JP4843956B2 - Method for producing norbornene derivatives - Google Patents

Description

  The present invention relates to a method for producing a norbornene derivative that is suitably used as a raw material monomer for a cyclic olefin-containing (co) polymer having a spiro structure capable of controlling the anisotropy of the refractive index. More specifically, the present invention relates to a method for obtaining a norbornene derivative by a Diels-Alder reaction between a cycloolefin having a spiro structure and a cyclopentadiene.

  The norbornene derivative is a useful monomer as a raw material monomer for transparent resins used in optical components. However, with the recent advancement of optical equipment functions and widespread use, birefringence and birefringence wavelength dispersion Precise control is required. Such controllability of optical characteristics is dominated not only by the resin processing technology and the high-order structure of the resin, but also by the structure of the resin raw material. In order to satisfy the above required characteristics, substituents that affect the optical characteristics It is indispensable to introduce a production method that can introduce a more effective substitution position. In addition, it is also required to produce norbornene derivatives at low cost.

  A norbornene derivative having a spiro skeleton is a useful monomer that can fix the orientation of a substituent that affects optical properties and can satisfy the above-described high requirements. Conventionally, a norbornene derivative having a spiro skeleton is a method of performing a cyclization reaction after the construction of the norbornene skeleton, or a method of performing a Diels-Alder reaction between an olefin compound having a cyclic structure such as itaconic anhydride and a cyclopentadiene. It is known that However, in the former method, the reactivity of the olefin moiety is very high due to the highly distorted structure of the norbornene skeleton, and there are limitations on the reagents that can be used in the cyclization reaction. As a result, the efficiency of the purification process is poor. In order to suppress side reactions, it is necessary to carry out the cyclization reaction at a dilute concentration, and a large amount of solvent is used. Patent Document 1 discloses an example of synthesizing a norbornene derivative having a fluorene skeleton through spirocarbons by this method, but expensive chemicals are used as synthetic materials and are difficult to manufacture industrially. It is. On the other hand, in the latter method, there are problems that there are few kinds of inexpensive raw material olefins (dienophiles) that can be used and the introduction positions of spiro carbon are limited.

Various problems involved in the production method of these norbornene derivatives having a conventional spiro skeleton are extremely serious, and development of a new production method is strongly desired.
JP 2004-323489 A

  An object of the present invention is to provide a method for producing a norbornene derivative which can introduce various substituents at more effective substitution positions and can be efficiently obtained from inexpensive raw materials.

  As a result of diligent studies to achieve the above object, the present inventors have achieved the above object of a method for producing a norbornene derivative including a Diels-Alder reaction between a cycloolefin having a spiro carbon and a cyclopentadiene. Based on this finding, the present invention has been completed.

That is, the present invention provides a method for synthesizing a norbornene derivative represented by the general formula (1) by a Diels-Alder reaction between a cycloolefin represented by the following general formula (2) and a cyclopentadiene. is there.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently a hydrogen atom; a halogen atom; 10 is a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a linking group which is a divalent hydrocarbon group or a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Represents an atom or group selected from the group consisting of a hydrocarbon group; and a polar group, wherein a, b, c, d, e, and f are each independently an integer of 0 to 2 (provided that b = c = 0) Except for certain cases), A is — (single bond); —O—; —S—; —SO—; —SO ₂ —; —CO—; —NR ¹¹ —; —SiR ¹² ₂ —; Represents an unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms (R ¹¹ and R ¹² each independently represents an oxygen atom, a nitrogen atom, A substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing a sulfur atom or a silicon atom). ]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , b, c, d, e, f,
Each A is as defined in the general formula (1). ]
In the present invention, the reaction mixture temperature during the Diels-Alder reaction is preferably in the range of 100 to 250 ° C.

In the present invention, it is preferable to use dicyclopentadiene and / or cyclopentadiene, or di (methylcyclopentadiene) and / or methylcyclopentadiene as the cyclopentadiene, and the cycloolefins in the above general formula (2) Cycloolefins in which b and c are each 1 are preferably used, and at least 6 of R ^{3 to} R ^{10 in} the general formula (2) are hydrogen atoms, and d and f are each 1 It is also preferable to use olefins.

In the present invention, it is preferable to synthesize a norbornene derivative in which a in general formula (1) is 0 or 1.

