JP2006265176A - Method for producing spiro compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for economically and efficiently producing a spiro compound. <P>SOLUTION: The spiro compound represented by formula (4) is produced by condensing cyclization reaction of a compound represented by formula (1) with a compound represented by formula (2-1) in the presence of a base, wherein a metal hydride is used as the base. [In formula (1) and formula (4), R<SP>1</SP>to R<SP>8</SP>are each H, a halogen or the like; A is a single bond, a divalent (substituted) hydrocarbon or the like; and (a), (b) and (c) are 0 to 2. In formula (2-1), R<SP>9</SP>and R<SP>10</SP>are each a carbocyclic ring, a heterocycle or the like, which are mutually bonded; and X and Y are each H, a halogen, a phosphate or the like]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a process for producing a spiro compound used, for example, as a raw material monomer or raw material monomer precursor of a cycloolefin (co) polymer. More specifically, the present invention relates to a method for obtaining a spiro compound using a metal hydride as a base in a spiro ring formation reaction by condensation cyclization of a compound having an active methylene group with a compound having two leaving groups in the same molecule. .

  Since a compound having a spiro skeleton can fix various substituents, it is possible to control the anisotropy of the refractive index three-dimensionally and is suitable as an optical material or a raw material thereof. In particular, a norbornene derivative having a spiro skeleton has utility value because its ring-opening polymer or addition polymer not only has excellent transparency, heat resistance, low water absorption, etc., but also can easily control the refractive index anisotropy. It is expensive.

  Conventionally, norbornene derivatives having a spiro skeleton include (1) a method of performing a cyclization reaction after the construction of the norbornene skeleton, (2) a method of performing a Diels-Alder reaction between an olefin having a spiro skeleton and a cyclopentadiene, or ( 3) For example, it is known to be obtained by a Diels-Alder reaction between an olefin compound having a cyclic structure such as itaconic anhydride and cyclopentadiene. However, in the method (1), 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. Since side reactions are likely to occur, there are problems such as poor efficiency in the purification process and low yield. Patent Document 1 discloses an example of synthesizing a norbornene derivative having a fluorene skeleton through a spiro carbon by this method, but the spiro ring formation reaction is a reaction at an extremely low temperature, and the yield is low. There was a problem. In the method (2), a spiro compound can be efficiently obtained in some cases, but has the same problems as in (1) in the synthesis of olefins having a spiro skeleton as a raw material. On the other hand, in the method (3), spiro compounds can be efficiently obtained in some cases, but there are problems in that there are few types of inexpensive raw material olefins (dienophiles) that can be used, and spiro carbon introduction positions are limited.

  In order to highly control the optical properties, it is preferable to introduce the substituent at a substitution position where the effect of the substituent can be expressed to the maximum. Therefore, the method (1) or (2) is preferably used. However, in any case, the process that is dominant in terms of productivity and cost in the entire process of monomer production is the process of building a spiro ring.

For this reason, the various problems included in the conventional methods for producing norbornene derivatives or norbornene derivative precursors having a spiro skeleton are extremely serious, and development of new production methods is strongly desired.
JP 2004-323489 A

  An object of the present invention is to provide a method for producing a spiro compound that can efficiently and inexpensively obtain a spiro compound that can be a synthesis raw material of a norbornene derivative having a spiro skeleton or a norbornene derivative having a spiro skeleton.

As a result of diligent studies to achieve the above object, the present inventors have determined that a spiro ring is formed by condensation cyclization between a compound having an active methylene group and a compound having two leaving groups in the same molecule. The inventors have found that a method for producing a spiro compound using a metal hydride as a base satisfies the above object, and have completed the present invention based on the findings.

  That is, the present invention has a compound having an active methylene group represented by the following general formula (1) and a leaving group represented by the following general formula (2-1) or the following general formula (2-2). A spiro, characterized in that a metal hydride is used as a base in the production of a spiro compound represented by the following general formula (4) or (5) by subjecting the compound to a condensation cyclization reaction in the presence of a base. A method for producing a compound is provided.

