JP4775759B2 - Novel alicyclic compound, process for producing the same and polymer of the compound - Google Patents
Novel alicyclic compound, process for producing the same and polymer of the compound Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims description 40
- 150000001334 alicyclic compounds Chemical class 0.000 title claims description 16
- 229920000642 polymer Polymers 0.000 title claims description 11
- 238000000034 method Methods 0.000 title description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 230000011987 methylation Effects 0.000 claims description 3
- 238000007069 methylation reaction Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000012776 electronic material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005698 Diels-Alder reaction Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 diene compound Chemical class 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- QJMYXHKGEGNLED-UHFFFAOYSA-N 5-(2-hydroxyethylamino)-1h-pyrimidine-2,4-dione Chemical compound OCCNC1=CNC(=O)NC1=O QJMYXHKGEGNLED-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011984 grubbs catalyst Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、新規脂環式化合物、その製造法および当該化合物の重合体に関する。 The present invention relates to a novel alicyclic compound, a production method thereof, and a polymer of the compound.
近年、電子材料、光学材料の分野では、各種性能を向上させるべく、種々の新規材料が検討されている。特に、脂環式化合物については、電子材料、光学材料等の分野で優れた特性が期待できるため、開発が行われている。本願人も先に種々の新規脂環式化合物を提案している（例えば、特許文献１、２参照）が、さらなる高性能を付与しうる材料が求められている。 In recent years, various new materials have been studied in the fields of electronic materials and optical materials in order to improve various performances. In particular, alicyclic compounds have been developed because excellent properties can be expected in fields such as electronic materials and optical materials. The present applicant has previously proposed various novel alicyclic compounds (see, for example, Patent Documents 1 and 2), but a material capable of imparting further high performance is required.
ところで、これらの用途において天然物由来の材料を有効利用できれば、環境負荷を低減することができるものと期待される。 By the way, it is expected that the environmental load can be reduced if materials derived from natural products can be effectively used in these applications.
本発明は、天然物由来原料を用いた電子材料、光学材料等として良好な物性を有する新規な化合物および当該化合物を用いて得られる重合体を提供することを目的とする。 An object of the present invention is to provide a novel compound having good physical properties as an electronic material, an optical material or the like using a natural product-derived raw material, and a polymer obtained using the compound.
本発明者は、テルペン類を原料とする脂環式化合物について鋭意検討したところ、電子材料、光学材料として良好な物性を有することが期待できる化合物および当該化合物を合成する方法を見出し、本発明を完成させた。 As a result of intensive studies on alicyclic compounds using terpenes as raw materials, the present inventors have found a compound that can be expected to have good physical properties as an electronic material and an optical material, and a method for synthesizing the compound. Completed.
すなわち、本発明は、一般式（１）： That is, the present invention relates to the general formula (1):
（式中、Ｒ１、Ｒ２、Ｒ１´およびＲ２´は、一般式（２）： (Wherein, R 1, R 2, R 1'and R 2'is formula (2):
（式中、ａは１〜１２の整数を表す。）で表される官能基、メチル基または水素原子であって、それぞれ同一でも、異なっていてもよい。ただし、Ｒ１、Ｒ２、Ｒ１´およびＲ２´の少なくとも一つは水素原子およびメチル基以外の基である。）で表される脂環式化合物；一般式（４）：
(In the formula, a represents. An integer of 1 to 12), a functional group, methylation group or a hydrogen atom represented by, in each same or may be different. Provided that at least one of R 1, R 2, R 1'and R 2'is a group other than a hydrogen atom and a methyl group. ) Alicyclic compound represented by general formula (4):
（式中、Ｒ4、Ｒ５、Ｒ４´およびＲ５´は、一般式（５）：−ＣＯＲ6（式中、Ｒ6は水酸基、炭素数１〜４のアルコキシ基を表す。）、メチル基または水素原子を表し、それぞれ同一でも、異なっていてもよい。ただし、Ｒ４、Ｒ５、Ｒ４´およびＲ５´の少なくとも一つは水素原子およびメチル基以外の基である。）で表される化合物に、一般式（６）： (Wherein, R 4, R 5, R 4' and R 5'are general formula (5): - COR 6 (wherein, R 6 represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms). It represents a methyl group or a hydrogen atom, in each identical or different. However, R 4, R 5, at least one of R 4'and R 5'are groups other than a hydrogen atom and a methyl group.) In the compound represented by general formula (6):
（式中、Ｘはハロゲン基または水酸基、ａは１〜１２の整数を表す。）で表される化合物を反応させることを特徴とする一般式（１）で表される脂環式化合物の製造方法；前記脂環式化合物を重合させて得られる重合体；前記脂環式化合物または前記重合体を含有する光学材料；前記脂環式化合物または前記重合体を含有する電子材料；前記重合体を成形して得られるレンズに関する。
(Wherein, X represents a halogen group or a hydroxyl group, and a represents an integer of 1 to 12. ) A compound represented by the general formula (1) is reacted. A polymer obtained by polymerizing the alicyclic compound; an optical material containing the alicyclic compound or the polymer; an electronic material containing the alicyclic compound or the polymer; The present invention relates to a lens obtained by molding.