  In the method for producing a norbornene derivative according to the present invention, a norbornene derivative is synthesized by a Diels-Alder reaction between a cycloolefin having a spiro carbon and a cyclopentadiene, and by selecting the reaction conditions and raw materials to be used, Various substituents can be introduced at more effective substitution positions.

  The method for producing a norbornene derivative according to the present invention is more efficient than other synthetic routes using the same raw materials and materials (base, solvent, catalyst, etc.). Furthermore, any of the synthetic materials used in the present invention can be manufactured inexpensively or inexpensively, and is highly usable because it can be used industrially.

  Since the norbornene derivative obtained by the production method of the present invention fixes various substituents in the direction perpendicular to the norbornene ring by a spiro bond, the content of the polymer obtained using such a norbornene derivative is appropriately set. It is possible to freely control birefringence and wavelength dispersion by adjusting to.

  The norbornene derivative obtained by the production method of the present invention is very useful as an optical resin precursor monomer, and polymers obtained by using the norbornene derivative are optical discs, magneto-optical discs, optical lenses (Fθ lenses, pickup lenses, laser printers). Lens, camera lens, etc.), eyeglass lens, optical film / sheet (display film, retardation film, polarizing film, polarizing plate protective film, diffusion film, antireflection film, liquid crystal substrate, EL substrate, electronic paper substrate, Touch panel substrates, PDP front plates, etc.), transparent conductive film substrates, optical fibers, light guide plates, optical cards, optical mirrors, ICs, LSIs, LED encapsulants, etc. Application to optical materials is possible.

Hereinafter, the present invention will be specifically described.
<Reaction reagent>
Among the raw materials used in the present invention, as cyclopentadiene, cyclopentadiene represented by the following general formula (3) and / or cyclopentadiene represented by (4) can be used, but from the viewpoint of cost, Is dicyclopentadiene or di (methylcyclopentadiene), more preferably dicyclopentadiene.

[Wherein R ¹ is as defined in the general formula (1)]
In addition, among the raw materials used in the present invention, cycloolefins represented by the above general formula (2) can be used as the dienophile.

In the general formulas (1) to (4), R ^{1 to} R ¹⁰ are each independently a hydrogen atom; a halogen atom; a linking group or an oxygen atom that is a divalent hydrocarbon group having 1 to 10 carbon atoms; A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing a nitrogen atom, a sulfur atom or a silicon atom; and an atom or group selected from the group consisting of polar groups.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group and allyl group; Groups, alkylidene groups such as propylidene groups; aromatic groups such as phenyl groups, naphthyl groups, anthracenyl groups, and the like. These hydrocarbon groups may be substituted, and examples of the substituent include halogen atoms such as fluorine, chlorine and bromine, phenylsulfonyl group and cyano group.

In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure or may be bonded via a linking group. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, — (CH ₂ ) _q —, q is an alkylene group represented by an integer of 1 to 10); an oxygen atom, a nitrogen atom, A linking group containing a sulfur atom or a silicon atom (for example, a carbonyl group (—CO—), a carbonyloxy group (—COO—), a sulfonyl group (—SO ₂ —), a sulfonyl ester group (—SO ₂ —O—), Ether bond (-O-), thioether bond (-S-
), Imino group (—NH—), amide bond (—NHCO—), siloxane bond (—Si (R ₂ ) O— (where R is an alkyl group such as methyl or ethyl)); or two of these The above is a combination of the above.

  Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, a triorganosilyl group, Examples thereof include an amino group, an acyl group, an alkoxysilyl group, a sulfonyl group, and a carboxyl group. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, and an aryl such as a benzoyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, Biphenylyloxycarbonyl group and the like; examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethylsilyl group and triethylsilyl group. Group and the like; examples of the amino group include primary amino groups such as, alkoxysilyl The group for example a trimethoxysilyl group, triethoxysilyl group, and the like.

  a, b, c, d, e, and f are each independently an integer of 0 to 2 (except when b = c = 0), a is preferably 0 or 1, and b and c are Preferably, it is 1, d and f are preferably each independently 0 or 1, and e is preferably 0 or 1.

In R ¹¹ and R ¹² in —NR ¹¹ — and —SiR ¹² ₂ — represented by A, examples of the linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom include the same groups described above, and are substituted or unsubstituted. Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include the same groups as described above. The substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms represented by A is preferably — (CH ₂ ) _n — (n is 0 or an integer of 1 to 3).