[In the formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom; a halogen atom; a linking group which is a divalent hydrocarbon group having 1 to 10 carbon atoms; or an oxygen atom, a nitrogen atom, sulfur A substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an atom or a silicon atom; and an atom or group selected from the group consisting of polar groups; , B and c are each independently 0 to 2, and A is a single bond; —O—; —S—; —SO—; —SO ₂
—; —CO—; —NR ¹⁷ —; —SiR ¹⁸ ₂ — (wherein R ¹⁷ and R ¹⁸ represent a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a halogen atom). Or a substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms. ]

[In the formulas (2-1) and (2-2), R ⁹ and R ¹⁰ each independently have a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. A substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms; and an atom or group selected from the group consisting of polar groups, or a carbocyclic or heterocyclic group in which R ⁹ and R ¹⁰ are bonded to each other Represents a ring (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure), and X and Y are each independently a halogen atom or sulfone. Acid ester group (R ¹⁹ SO ₃ —, R ¹⁹ may have a halogen atom and has 1 to 30 carbon atoms.
Monovalent hydrocarbon group), phosphoric acid ester group ((R ²⁰ O) R ²¹ P (O) O—, R ²⁰ and R ²¹ are each an optionally substituted halogen atom having 1 to 30 carbon atoms. A divalent hydrocarbon group), or a divalent group in which X and Y are integrated (R ²¹ P (O) (O—) ₂ , R ²⁰ and R ²¹ may have a halogen atom). A monovalent hydrocarbon group having 1 to 30 carbon atoms). ]

[In the formulas (4) and (5), R ^{1 to} R ¹⁰ , a, b, c, and A represent the general formulas (1), (2-
1) and as defined in (2-2)].
In the present invention, it is preferable to use a hydride of at least one metal selected from the group consisting of lithium, sodium and potassium as the base, and the amount of the metal hydride used is represented by the above general formula (1). The molar ratio of the compound ([compound represented by formula (1)] / [metal hydride]) is preferably 1/1 to 1/4.

In the compound having an active methylene group, at least any six of R ^{1 to} R ^{8 in} the general formula (1) are hydrogen atoms, and a and c are each independently 0 or 1. Preferably, the compound having a leaving group represented by the general formula (2-1) is also preferably a compound having a norbornene skeleton represented by the following general formula (3).

[In the formula (3), R ^{11 to} R ¹⁶ each independently represents a hydrogen atom; a halogen atom; a substituted or unsubstituted which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Represents a monovalent hydrocarbon group having 1 to 30 carbon atoms; and an atom or group selected from the group consisting of polar groups, d, e and f each represent 0 to 2, and X and Y each represent a general formula As defined in (2-1). ]
In this invention, it is preferable that the reaction liquid temperature at the time of condensation cyclization reaction is -50-100 degreeC.
Moreover, it is preferable to perform the condensation cyclization reaction in the presence of an aprotic polar solvent.

  Further, in the present invention, after completion of the condensation cyclization reaction, distillation, sublimation purification, extraction using water, extraction using C1-6 alcohols or crystallization, or a combination thereof, from the reaction mixture. It is preferable to purify and separate the spiro compound.

  The method for producing a spiro compound according to the present invention synthesizes a spiro compound using a metal hydride as a base in a condensation cyclization reaction between a compound having an active methylene group and a compound having a leaving group. By selecting the reaction conditions and raw materials to be used, a spiro compound can be obtained efficiently and inexpensively.

  Further, the method for producing a spiro compound according to the present invention is more efficient than the method for synthesizing the same compound using other bases. Furthermore, any of the synthetic reagents used in the present invention can be manufactured at low cost or low cost, and is highly usable because it is industrially usable.

  The spiro compound obtained by the production method of the present invention is very useful as a norbornene derivative precursor and an optical resin precursor monomer, and its structure fixes various substituents in the vertical direction with the cycloolefin moiety by spiro bonds. Therefore, in a polymer derived using such a spiro compound, birefringence and wavelength dispersion can be freely controlled by appropriately adjusting the content thereof.

  The spiro compound obtained by the production method of the present invention is very useful as a norbornene derivative precursor or optical resin precursor monomer, and polymers derived therefrom are optical disks, magneto-optical disks, optical lenses (Fθ lenses, pickup lenses). , Laser printer 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 substrate, PDP front plate, etc.), transparent conductive film substrate, optical fiber, light guide plate, optical card, optical mirror, IC, LSI, LED encapsulant, etc. It can be applied to optical materials.