本発明の脂環式化合物は、重合性官能基を有するため、従来の電子材料、光学材料に新規な特性を容易に組み込むことができるものである。また、当該化合物の重合体は、電子材料、光学材料として良好な物性を有するものと期待できる。 Since the alicyclic compound of the present invention has a polymerizable functional group, it can easily incorporate new characteristics into conventional electronic materials and optical materials. The polymer of the compound can be expected to have good physical properties as an electronic material or an optical material.
本発明の新規な脂環式化合物は、α−ピネンを、例えば、「渡辺雄一著、α−ピネンおよびｐ−メンタジエンの硫酸水溶液による異性化、工業化学雑誌、1962年、第65巻、第10号、1572−1573頁」に記載された方法により一般式（８）： The novel cycloaliphatic compound of the present invention can be obtained by using α-pinene, for example, “Yuichi Watanabe, isomerization of α-pinene and p-mentadiene with an aqueous sulfuric acid solution, Industrial Chemical Journal, 1962, Vol. 65, No. 10 No., pages 1572-1573 ”, the general formula (8):
で表されるジエン化合物とし、当該ジエン化合物に、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステルなどの不飽和モノカルボン酸類、無水マレイン酸、マレイン酸、マレイン酸エステルなどの不飽和ジカルボン酸類などの不飽和カルボン酸類をディールスアルダー反応させ、必要により加水分解させることにより得られた前記一般式（４）で表される化合物に一般式（６）： In the diene compound, unsaturated dicarboxylic acids such as (meth) acrylic acid, (meth) acrylic acid alkyl ester and the like, and unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and maleic acid ester The compound represented by the general formula (4) obtained by reacting an unsaturated carboxylic acid such as Diels-Alder and optionally hydrolyzing the compound is represented by the general formula (6):
（式中、Ｘはハロゲン基または水酸基、ａは１〜１２の整数を表す。）を表す。）で表される化合物を反応させることにより得られる。
(Wherein X represents a halogen group or a hydroxyl group, and a represents an integer of 1 to 12 ) . It is obtained by reacting a compound represented by
一般式（８）で表される化合物に不飽和カルボン酸類をディールスアルダー反応させる際の反応条件としては、特に限定されず公知の反応条件を採用すれば良い。例えば一般式（８）で表される化合物１モルに対し、（メタ）アクリル酸または（メタ）アクリル酸アルキルエステルを１．０〜２０モル程度用い、温度を５０〜１８０℃程度に加熱すればよい。反応圧力は特に限定されないが、通常、１〜２０ＭＰａ程度とすることが反応を速やかに進行させることができるため好ましい。 The reaction conditions for causing the Diels-Alder reaction of unsaturated carboxylic acids with the compound represented by the general formula (8) are not particularly limited, and known reaction conditions may be employed. For example, with respect to 1 mol of the compound represented by the general formula (8), about 1.0 to 20 mol of (meth) acrylic acid or (meth) acrylic acid alkyl ester is used and the temperature is heated to about 50 to 180 ° C. Good. Although reaction pressure is not specifically limited, Usually, it is preferable to set it as about 1-20 MPa since reaction can be advanced rapidly.