Specific examples of the cycloolefins represented by the general formula (2) include the following compounds.

  Of the cycloolefins represented by the general formula (2), it is more preferable to use cycloolefins in which b and c in the formula (2) are each 1. When b and c in formula (2) are each 1, the strain of the ring structure formed is small, so that the thermal or chemical stability is excellent. Moreover, since the yield at the time of manufacture of the cycloolefin represented by General formula (2) increases for the same reason, it is preferable. If b and c in formula (2) are each greater than 2, the steric position of the substituent to be introduced is not fixed, and various excellent characteristics resulting from the introduction of these substituents are not sufficiently exhibited. There is.

Furthermore, it is preferable to use cycloolefins in which d and f in the general formula (2) are each independently 0 or 1, and at least 6 of R ^{3 to} R ¹⁰ are hydrogen atoms.
As such cycloolefins, preferably spiro [fluorene-9,4′-cyclopentene], spiro [2,7-dimethoxyfluorene-9,4′-cyclopentene],
Spiro [2,7-diethoxyfluorene-9,4′-cyclopentene], spiro [3,6-dimethoxyfluorene-9,4′-cyclopentene], spiro [2-methoxyfluorene-9,4′-cyclopentene], Spiro [2-ethoxyfluorene-9,4′-cyclopentene], more preferably spiro [fluorene-9,4′-cyclopentene], spiro [2,7-dimethoxyfluorene-9,4′-cyclopentene], spiro [3 , 6-dimethoxyfluorene-9,4′-cyclopentene], spiro [2-methoxyfluorene-9,4′-cyclopentene], most preferably spiro [fluorene-9,4′-cyclopentene].

The cycloolefins represented by the general formula (2) are, for example, 2-butene-1,4-
It can be obtained by converting the hydroxyl group of an alcohol such as a diol into a suitable leaving group such as a tosyl group and then condensing and cyclizing with a compound having an active methylene group such as fluorene in the presence of a base. (Hereafter, abbreviated as “Method A”). Also, for example, in the presence of a base, the presence of a metathesis reaction catalyst after synthesizing 9,9-diallylfluorene by condensing a vinyl compound such as 2 equivalents of allyl chloride with a compound having an active methylene group such as fluorene It can also be obtained by carrying out a ring closure reaction below (hereinafter abbreviated as “Method B”). (The above specific numerical values and substance names are not intended to limit the present invention.)
<Specific explanation of Method A>
Examples of alcohols that can be used in Method A include 2-butene-1,4-diol, 2-pentene-1,5-diol, and 3-hexene-1,6-diol. These geometric isomers of the olefin moiety may be any and may be a mixture of two kinds, but are preferably cis isomers.

  A known method can be used to convert the hydroxyl group of these diols into a leaving group (sulfonic acid ester, phosphoric acid ester, halogen atom, etc.). Examples of such a conversion reagent include sulfonic acid derivatives such as benzenesulfonic acid chloride, p-toluenesulfonic acid chloride, p-bromobenzenesulfonic acid chloride, methanesulfonic acid chloride, trifluoromethanesulfonic acid chloride; phenylphosphonic acid dichloride, Phosphoric acid derivatives such as methylphosphonic acid dichloride; halogenating agents such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl bromide, phosphorus tribromide, phosphorus oxychloride; trimethylsilyl chloride, acetonitrile, and lithium bromide, bromide Examples of the halogenating agent include sodium, potassium bromide, calcium bromide, potassium iodide, or sodium iodide. Further, when the hydroxyl group is substituted with a halogen atom, it may be substituted with a halogen atom having higher detachability by a halogen exchange reaction.