Hereinafter, the present invention will be specifically described.
<Reaction reagents and conditions>
The present invention provides a condensation of a compound having an active methylene group represented by the general formula (1) with a compound having a leaving group represented by the general formula (2-1) or the general formula (2-2). In the spiro ring formation reaction by cyclization, a metal hydride is used as an essential reagent as a base. A specific example of the metal hydride to be used is preferably a hydride of at least one metal selected from the group consisting of lithium, sodium and potassium, more preferably potassium hydride or sodium hydride. Particularly preferred is sodium hydride from the viewpoint of cost. These metal hydrides may be used as a dry powder, paraffins may be used as a protective medium, and those dissolved or dispersed in other organic solvents can also be used.

  The amount of the metal hydride used is 1/1 to 1 in a molar ratio with the compound represented by the general formula (1) ([compound represented by the general formula (1)] / [metal hydride]). / 4 is preferable, more preferably 1/1 to 1/3, and particularly preferably 1/1 to 1 / 2.5. If the amount of metal hydride used is less than this range, the yield of the target product may be low, and if it exceeds this range, side reactions may occur, which is not preferred.

The metal hydride may be used alone or in combination with a plurality of metal hydrides, or may be used in combination with other bases.
Examples of other bases include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and calcium carbonate; pyridine, trimethylamine, triethylamine, and the like. Tertiary amine; ammonium hydroxide such as ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide; n-butyllithium, s-butyllithium, t-butyllithium, phenyllithium, etc. Organolithiums; metal amides such as sodaamide and lithium diisopropylamide; metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxy, sodium t-butoxy; sodium, potassium, lithium It can be exemplified alkali metals such as beam.

  When a plurality of bases are used in combination, the amount used is 1/1 (molar ratio ([compound represented by formula (1)] / [total number of moles of base (converted to the number of moles of anion species)]). It is preferably 0.5 to 1 / 5.5, more preferably 1 / 1.7 to 1/5, and particularly preferably 1/2 to 1 / 4.5.

The compound having an active methylene group used in the present invention is a compound represented by the above general formula (1). In the general formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom; a halogen atom; A linking group which is a divalent hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon atom which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom 1 to 30 monovalent hydrocarbon groups; 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 monovalent hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as a methyl group, an ethyl group, and a propyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; and alkenyl groups such as a vinyl group and an allyl group. Groups: alkylidene groups such as ethylidene group and propylidene group; aromatic groups such as phenyl group, p-methylphenyl group, naphthyl group and anthracenyl group. 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); oxygen atom, 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 or more of these A combination of these can be listed.

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. Le 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.

As R ¹⁷ and R ¹⁸ in —NR ¹⁷ — and —SiR ¹⁸ ₂ — represented by A in Formula (1), a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a halogen atom R ¹
Examples include the same group as the hydrocarbon group having 1 to 30 carbon atoms represented by -R ⁸ and a group in which a halogen atom is substituted for these groups. Further, the substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms represented by A in the general formula (1) is preferably — (CH ₂ ) _n — (n is 0 or 1 to 3). Integer).

a, b and c are each independently 0 to 2, and among them, b is preferably 0 or 1 from the viewpoint of availability or production.
The compound represented by the general formula (1) is not particularly limited as long as it satisfies the above definition, but at least any six of R ^{1 to} R ^{8 in} the general formula (1) are hydrogen atoms. It is preferable to use a compound having an active methylene group in which a and c are each independently 0 or 1, and more preferably a and c are 1.

  Examples of the compound represented by the general formula (1) include the following.

The compound having a leaving group used in the present invention is a compound represented by the above general formula (2-1) or (2-2). R ⁹ and R ¹⁰ in the general formula (2-1) are represented by the general formula (1)
Examples thereof include the same groups as R ^{1 to} R ⁸ therein, and R ⁹ and R ¹⁰ may be bonded to each other to form a carbocyclic or heterocyclic ring.

X and Y are each independently a halogen atom or a sulfonate group (R ¹⁹ SO ₃
-, R ¹⁹ is a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a halogen atom), phosphate group ((R ²⁰ O) R ²¹ P (O) O-, R ²⁰ and R ²¹ is a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a halogen atom), or a divalent group R ²¹ P (O) (O—) _{2 in which} X and Y are integrated. , R ²⁰ and R ²¹ each have 1 to 3 carbon atoms which may have a halogen atom
Represents a monovalent hydrocarbon group of 0). Examples of R ^{19 to} R ²¹ include the same groups as the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{1 to} R ⁸ in the general formula (1), and groups obtained by substituting halogen groups for these groups.

