modifications are possible within the scope of the present invention. The following examples illustrate the invention in detail.

[Production Example 1] (Production of Intermediate Compound A)

To a 1 L reaction flask which was purged with nitrogen, 75 g of 2-naphthylhydrazine hydrochloride and 113 g of ethanol were added, and 68 g of dihydrofurfurylmethyl ketone was added dropwise under a nitrogen stream at 60 ° C (note that heat was generated). Further, 71 g of 32% hydrochloric acid was added dropwise and refluxed for 8 hours. After cooling, 400 g of toluene and 200 g of warm water were added, and a 50% aqueous sodium hydroxide solution was added thereto to adjust the reaction solution to pH 8 or higher, followed by oil-water separation. The oil phase was washed three times with 300 g of warm water, dehydrated, and the solvent was evaporated in vacuo. The residue thus obtained was purified by column chromatography to give 61 g of Intermediate Compound A (yield: 55.8%).

Physical data of intermediate compound A:

¹ H-NMR (CDCl ₃ )

Δ7.94~7.92(m,1H),7.86(d,J=8.4 Hz,1H), 7.76(d,J=8.4 Hz,1H), 7.59~7.75(m,1H), 7.42~7.31(m, 6H), 3.70 (d, J = 16.8 Hz, 2H), 3.20 (d, J = 16.8 Hz, 2H), 2.17 (s, 3H)

[Production Example 2] (Production of Intermediate Compound B)

14.1 g of the intermediate compound A obtained above, 56.8 g of methyl iodide and 27 g of ethyl acetate were placed in a reaction flask, and reacted at 50 ° C for 24 hours, and after cooling to room temperature, crystallization was carried out. Filtration of the crystals gave 17.5 g of Intermediate Compound B (yield 46.4%).

Physical data of intermediate compound B:

¹ H-NMR (d ₆ -DMSO)

Δ8.34~8.32(d,1H), 8.24~8.22(d,1H), 8.15~8.13(d,1H), 7.70~7.57(m,3H),7.49~7.38(m,4H),4.11(s , 3H), 3.77~3.66 (dd, 4H), 2.64(s, 3H)

[Production Example 3] (Production of Intermediate Compound C)

3 g of the intermediate compound A, 1.82 g of ethyl iodide and 6 g of ethyl acetate were placed in a reaction flask, and the mixture was reacted at 70 ° C for 20 hours, and after cooling to room temperature, crystallization was carried out. Filtration of the crystals gave 1.65 g of Intermediate Compound C (yield 34.1%).

Physical data of intermediate compound C:

¹ H-NMR (CDCl ₃ )

δ 8.86~8.04 (d, J=8.8 Hz, 1H), 7.98 (d, J=8.8 Hz, 1H), 7.76 (d, J=9.2 Hz, 1H), 7.59~7.48 (m, 3H), 7.38 ~7.30 (m, 4H), 4.71 (q, J = 5.6 Hz, 2H), 3.87 (d, J = 17.6 Hz, 2H), 3.77 (d, J = 17.6 Hz, 2H), 2.93 (s, 3H) , 1.64 (t, J = 5.6 Hz, 3H)

[Manufacturing Example 1] (Production of Compound No. 2 hexafluoride phosphorus salt)

To the reaction flask which had been replaced with nitrogen, 3 g of the intermediate compound B, 3.7 g of the intermediate compound a represented by the following formula, 45 g of chloroform, and 0.6 g of pyridine were added, and the mixture was reacted at 60 ° C for 2 hours. 30 g of water and 1.3 g of potassium hexafluoride were added, and the mixture was stirred for 30 minutes to carry out salt exchange. After the aqueous layer was removed, the organic layer was washed three times with water (30.0 g) and dried over anhydrous sodium sulfate. 24.0 g of methanol was added to the residue to carry out crystallization, and the crystals were collected by washing, and then vacuum-dried at 100 ° C to obtain 3.9 g of green crystals of the compound No. 2 phosphorus hexafluoride. The rate is 81.7%).