Examples of the base used when synthesizing cycloolefins by a condensation cyclization reaction include organic lithium such as n-butyllithium, s-butyllithium, t-butyllithium, and phenyllithium; sodaamide, lithium diisopropylamide, and the like. Metal amides; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxy; metal carbonates such as potassium carbonate and sodium carbonate; sodium hydride and the like Metal hydrides; alkali metals such as sodium, potassium and lithium can be exemplified. In Ohwada, Tomohiko J. Am. Chem. Soc .; 114; 23; 8818 (1992), an example is shown in which a fluorene anion is generated with n-butyllithium and reacted with 2,4-dihalobutane to synthesize a spirocyclic compound. , Jason, Mark E. et al., J. Org. Chem .; 56:11; 3664 (1991) generates a fluorene anion with t-butoxypotassium and reacts with 1,4-dibromobutane to spirocyclic. Examples of synthesizing compounds are disclosed. The medium for carrying out the condensation cyclization reaction using these bases may be a homogeneous phase or a solid / liquid or liquid / liquid two-phase system, and the solubility of the metal compound used is low. In some cases, a small amount of a known phase transfer catalyst may be added.
<Specific explanation of Method B>
Examples of vinyl compounds that can be used in Method B include allyl chloride, allyl bromide, 4-chloro-1-butene, 4-bromo-1-butene, and the like. These vinyl compounds may be used singly or in combination, and may be substituted with halogen atoms having higher detachability by a halogen exchange reaction.

  Examples of the base that can be used in the condensation reaction with the compound having an active methylene group include the same bases that can be used in the condensation cyclization reaction of Method A. Further, the medium for performing the condensation reaction using these bases may be a homogeneous phase or a solid / liquid or liquid / liquid two-phase system, and the solubility of the metal compound used is low. In some cases, a small amount of a known phase transfer catalyst may be added.

As the metathesis reaction catalyst, a catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) is preferably used.
Examples of such a catalyst include (I), for example, (a) at least one selected from compounds of W, Mo, Re, V and Ti, and (b) an alkali metal element (for example, Li, Na, K). , Alkaline earth metal elements (for example, Mg, Ca), Group 12 elements (for example, Zn, Cd, Hg), Group 13 elements (for example, B, Al), Group 14 elements (for example, Si, Sn) , Pd) and the like, and a metathesis catalyst comprising a combination with at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond. In order to enhance the activity of the catalyst, the additive (c) described later may be added.

Specific examples of the component (a) include, for example, WCl ₆ , MoCl ₅ , ReOCl ₃ , VO.
Examples include compounds described in JP-A-1-240517 such as Cl ₃ and TiCl ₄ . These can be used singly or in combination of two or more.

Specific examples of the component (b) include, for example, n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , ( Examples thereof include compounds described in JP-A-1-240517 such as C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like. These can be used singly or in combination of two or more.

  As the additive for the component (c), for example, alcohols, aldehydes, ketones, amines and the like can be preferably used, and further, compounds described in JP-A-1-240517 can be used. Can do. These can be used singly or in combination of two or more.

For the ring-closing metathesis reaction, a metathesis catalyst composed of (II) a transition metal-carbene complex or a metallacyclobutane complex of groups 4 to 8 of the periodic table can also be preferably used. Specific examples include, for example, W (= N-2,6-C ₆ H ₃ ⁱ Pr ₂ ) (= CH ^t Bu) (O ^t Bu) ₂ , Mo (= N-2,6-C ₆ H _{3 ^{i Pr 2) (= CH t}} Bu) (O t Bu) 2, Ru (= CHCH = CPh 2) (PPh 3) 2 Cl 2, Ru (= CHPh) [P (C 6 H 11) 3] 2 Cl ₂ etc. are mentioned. These can be used singly or in combination of two or more.

The catalysts (I) and (II) may be used in combination.
Syn. Lett., 10, 1618 (1999). Diallylfluorene was synthesized by the reaction of allyl bromide and fluorene in the presence of potassium metal, followed by Ru (= CHPh) [P (C ₆ H ₁₁ ) ₃ ]. An example in which spiro [fluorene-9,4′-cyclopentene] was synthesized by a ring-closing reaction using ₂ Cl ₂ as a metathesis catalyst is disclosed.
<Reaction conditions>
In the present invention, the Diels-Alder reaction between the cycloolefin represented by the general formula (2) and the cyclopentadiene is an essential step, and the reaction condition is that the reaction mixture temperature is in the range of 100 to 250 ° C. Preferably, it is 120-240 degreeC, More preferably, it is 140-220 degreeC. When the reaction mixture temperature is lower than these ranges, the reaction rate is slow and the productivity is deteriorated. When the reaction mixture temperature is high, the reverse reaction (side reaction) proceeds to lower the yield of the target product.