R ⁹ and R ¹⁰ in the general formula (2-2) include the same groups as R ^{1 to} R ⁸ in the general formula (1), and preferably a hydrogen atom or an electron from the reactivity of the Diels-Alder reaction. An attractive group, more preferably a hydrogen atom.

In the present invention, as the compound having a leaving group, in the compound represented by the general formula (2-1), a compound in which R ⁹ and R ¹⁰ are bonded to each other to form a carbocycle or a heterocycle is used. Preferably, such a compound includes a compound having a substituted or unsubstituted norbornene skeleton represented by the general formula (3).

As R < ¹¹ > -R < ¹⁶ > in General formula (3), the same group as R < ¹ > -R < ⁸ > in General formula (1) is mentioned. Moreover, d, e, and f in General formula (3) represent 0-2, respectively, More preferably, d is 0, Especially preferably, d is 0 and e is 0 or 1. When d and e are each larger than 2, the glass transition temperature of the polymer synthesized from the norbornene derivative obtained is unnecessarily high, resulting in poor workability and insufficient strength.

Examples of X and Y include the same atoms or groups as in general formula (2-1).
Examples of the compound represented by the general formula (3) include the following.

These compounds represented by the general formula (3) can be obtained by Diels-Alder reaction between cyclopentadiene and cis-2-butene-1,4-diol or trans-2-butene-1,4-diol. A method of converting a hydroxyl group of a compound into a leaving group, a carbonyl moiety of a compound obtained by Diels-Alder reaction of cyclopentadiene with maleic anhydride, maleic acid, maleic acid esters, fumaric acid, or fumaric acid esters. A method of converting a hydroxyl group produced by a reduction reaction into a leaving group after reduction, using the hydroxyl group of cis-2-butene-1,4-diol or trans-2-butene-1,4-diol as a leaving group Method of performing Diels-Alder reaction with cyclopentadiene after conversion, maleic anhydride, maleic acid, malein Esters, fumaric acid or by reduction of the carbonyl moiety of fumaric acid esters, can be obtained by a method of performing Diels-Alder reaction with cyclopentadiene compound after converting the hydroxyl group produced by the reduction reaction to a leaving group.

  The geometric isomerism of the olefin moiety of the dienophile used in the Diels-Alder reaction may be either cis-trans or a mixture of two kinds, but is preferably a cis isomer. A known method can be used for converting the hydroxyl group of the diol to 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, and trifluoromethanesulfonic acid chloride; methoxy (phenyl) phosphone Phosphoric acid derivatives such as acid chloride, phenylphosphonic acid dichloride, methoxy (methyl) phosphonic acid chloride, methylphosphonic acid dichloride; thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl bromide, phosphorus tribromide, phosphorus oxychloride, etc. Halogenating agents; hydrogen halides such as hydrogen chloride and hydrogen bromide; trimethylsilyl chloride, acetonitrile, and lithium bromide, sodium bromide, potassium bromide, calcium bromide, potassium iodide, or sodium iodide And halogenated agent used in combination and the like. 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.

  Charge ratio of the condensation cyclization reaction between the compound having an active methylene group represented by the general formula (1) and the compound having a leaving group represented by the general formula (2-1) or the general formula (2-2) Is 3/1 to 1/3 in molar ratio ([compound represented by general formula (1)] / [compound represented by general formula (2-1) or general formula (2-2)]), Preferably it is 2/1 to 1/2. When the molar ratio of each reagent is outside the above range, two compounds represented by the general formula (1) are substituted for the compound represented by the general formula (2-1) or the general formula (2-2). A by-product may be produced, or the yield may be reduced due to insufficient concentration of the compound represented by the general formula (1).

  Further, a condensation cyclization reaction between a compound having an active methylene group represented by the general formula (1) and a compound having a leaving group represented by the general formula (2-1) or the general formula (2-2) The reaction temperature at the time is −50 to 100 ° C., preferably −40 to 90 ° C., more preferably −30 to 80 ° C. If the reaction temperature is outside this range, the selectivity of the main reaction may be reduced, or the reaction rate may be slow, leading to a reduction in productivity.