ディールスアルダー反応によって得られた化合物は必要に応じて蒸留等の方法により精製してもよい。各エステル体を用いる場合には、加水分解を行いカルボン酸とした後にエステル化反応を行ってもよく、直接エステル交換でエステル化してもよい。加水分解は、当該化合物を、酸またはアルカリおよび水の存在下溶媒中で行えばよい。 You may refine | purify the compound obtained by Diels Alder reaction by methods, such as distillation, as needed. When each ester is used, it may be hydrolyzed to obtain a carboxylic acid, followed by esterification, or may be directly esterified by transesterification. The hydrolysis may be performed in a solvent in the presence of an acid or alkali and water.
本発明の脂環構造を有する化合物は、前記方法で得られた一般式（４）で表される化合物に、一般式（６）で表される化合物を反応させるものである。一般式（６）で表される化合物としては、例えば、エピクロロヒドリン、グリシドール等が挙げられる。
The compound having an alicyclic structure of the present invention is obtained by reacting the compound represented by the general formula (4) obtained by the above method with the compound represented by the general formula (6 ) . Examples of the compound represented by the general formula (6) include epichlorohydrin and glycidol .
一般式（４）で表される化合物として、エステル類（Ｒ４、Ｒ５、Ｒ４´およびＲ５´の少なくとも１つが、−ＣＯＲ６で表される官能基であって、Ｒ６がアルコキシ基のもの）を用い、加水分解を経ずに直接エステル交換を行う場合には、一般式（６）で表される化合物のＸが水酸基のものを用いる。当該反応は、例えば、溶媒および触媒の存在下で、一般式（４）で表される化合物１モルに対し一般式（６）で表される化合物１〜２０モル程度を、反応温度２０℃〜１５０℃程度で、２〜２０時間程度加熱すればよい。反応に用いる溶媒としては、反応に不活性で反応条件にて使用できるものであれば特に制限されるものではないが、副生するアルコールを系外に留去するためには沸点の高い溶媒を用いるのが好ましく、例えば、ヘプタン、シクロヘキサン等の脂肪族および脂環系の炭化水素、トルエン、キシレン等の芳香族系溶媒等を例示することができる。触媒としては硫酸、パラトルエンスルホン酸などの酸性触媒、水酸化ナトリウム、カリウムエチラート、トリエチルアミン、などの塩基性触媒を、一般式（４）で表される化合物１モルに対し、０．００１〜０．１モル程度用いることが好ましい。
As the compound represented by formula (4), at least one of the esters (R 4, R 5, R 4'and R 5', a functional group represented by -COR 6, R 6 is alkoxy When the transesterification is performed directly without hydrolysis, the compound represented by the general formula (6) has a hydroxyl group as X. In the reaction, for example, in the presence of a solvent and a catalyst, about 1 to 20 mol of the compound represented by the general formula (6 ) is added at a reaction temperature of 20 ° C. to 1 mol of the compound represented by the general formula (4). What is necessary is just to heat at about 150 degreeC for about 2 to 20 hours. The solvent used in the reaction is not particularly limited as long as it is inert to the reaction and can be used under the reaction conditions. However, in order to distill off the by-produced alcohol out of the system, a solvent having a high boiling point is used. For example, aliphatic and alicyclic hydrocarbons such as heptane and cyclohexane, and aromatic solvents such as toluene and xylene can be exemplified. As the catalyst, an acidic catalyst such as sulfuric acid and p-toluenesulfonic acid, and a basic catalyst such as sodium hydroxide, potassium ethylate, triethylamine, and the like are used in an amount of 0.001 to 1 mol per 1 mol of the compound represented by the general formula (4). It is preferable to use about 0.1 mol.