  The quantitative relationship between the cycloolefin represented by the general formula (2) and the cyclopentadiene when performing the Diels-Alder reaction is usually a molar ratio of cycloolefin / cyclohexane represented by the general formula (2). Pentadiene = 1 / 0.6 to 1/20, preferably 1 / 0.7 to 1/15, more preferably 1 / 0.8 to 1/10 (cyclopentadiene such as dicyclopentadiene When it is a dimer of a cyclic conjugated diene or when a mixture of a dimer of a cyclic conjugated diene and a monomer is used, the charge ratio within the above range is calculated by converting the molar ratio as the cyclic conjugated diene monomer. And). If the amount of cyclopentadiene to be added is less than this range, relatively expensive cycloolefins remain unreacted, which is not preferable. Further, when the amount of cyclopentadiene is larger than this range, the further reaction between the norbornene derivative represented by the general formula (1) and the cyclopentadiene produced, or the Diels-Alder reaction between the cyclopentadiens proceeds. This is not preferable because the yield of the target product may decrease.

  In addition, the raw materials for the Diels-Alder reaction may be charged at the same time in the ratio of the cycloolefins and cyclopentadiene represented by the general formula (2) within the above range, or the general formula (2) A cyclopentadiene may be added while heating the cycloolefin represented by the formula, and a Diels-Alder reaction may be performed. When the Diels-Alder reaction is carried out by the latter method, the addition rate of cyclopentadiene is preferably 3 to 500 wt% per hour, preferably 4 to 300 wt% per hour, more preferably 100 wt% of the total weight of cyclopentadiene used. Is 5 to 100 wt% per hour. When the rate of addition is slower than these ranges, the productivity is poor, and when it is fast, further reaction between the norbornene derivative represented by the above general formula (1) and cyclopentadiene or Diels-Alder reaction between cyclopentadiene May decrease and the yield of the target product may decrease. Although the value of a in the general formula (1) can be controlled by this addition rate, the addition method may be continuous addition, and if the average addition rate is in the range of the addition rate, it is divided addition. Also good.

The Diels-Alder reaction can be performed in the absence of a solvent or in a solvent. The solvent that can be used is not particularly limited as long as the cycloolefins and cyclopentadienes represented by the general formula (2) are soluble under heating. For example, The Diels-Alder Reaction (Francesco Fringuelli, Aldo Taticchi, JOHN Solvents described in WILEY & SONS, LTD) can be preferably used. More specifically, for example, alkanes such as pentane, hexane, heptane, octane, nonane, decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; benzene, toluene, xylene, ethylbenzene, cumene, etc. Aromatic hydrocarbons; Chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform, tetrachloroethylene, aryl halides, etc .; ethyl acetate, n-butyl acetate, iso-butyl acetate And saturated carboxylic acid esters such as methyl propionate; ethers such as dibutyl ether, tetrahydrofuran, and dimethoxyethane. Among these, aromatic or aliphatic from the viewpoint of solubility Hydrogen is preferred. These can be used singly or in combination of two or more. The amount of these reaction solvents used is such that the weight ratio of “solvent: all raw materials” is usually 0: 1 to 10: 1, preferably 0: 1 to 5: 1. . When the amount of the solvent used is larger than this range, not only the reaction rate is slowed but also the capacity is increased, leading to a decrease in productivity.

  The reaction time for performing the Diels-Alder reaction is usually 1 to 50 hours, preferably 2 to 40 hours, and more preferably 3 to 30 hours. If the reaction time is shorter than this range, the reaction is insufficient, so that the yield is lowered, and if it is longer, the productivity is deteriorated.

  A catalyst can also be used for the Diels-Alder reaction. As such a catalyst, for example, a catalyst described in The Diels-Alder Reaction (Francesco Fringuelli, Aldo Taticchi, JOHN WILEY & SONS, LTD) can be preferably used.