  The reaction may be a bulk reaction, but may be performed in various solvents. Specific examples of solvents that can be used include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; benzene, toluene, xylene, ethylbenzene, cumene Aromatic hydrocarbons such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform, tetrachloroethylene, aryl halides, etc .; ethyl acetate, n-butyl acetate, iso acetate -Saturated carboxylic acid esters such as butyl and methyl propionate; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane; dimethyl sulfoxide, sulfolane Dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone, can be mentioned aprotic polar solvents such as acetonitrile, which can be used singly or in combination. Of these, aprotic polar solvents such as dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone, and acetonitrile are preferable and particularly preferable in terms of solubility, reaction selectivity, and reaction rate. Are dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone.

The amount of solvent used is a weight ratio ({solvent} / {[compound represented by general formula (1)] + [compound represented by general formula (2-1) or general formula (2-2)] + [Base]})
0/1, preferably 7/1 to 0.1 / 1, particularly preferably 5/1 to 0.2 / 1. If the amount of the solvent used is outside this range, productivity may be reduced or the reaction system may be non-uniform.

  Preparation of a compound having an active methylene group represented by general formula (1), a compound having a leaving group represented by general formula (2-1) or general formula (2-2), a base, and a solvent In the method, each reagent may be charged all at once, or may be added dividedly or continuously.

During the condensation cyclization reaction between the compound having an active methylene group represented by the general formula (1) and the compound having a leaving group represented by the general formula (2-1) or the general formula (2-2) The reaction time is usually 0.1 to 50 hours, preferably 0.2 to 35 hours, more preferably 0.3 to 24 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.
<Purification method>
The spiro compound thus obtained can be purified / separated by distillation, sublimation purification, extraction, crystallization, or a combination thereof. Purification methods and purification conditions vary depending on the physical and chemical properties of the raw materials, products, and by-products used, but purification by distillation when the boiling point of the spiro compound is an industrially distillable temperature and pressure / Separation is preferred, but the oligomer component may be removed or purified for higher purity by extraction or crystallization before or after distillation. The pressure during distillation may be atmospheric pressure or reduced pressure, and the temperature is usually 20 to 250 ° C, preferably 30 to 220 ° C, more preferably 40 to 200 ° C. If the temperature is outside this range, it may be difficult to liquefy the distilled gas or the target product may be thermally decomposed. Moreover, when it has sublimation property, it can also refine | purify by sublimation purification.

  When the spiro compound 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. Further, when there is a sufficient difference in solubility between the spiro compound and the raw material or by-product, it can be purified by extraction and / or crystallization. For extraction or crystallization, water or a known organic solvent can be used. When performing purification by extraction or crystallization, more specifically, it is preferable to purify by extraction using water and / or extraction using alcohol having 1 to 6 carbon atoms.

  The extraction step with water may be liquid / liquid two-phase extraction or solid / liquid two-phase extraction. In the extraction step with water, when performing extraction of a liquid / liquid two-phase system, the organic phase may be bulk, but among the same ones listed as the reaction solvent, water-insoluble ones can be mentioned. When the reaction mixture solidifies upon contact with water, solid / liquid two-phase extraction can be applied. The amount of water used in the extraction step with water is 0.5 / 1 to 100/1, preferably 1/1 to 50 / in weight ratio ([water] / [sum of all substances used in reaction]). 1, more preferably 1/1 to 30/1. If the amount of water used is outside this range, removal of the water-soluble salt by-produced may be insufficient or productivity may be reduced.

Examples of the alcohol having 1 to 6 carbon atoms used for extraction or crystallization include methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, isobutanol, t-butanol, pentanol, hexanol and cyclohexanol. Preferably, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, isobutanol, more preferably methanol, ethanol, propanol, isopropanol. These solvents may be used singly or in combination, and may be used in combination with other solvents. These alcohols are used in a weight ratio of [alcohols] / [sum of the weight of all substances used in the reaction] = 0.01 / 1 to 50/1, preferably 0.02 / 1 to 40/1. More preferably, it is 0.03 / 1 to 30/1. If the amount of alcohol used is outside this range, removal of impurities such as raw materials may be insufficient or the yield of the target product may be reduced.

  The extraction or crystallization may be performed a plurality of times using water or an organic solvent in the above range. Moreover, the temperature which performs extraction or crystallization is 0-100 degreeC normally, Preferably it is 5-90 degreeC, More preferably, it is 10-80 degreeC. If the temperature is outside this range, productivity may deteriorate or removal of impurities may be insufficient.