一般式（４）で表される化合物として、カルボン酸（Ｒ４、Ｒ５、Ｒ４´およびＲ５´の少なくとも１つが、一般式（５）で表される官能基であって、Ｒ６が水酸基のもの）を用いる場合、一般式（６）で表される化合物との反応は、例えば、溶媒および触媒の存在下で、一般式（４）で表される化合物１モルに対し一般式（６）で表される化合物１〜２０モルを、反応温度２０℃〜１５０℃程度で、２〜２０時間程度加熱すればよい。一般式（６）で表される化合物としてハロゲン化物（Ｘがハロゲン基のもの）を用いる場合、反応に用いる溶媒としては、反応に不活性で反応条件にて使用できるものであれば特に制限されるものではなく、例えば、テトラヒドロフラン、ジエチルエーテル、エチルイソプロピルエーテル等のエーテル系溶媒、トルエン、キシレン等の芳香族系溶媒等を例示することができる。触媒としてはテトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライドなどの塩基性触媒を、一般式（４）で表される化合物１モルに対し、０．００１〜０．１モル程度用いることが好ましい。 As the compound represented by formula (4), carboxylic acid (R 4, R 5, at least one of R 4'and R 5', a functional group represented by the general formula (5), R 6 In the presence of a hydroxyl group), the reaction with the compound represented by the general formula (6) is performed, for example, in the presence of a solvent and a catalyst with respect to 1 mol of the compound represented by the general formula (4). What is necessary is just to heat about 1-20 mol of compounds represented by (6) at a reaction temperature of about 20 ° C to 150 ° C for about 2 to 20 hours. When a halide (X is a halogen group) is used as the compound represented by the general formula (6), the solvent used for the reaction is not particularly limited as long as it is inert to the reaction and can be used under the reaction conditions. Examples thereof include ether solvents such as tetrahydrofuran, diethyl ether and ethyl isopropyl ether, and aromatic solvents such as toluene and xylene. As the catalyst, a basic catalyst such as tetramethylammonium chloride or tetraethylammonium chloride is preferably used in an amount of about 0.001 to 0.1 mol with respect to 1 mol of the compound represented by the general formula (4).
一般式（６）で表される化合物として、アルコール類（Ｘが水酸基のもの）を用いる場合には、共沸で水を除去しながら反応を行うことが好ましく、溶媒としては、水と共沸する芳香族系溶媒等を用いることが好ましく、また、触媒としてエステル化触媒を使用することが好ましい。エステル化触媒としては、硫酸、パラトルエンスルホン酸等が挙げられる。触媒を用いる際の使用量は、特に限定されないが、一般式（４）で表される化合物１モルに対し、０．００１〜０．１モル程度であることが好ましい。なお、反応が進行しにくい場合には、公知の方法によって、カルボキシル基を酸塩化物とした後に反応させても良い。 When an alcohol (X is a hydroxyl group) is used as the compound represented by the general formula (6), the reaction is preferably carried out while removing water azeotropically, and the solvent is azeotropic with water. It is preferable to use an aromatic solvent or the like, and it is preferable to use an esterification catalyst as the catalyst. Examples of the esterification catalyst include sulfuric acid and p-toluenesulfonic acid. Although the usage-amount at the time of using a catalyst is not specifically limited, It is preferable that it is about 0.001-0.1 mol with respect to 1 mol of compounds represented by General formula (4). In addition, when reaction does not advance easily, you may make it react after making a carboxyl group into acid chloride by a well-known method.
前記方法により得られた反応物は、蒸留、シリカゲルカラムクロマトグラフィー等の各種公知の精製方法で精製することにより、一般式（１）で表される化合物が得られる。 The reaction product obtained by the above method is purified by various known purification methods such as distillation and silica gel column chromatography to obtain the compound represented by the general formula (1).