Furthermore, a known polymerization inhibitor or polymerization inhibitor can be used for the Diels-Alder reaction. Examples of such polymerization inhibitors or inhibitors include t-butylcatechol, 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-ethyl-6-t-butylphenol), Hydroquinone, benzoquinone, 2,6-dichlorobenzoquinone, 2,5-di-t-butylhydroquinone, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4 , 4'-thiobis- (6-tert-butyl-3-methylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, octadecyl 3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol Such as phenolic or hydroquinone compounds, amine compounds such as diphenylpicrylhydrazine and diphenylamine, organic sulfur compounds such as dithiobenzoyl disulfide, p, p'-ditolyltris sulfide, dibenzyltetrasulfide, tetraethylthiuram disulfide Nitro compounds such as dinitrobenzene, nitroso compounds such as 2-methyl-2-nitrosopropane, metal salts such as tri (benzoyloxy) iron, ferric bromide, ferric chloride, cupric chloride By using such additives, it is possible to inhibit or suppress the thermal polymerization of the raw olefins and improve the yield of the target product.

The structure of the norbornene derivative represented by the general formula (1) obtained by the Diels-Alder reaction between the cycloolefin represented by the general formula (2) and the cyclopentadiene is represented by a in the general formula (1). Is preferably 0 or 1. When a is larger than 2, the glass transition temperature of the polymer synthesized from the obtained norbornene derivative becomes unnecessarily high, resulting in poor workability and insufficient strength.
<Purification method>
The reaction product thus obtained can be purified / separated by distillation, extraction or crystallization, or a combination thereof. Although the purification method and purification conditions differ depending on the physical and chemical properties of the raw materials, products, and by-products used, the boiling point of the reaction product (norbornene derivative represented by the general formula (1)) is industrially Purification / separation by distillation is preferred when the temperature and pressure are such that distillation is possible, but purification for higher oligomer purity or removal may be performed by extraction or crystallization before or after distillation. If the Diels-Alder reaction product has a high boiling point and is difficult to distill, it can be purified by a combination of removal of components having a low boiling point by distillation and extraction and / or crystallization. Furthermore, when there is a sufficient difference in solubility between the Diels-Alder reaction product and the raw material or by-product, it can be purified by extraction and / or crystallization. A known organic solvent can be used for extraction or crystallization. The separated raw material can be reused. By purifying these techniques, impurities that can be polymerization inhibitors in the next step of ring-opening polymerization or addition polymerization can be removed to an allowable concentration or less.

  The norbornene derivative obtained by the production method of the present invention can be made into a desired polymer by ring-opening polymerization, ring-opening polymerization and subsequent hydrogenation reaction, addition polymerization, radical polymerization, cationic polymerization, anionic polymerization and the like. In addition, the norbornene derivative of the present invention can be copolymerized with an optional copolymerizable compound as necessary to obtain a copolymer.

The polymer synthesized from the norbornene derivative obtained by the production method of the present invention exhibits excellent transparency, heat resistance and low water absorption, and can arbitrarily control the birefringence value and its wavelength dispersion depending on the application. To optical disc, magneto-optical disc, optical lens (Fθ lens, pickup lens, laser printer lens, camera lens, etc.), spectacle lens, optical film / sheet (display film, retardation film, polarizing film, polarizing plate protection) Film, diffusion film, antireflection film, liquid crystal substrate, EL substrate, electronic paper substrate, touch panel substrate, PDP front plate, etc.), transparent conductive film substrate, optical fiber, light guide plate, optical card, optical mirror, IC, LSI It can be suitably applied as a molding material such as an LED sealing material.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

<Synthesis of spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] [3] decene>
cis-1,4-dichloro-2-butene 14.88 g (0.12 mol), fluorene 16.60 g (0.1 mol), 50 wt% aqueous sodium hydroxide 80 g, triethylbenzylammonium chloride 0.4 g (0.0013 mol) Then, 2 mL of dimethyl sulfoxide was charged into a flask equipped with a condenser, a stirrer, and a thermometer, and reacted at 95-100 ° C. for 4 hours. Thereafter, 40 mL of toluene was added to the reaction mixture, the organic phase and the aqueous phase were separated, and the organic phase was washed 3 times with 20 mL of distilled water. The reaction mixture was concentrated and purified by distillation to obtain a mixture containing 70% of spiro [fluorene-9,4′-cyclopentene] [boiling point: 138 to 148 ° C. (1 mmHg), target product yield = 23%]. ¹ H-NMR of the obtained mixture
And ¹³ C-NMR spectra (both measured in deuterated chloroform) are shown in FIGS. 1 and 2, respectively.