The raw materials and / or solvents separated by distillation, extraction, or crystallization can be recovered, purified as necessary, and reused.
The spiro compound obtained by the production method of the present invention is useful as a norbornene derivative precursor and an optical resin precursor. The resulting spiro compound is ring-opening polymerization, ring-opening polymerization and subsequent hydrogenation reaction, addition polymerization, radical polymerization. The desired polymer can be obtained by cationic polymerization, anionic polymerization or the like. In addition, the spiro compound obtained by the production method of the present invention can be copolymerized with an arbitrary copolymerizable compound as necessary to obtain a copolymer.

  The polymer derived from the spiro compound 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>
5,6-di (p-toluenesulfonyloxymethyl) bicyclo [2.2.1] hept-2
-1586 g (3.4 mol) of ene and 569 g (3.4 mol) of fluorene were dissolved in 8000 g of dimethyl sulfoxide, and the temperature was adjusted to 20 ° C. This solution has a temperature of 25 ° C.
253g of sodium hydride containing 35wt% liquid paraffins while maintaining the following
(6.9 mol) was gradually added and stirred. The reaction was monitored by TOSHO HLC-8220GPC (column: TOSHO SuperHZ2000x2 and SuperHZ1000x1, solvent: tetrahydrofuran, detector: RI and UV, flow rate: 0.5 mL, temperature: 40 ° C.), after completion of sodium hydride addition The target product yield reached 68% in 4 hours and reached 76% in 8 hours.

After reacting for 8 hours, 5000 g of methanol was poured into the reaction mixture and stirred at 20 ° C. for 1 hour, and then the precipitate was collected by filtration. The obtained solid was washed again with 3000 g of methanol. The recovered material was dried to obtain a milky white solid with a recovery rate of 74%. It was confirmed by ¹ H-NMR that the obtained compound was the target spiro [fluorene-9,8′-tricyclo [4.3.0.1 ^2.5 ] [3] decene]. Spiro [fluorene-9,8′-tricyclo [4.
The ¹ H-NMR spectrum of 3.0.1 ^2.5 ] [3] decene] is shown in FIG. 1, and the IR spectrum is shown in FIG.

<Synthesis of spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] [3] decene>
As a result of carrying out the reaction with the same procedure, reaction conditions, and charged amount (weight) as in Example 1 except that dimethylacetamide was used as a solvent, the target product yield at a reaction time of 3 hours was 55% for 6 hours. It reached 72%. After reacting for 6 hours, purification was carried out in the same manner as in Example 1 to obtain the desired product in a yield of 65%.
[Comparative Example 1]
<Synthesis of spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] [3] decene>
As a result of carrying out the reaction with the same procedure, reaction conditions, and charge amount (number of moles) as in Example 1 except that t-butoxypotassium was used as the base, the target product yield in a reaction time of 3 hours was 58%. Some raw materials almost disappeared due to side reactions. After reacting for 3 hours, purification was conducted in the same manner as in Example 1 to obtain the desired product in a yield of 49%.
[Comparative Example 2]
<Synthesis of spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] [3] decene>
As a result of carrying out the reaction with the same procedure, reaction conditions, and charged amount (number of moles) as in Example 1 except that sodium hydroxide was used as the base, the target product formation rate at a reaction time of 3 hours was 31%. The target product formation rate at 20 hours was 48%, and during the reaction for 20 hours, the raw materials were almost lost due to side reactions. After reacting for 20 hours, purification was conducted in the same manner as in Example 1 to obtain the desired product in a yield of 35%.
[Comparative Example 3]
<Synthesis of spiro [fluorene -9,8'- tricyclo [4.3.0.1 ^2.5] [3] decene>
15.52 g (0.0934 mol) of fluorene was dissolved in 165 mL of dehydrated THF (tetrahydrofuran). Next, 117 mL of a 1.6 mol / L hexane solution of n-butyllithium was gradually added dropwise while maintaining the temperature of the reaction system at −78 ° C. in a dry ice bath. After completion of dropping, stirring was continued for 1 hour while maintaining the reaction system at -78 ° C. In this reaction solution, 5,6-di (p-toluenesulfonyloxymethyl) bicyclo [2.2.1] hept-2 was added.
A solution prepared by previously dissolving 21.60 g (0.0467 mol) of -ene in 500 mL of THF was gradually added dropwise while maintaining the temperature of the reaction system at -78 ° C. After completion of the dropwise addition, stirring was continued for 1 hour in a dry ice bath, and then the cooling bath was removed, and stirring was continued until the reaction system completely returned to room temperature (about 3 hours). The reaction solution was concentrated after quenching by adding saline. Thereafter, the reaction mixture was dissolved in cyclohexane, washed with distilled water three times, and dried using sodium sulfate. Thereafter, the solvent was removed by heating under reduced pressure, and the resulting solid was recrystallized using methanol to obtain 5.68 g (43%) of pale yellow crystals.