前記方法により得られた一般式（１）で表される脂環式化合物はエポキシ基または重合性二重結合を有するものであるから、エポキシ樹脂原料、ポリウレタン樹脂原料やラジカル重合体原料などとして用いることができる。また、当該化合物は、分子中にシクロオレフィン構造を有するものであるため、Ｇｒｕｂｂｓ触媒等により開環重合および付加重合させることも可能であり、例えばエポキシ基を有する当該脂環化合物からはエポキシ基を有するシクロオレフィンポリマーを得ることができる。 Since the alicyclic compound represented by the general formula (1) obtained by the above method has an epoxy group or a polymerizable double bond, it is used as an epoxy resin raw material, a polyurethane resin raw material, a radical polymer raw material, or the like. be able to. Further, since the compound has a cycloolefin structure in the molecule, it can also be subjected to ring-opening polymerization and addition polymerization using a Grubbs catalyst or the like. For example, an epoxy group is removed from the alicyclic compound having an epoxy group. A cycloolefin polymer having the same can be obtained.
前記方法により得られた分子内にビニル基を有する脂環式化合物は、単独で重合させてまたは他の公知のモノマーと共重合させることにより、不飽和脂環構造を有する重合体を得ることができる。重合させる場合の重合条件としては、例えば、公知のラジカル重合条件を採用すれば良い。共重合させるモノマーとしては特に制限されないが、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸、無水マレイン酸などが挙げられる。これらの中では、光学材料としては、（メタ）アクリル酸メチルを用いることが好ましい。 The alicyclic compound having a vinyl group in the molecule obtained by the above method can be polymerized alone or copolymerized with other known monomers to obtain a polymer having an unsaturated alicyclic structure. it can. As polymerization conditions for polymerization, for example, known radical polymerization conditions may be employed. Although it does not restrict | limit especially as a monomer to copolymerize, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, (meth) acrylic acid isobornyl, (meth) acrylic acid hydroxyethyl, (meth) Examples include acrylic acid and maleic anhydride. In these, it is preferable to use methyl (meth) acrylate as an optical material.
以下に、実施例をあげて本発明をさらに具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。また、各化合物のスペクトル測定には、次の装置を使用した。
ＮＭＲ：ＧＥＭＩＮＩ−３００（Ｖａｒｉａｎ社製）
ＩＲ：ＮＥＸＵＳ６７０（サーモエレクトロン社製）
ガスクロマトフィー（ＧＣ）：ＧＣ６８９０（アジレント社製）
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Moreover, the following apparatus was used for the spectrum measurement of each compound.
NMR: GEMINI-300 (manufactured by Varian)
IR: NEXUS670 (manufactured by Thermo Electron)
Gas chromatography (GC): GC6890 (manufactured by Agilent)
合成例１（ディールスアルダー反応）
１リットルのオートクレーブに、α−テルピネン３１２．０ｇ、アクリル酸メチル１８７．７ｇを仕込み気密の後、１９０℃、反応容器内圧力は２９０ｋＰａにて、４時間反応させ、蒸留精製することにより目的物であるディールスアルダー付加体Ａを得た。得られた目的の付加体Ａの純度は、９９．０％（ＧＣ法）であった。
Synthesis Example 1 (Diels Alder reaction)
A 1 liter autoclave was charged with 312.0 g of α-terpinene and 187.7 g of methyl acrylate. After airtightness, the mixture was reacted at 190 ° C. and a pressure in the reaction vessel of 290 kPa for 4 hours and purified by distillation. A Diels Alder adduct A was obtained. The purity of the obtained target adduct A was 99.0% (GC method).