4.55 g (0.0146 mol) of a mixture containing spiro [fluorene-9,4′-cyclopentene] obtained as described above was heated to 180 ° C., and dicyclopentadiene was added at 0.38 g / h. A total of 7.2 g (0.0548 mol) was added at an average addition rate. At the same time, the reaction temperature was increased at an average rate of 2 ° C./min to 210 ° C. After addition of the entire amount of dicyclopentadiene, the reaction was continued for another 30 minutes, and the reaction mixture was recrystallized from methanol to produce spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3]. Decene] was obtained in 22% yield. FIG. 3 shows the ¹ H-NMR spectrum (measured in deuterated chloroform) of the resulting spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene]. .

<Synthesis of Spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene]>
A stainless steel reaction of 1.01 g (3.2 mmol) of a mixture containing 70% spiro [fluorene-9,4′-cyclopentene] obtained in the same manner as in Example 1 and 0.9 g (3.4 mmol) of dicyclopentadiene The vessel was charged and reacted at 200 ° C. for 7 hours. The reaction mixture was recrystallized from methanol to obtain spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene] in 9% yield.
[Comparative example]
<Synthesis of Spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene]>
A stainless steel reaction vessel was charged with 18.75 g (0.15 mol) of cis-1,4-dichloro-2-butene and 39.66 g (0.3 mol) of dicyclopentadiene.
For 4 hours. Thereafter, the mixture was purified by distillation to obtain a mixture containing 90% of 5,6-di (chloromethyl) -2-norbornene [boiling point: 108 to 112 ° C. (10 mmHg), target product yield = 44%].

The obtained 5,6-di (chloromethyl) -2-norbornene 5.348 g (0.028 mol), fluorene 4.652 g (0.028 mol), 50 wt% aqueous sodium hydroxide solution 19 g, triethylbenzylammonium chloride 0.13 g (0.0006 mol) and 0.6 mL of dimethyl sulfoxide were charged into a flask equipped with a condenser, a stirrer, and a thermometer, and reacted at 95 to 100 ° C. for 4 hours. Thereafter, 20 mL of toluene was added to the reaction mixture, the organic phase and the aqueous phase were separated, and the organic phase was washed 3 times with 20 mL of distilled water. Spiro [fluorene-9,8'- quantified by gas chromatography analysis after concentration of organic phase
The yield of tricyclo [4.3.0.1 ^2,5 ] [3] decene] was 0.3% and could not be isolated.

1 is a ¹ H-NMR spectrum of a mixture obtained in Example 1. 3 is a ¹³ C-NMR spectrum of the mixture obtained in Example 1. FIG. ^{1 is} a ¹ H-NMR spectrum of spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene].

Claims (6)

A process for producing a norbornene derivative, comprising synthesizing a norbornene derivative represented by the following general formula (1) by a Diels-Alder reaction between a cycloolefin represented by the following general formula (2) and a cyclopentadiene;

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ are each independently Represents a hydrogen atom; a halogen atom; an alkoxy group having 1 to 10 carbon atoms; an atom or group selected from the group consisting of phenoxy groups, a is 0 or 1, and b and c are each independently an integer of 1 or 2 And d, e, f are 1, A is — (single bond); —O— ; —S—; —SO—; —SO ₂ —; —CO—; —NR ¹¹ — (R ¹¹ is Represents an alkyl group having 1 to 30 carbon atoms or an aromatic group) .

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , b, c, d, e, f, and A are each defined by the general formula (1). Street.)   The process for producing a norbornene derivative according to claim 1, wherein the temperature of the reaction mixture during the Diels-Alder reaction is in the range of 100 to 250 ° C.   The method for producing a norbornene derivative according to claim 1 or 2, wherein dicyclopentadiene and / or cyclopentadiene, or di (methylcyclopentadiene) and / or methylcyclopentadiene is used as the cyclopentadiene.   The method for producing a norbornene derivative according to any one of claims 1 to 3, wherein cycloolefins in which b and c in formula (2) are each 1 are used. At least six but the production method of the norbornene derivative according to claim 1, characterized in that the use of cycloolefins a hydrogen atom of R ³ to R ¹⁰ in the general formula (2). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^{10 in the} general formula (1) are hydrogen atoms, a is 0, b, 6. The method for producing a norbornene derivative according to claim 1, wherein a norbornene derivative in which c, d, e, and f are 1 and A is- (single bond) is synthesized.

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