1 shows the ¹ H-NMR spectrum of the compound obtained in Example 1. FIG. FIG. 2 shows the IR spectrum of the compound obtained in Example 1.

Claims (8)

The presence of a base comprising a compound having an active methylene group represented by the following general formula (1) and a compound having a leaving group represented by the following general formula (2-1) or the following general formula (2-2) A process for producing a spiro compound, wherein a metal hydride is used as the base when a spiro compound represented by the following general formula (4) or (5) is produced by a condensed cyclization reaction below;

[In the formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom; a halogen atom; a linking group which is a divalent hydrocarbon group having 1 to 10 carbon atoms; or an oxygen atom, a nitrogen atom, sulfur A substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an atom or a silicon atom; and an atom or group selected from the group consisting of polar groups; , B and c are each independently 0 to 2, and A is a single bond; —O—; —S—; —SO—; —SO ₂
—; —CO—; —NR ¹⁷ —; —SiR ¹⁸ ₂ — (wherein R ¹⁷ and R ¹⁸ represent a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a halogen atom). Or a substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms. ]

[In the formulas (2-1) and (2-2), R ⁹ and R ¹⁰ each independently have a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. A substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms; and an atom or group selected from the group consisting of polar groups, or a carbocyclic or heterocyclic group in which R ⁹ and R ¹⁰ are bonded to each other Represents a ring (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure), and X and Y are each independently a halogen atom or sulfone. Acid ester group (R ¹⁹ SO ₃ —, R ¹⁹ may have a halogen atom and has 1 to 30 carbon atoms.
Monovalent hydrocarbon group), phosphoric acid ester group ((R ²⁰ O) R ²¹ P (O) O—, R ²⁰ and R ²¹ are each an optionally substituted halogen atom having 1 to 30 carbon atoms. A divalent hydrocarbon group), or a divalent group in which X and Y are integrated (R ²¹ P (O) (O—) ₂ , R ²⁰ and R ²¹ may have a halogen atom). A monovalent hydrocarbon group having 1 to 30 carbon atoms). ]

[In the formulas (4) and (5), R ^{1 to} R ¹⁰ , a, b, c, and A represent the general formulas (1), (2-
As defined in 1) and (2-2). ].   2. The method for producing a spiro compound according to claim 1, wherein the base is a hydride of at least one metal selected from the group consisting of lithium, sodium and potassium.   The amount of the metal hydride used is 1/1 to 1 in terms of a molar ratio with the compound represented by the general formula (1) ([compound represented by the general formula (1)] / [metal hydride]). It is 1/4, The manufacturing method of the spiro compound of Claim 1 or 2 characterized by the above-mentioned. The compound having an active methylene group is characterized in that at least any six of R ^{1 to} R ^{8 in} the general formula (1) are hydrogen atoms, and a and c are each independently 0 or 1, The method for producing a spiro compound according to any one of claims 1 to 3. The compound having a leaving group represented by the general formula (2-1) is a compound having a norbornene skeleton represented by the following general formula (3). A method for producing a spiro compound according to item 1;

[In the formula (3), R ^{11 to} R ¹⁶ each independently represents a hydrogen atom; a halogen atom; a substituted or unsubstituted which may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom. Represents a monovalent hydrocarbon group having 1 to 30 carbon atoms; and an atom or group selected from the group consisting of polar groups, d, e and f each represent 0 to 2, and X and Y each represent a general formula As defined in (2-1). ].   The method for producing a spiro compound according to any one of claims 1 to 5, wherein the reaction solution temperature during the condensation cyclization reaction is -50 to 100 ° C.   The method for producing a spiro compound according to any one of claims 1 to 6, wherein the condensation cyclization reaction is carried out in the presence of an aprotic polar solvent.   After completion of the condensation cyclization reaction, the spiro compound is purified from the reaction mixture by distillation, sublimation purification, extraction with water, extraction or crystallization with an alcohol having 1 to 6 carbon atoms, or a combination thereof. It isolate | separates, The manufacturing method of the spiro compound of any one of Claims 1-7 characterized by the above-mentioned.

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