Intermediate compound a

Physical data of Compound No. 2 phosphorus hexafluoride:

Optical properties (dichloromethane 0.5x10 ^-5 g/ml): λ _max 602 nm

TGA: 302.9 ° C

¹ H-NMR (CDCl ₃ )

Δ7.95~7.88(m,4H), 7.77~7.14(m,13H),6.66(d,J=13.2 Hz,1H),6.58(d,J=13.2 Hz,1H),3.94(d,J= 18.0 Hz, 2H), 3.92~3.78 (m, 5H), 3.69 (s, 3H), 1.53 (s, 3H), 1.21 (s, 3H)

[Manufacturing Example 2] (Production of Compound No. 5 hexafluoride phosphorus salt)

To the reaction flask which had been replaced with nitrogen, 2 g of an intermediate compound C, 2.4 g of the above intermediate compound a, 30 g of chloroform, and 0.4 g of pyridine were added, and the mixture was reacted at 60 ° C for 2 hours. 30 g of water and 0.8 g of potassium hexafluoride were added, and the mixture was stirred for 30 minutes to carry out salt exchange. After the aqueous layer was removed, the organic layer was washed three times with water (20.0 g) and dried over anhydrous sodium sulfate. To the residue, 16.0 g of methanol was added and crystallized, and the crystals were collected by washing, and then vacuum-dried at 100 ° C to obtain 2.5 g of green crystals of the compound No. 5 hexafluoride phosphorus salt. The rate is 79.6%).

Physical data of Compound No. 5 phosphorus hexafluoride:

Optical properties (dichloromethane 0.5x10 ^-5 g/ml): λ _max 603nm

TGA: 306.2 ° C

¹ H-NMR (CDCl ₃ )

Δ7.95~7.87(m,4H), 7.76~7.70(m,2H), 7.64~7.27(m,10H),7.16~7.14(d,1H),6.69(d,J=13.2 Hz,1H), 6.62 (d, J = 13.2 Hz, 1H), 4.31 (bs, 2H), 3.96 to 3.91 (d, J = 18.0 Hz, 2H), 3.82 to 3.78 (d, J = 18.0 Hz, 2H), 3.69 (s) , 3H), 1.57 (bs, 6H), 1.2 (s, 3H)

[Manufacturing Example 3] (Production of Compound No. 9 hexafluoride phosphorus salt)

To the reaction flask which had been replaced with nitrogen, 2 g of an intermediate compound C, 2.9 g of an intermediate compound b represented by the following formula, 30 g of chloroform, and 0.4 g of pyridine were added, and the mixture was reacted at 60 ° C for 2 hours. 30 g of water and 0.8 g of potassium hexafluoride were added, and the mixture was stirred for 30 minutes for salt exchange. The aqueous layer was removed, and the organic layer was washed three times with water (30.0 g) and dried over anhydrous sodium sulfate. 24.0 g of methanol was added to the residue to carry out crystallization, and the crystals were collected by washing, and then vacuum-dried at 100 ° C to obtain 2.8 g of a green crystal of the compound No. 9 phosphorus hexafluoride. The rate is 83.5%).

Intermediate compound b

Physical data of Compound No. 9 hexafluoride phosphorus salt:

Optical properties (dichloromethane 0.5x10 ^-5 g/ml): λ _max 609nm

TGA: 242.6 ° C

¹ H-NMR (CDCl ₃ )

Δ7.97~7.90(m,5H), 7.79(d,J=8.8 Hz,1H), 7.70~7.66(m,2H), 7.60~7.56(m,2H),7.52~7.28(m,5H), 7.17 (d, J = 8.4 Hz, 1H), 7.00 (d, J = 8.8 Hz, 1H), 6.91 (t, J = 7.4 Hz, 1H), 6.81 to 6.73 (m, 3H), 6.61 (d, J) =13.6 Hz, 1H), 6.19 (d, J = 7.2 Hz, 2H), 4.35 (q, J = 8.2 Hz, 2H), 4.1 to 3.89 (m, 4H), 3.34 (s, 3H), 3.21 (d , J = 12.0 Hz, 1H), 2.30 (d, J = 12.0 Hz, 1H), 1.61 (t, J = 7.2 Hz, 3H), 1.39 (s, 3H)

Claims (3)

A spiroindoline-type cyanine dye represented by the following formula (I), Wherein Z ₁ and Z ₂ independently represent a condensed naphthalene ring or a fused benzene ring which may be substituted to form a benzofluorene ring or an anthracene ring together with the nitrogen-containing ring to which they are bonded; Y ₁ and Y ₂ may be the same or different and each represents an organic group having 1 to 18 carbon atoms; X ^- represents a counter ion; R ₁ , R ₂ may be the same or different and each is substituted or unsubstituted 1 a hydrocarbon group of -12 carbon atoms; or R ₁ and R ₂ are bonded to each other to form a 3-6 membered carbocyclic ring, which in turn may be fused to a benzene ring; R ₃ , R ₄ , R ₅ , R ₆ may be the same or different Substituents, and respectively represent a hydrogen atom, which may be a straight or branched alkyl group having 1 to 6 carbon atoms, may be a linear or branched alkenyl group having 2 to 6 carbon atoms, may be 3 a cycloalkyl group of 6 to 6 carbon atoms, which may be a cycloalkenyl group having 5 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkane having 1 to 7 carbon atoms. The base may be an alkoxycarbonyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amine group, an alkylamine group having 1 to 6 carbon atoms, and may be 1- a dialkylamino group of 6 carbon atoms, which may be an alkoxycarbonyl group having 3 to 7 carbon atoms An alkyl group, which may be an alkylthio group having 1 to 6 carbon atoms, may be an alkanesulfonyl group having 1 to 6 carbon atoms, may be an aryl group having 6 to 16 carbon atoms or may be 7- An arylcarbonyl group of 17 carbon atoms; R ₃ and R ₄ , R ₄ and R ₅ , or R ₅ and R ₆ may together with the carbon to which they are bonded form a 5-6 membered cycloalkyl group. The spiro-indane cyanine dye according to the first aspect of the patent application, which is a spiro-indane cyanine dye represented by the following formula (II), Wherein, the Z ₂ system represents a fused naphthalene ring to form a benzoin ruthenium ring or a fused benzene ring to form an enamel ring. In general, the benzoin prime ring system independently carries a 1H-benzo[e]fluorene skeleton or a 3H-benzo[g]fluorene skeleton; Y ₁ and Y ₂ may be the same or different and each represents 1 to 18 An organic group of carbon atoms; X ^- represents a counter ion; R ₁ , R ₂ may be the same or different and each substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms; or R ₁ and R _{2 is} linked to each other to form a 3-6 membered carbocyclic ring, which in turn may be fused to a benzene ring; R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different substituents, and each represents a hydrogen atom, which may be contained a linear or branched alkyl group of 1 to 6 carbon atoms, which may be a linear or branched alkenyl group having 2 to 6 carbon atoms, may be a cycloalkyl group having 3 to 6 carbon atoms, may be contained a cycloalkenyl group of 5 to 6 carbon atoms, which may be an alkoxy group having 1 to 6 carbon atoms, may be an alkylhydrazine group having 1 to 7 carbon atoms, may be an alkene having 1 to 6 carbon atoms An oxycarbonyl group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amine group, an alkylamine group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, or An alkoxycarbonylalkyl group having 3 to 7 carbon atoms, which may be an alkylthio group having 1 to 6 carbon atoms, may be 1- Alkanesulfonyl group of 6 carbon atoms, which may be an aryl group having 6 to 16 carbon atoms or an arylcarbonyl group having 7 to 17 carbon atoms; R ₃ and R ₄ , R ₄ and R ₅ , or R ₅ and R ₆ may also form a 5-6 membered cycloalkyl group together with the carbon to which they are bonded. A recordable recording medium characterized in that the recording layer contains a spiroindoline-type cyanine dye as in the first or second aspect of the patent application.