合成例２（加水分解反応）
ジムロート冷却管、温度計、滴下ロート、窒素ガス導入管、攪拌機を備えた反応容器に、水酸化ナトリウム２４．０ｇおよび水４８ｍｌを仕込み攪拌し、均一な溶液とした。メタノール１００ｍｌ、製造例１で得られたディールスアルダー付加体Ａ（メチルエステル）６６．７ｇ、エタノール１００ｍｌを加え、７０℃まで加熱・昇温し、２２時間反応させた。反応溶液を４０℃まで冷却し、イオン交換水１００ｍｌを加えトルエン１００ｍｌで２回洗浄し、不純物を除去した。その後、氷浴下、水層に３０％硫酸水溶液８０ｍｌを滴下し、３０分間攪拌を継続した。トルエン１００ｍｌで２回抽出を行い、有機層をイオン交換水１００ｍｌで３回洗浄した。有機層から減圧濃縮で溶媒を留去し、加水分解体Ａを得た。得られた加水分解体Ａの純度９９．８％（ＧＣ法）であった。
Synthesis example 2 (hydrolysis reaction)
A reaction vessel equipped with a Dimroth condenser, thermometer, dropping funnel, nitrogen gas inlet tube, and stirrer was charged with 24.0 g of sodium hydroxide and 48 ml of water and stirred to obtain a uniform solution. 100 ml of methanol, 66.7 g of Diels-Alder adduct A (methyl ester) obtained in Production Example 1 and 100 ml of ethanol were added, heated to 70 ° C., heated, and reacted for 22 hours. The reaction solution was cooled to 40 ° C., 100 ml of ion exchange water was added, and the mixture was washed twice with 100 ml of toluene to remove impurities. Thereafter, 80 ml of 30% aqueous sulfuric acid solution was added dropwise to the aqueous layer in an ice bath, and stirring was continued for 30 minutes. Extraction was performed twice with 100 ml of toluene, and the organic layer was washed 3 times with 100 ml of ion-exchanged water. The solvent was distilled off from the organic layer under reduced pressure to obtain hydrolyzate A. The purity of the obtained hydrolyzate A was 99.8% (GC method).
合成例３（エステル化反応）
ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、空気バブリング用導入管、攪拌機を備えた反応容器にエピクロロヒドリン１１１．０ｇ、炭酸ナトリウム９．０４ｇ、フェノチアジン０．０９３ｇを仕込み、攪拌開始した。系内に空気をバブリングしながら、１１０℃まで昇温した。製造例２で得られた加水分解体Ａ３１．２ｇとトルエン１６．９ｇの均一溶液を調整し、系内に滴下した。滴下終了後、テトラメチルアンモニウムクロライド０．０４６ｇを添加し、ディーンスターク水分器で系内から水を留出させながら、１時間反応させた後、４０℃まで冷却した。系内に３％水酸化ナトリウム水溶液３０ｍｌを加え有機層を洗浄した。ｐ−トルエンスルホン酸ナトリウム０．００８ｇを添加し、空気バブリングしながらトルエンと過剰エピクロロヒドリンを減圧留去した。反応溶液を、シリカゲルカラムクロマトグラフィー（展開溶媒ｎ−ヘキサン／酢酸エチル混合系）で分取し、脂環化合物Ａ（一般式（１）において、Ｒ１が一般式（２）で表される官能基（ａは１）、Ｒ２が水素、および一般式（１）において、Ｒ１が水素、Ｒ２が一般式（２）で表される官能基（ａは１）の混合物。）を得た。
Synthesis Example 3 (Esterification reaction)
A reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, air bubbling inlet, and stirrer was charged with 111.0 g of epichlorohydrin, 9.04 g of sodium carbonate, and 0.093 g of phenothiazine. The stirring was started. The temperature was raised to 110 ° C. while bubbling air into the system. A homogeneous solution of hydrolyzate A 31.2 g obtained in Production Example 2 and 16.9 g of toluene was prepared and dropped into the system. After completion of the dropwise addition, 0.046 g of tetramethylammonium chloride was added, the mixture was reacted for 1 hour while distilling water from the system with a Dean-Stark moisture device, and then cooled to 40 ° C. 30 ml of a 3% aqueous sodium hydroxide solution was added to the system to wash the organic layer. 0.008 g of sodium p-toluenesulfonate was added, and toluene and excess epichlorohydrin were distilled off under reduced pressure while bubbling air. The reaction solution was fractionated by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate mixed system), and the alicyclic compound A (the functional group in which R 1 is represented by the general formula (2) in the general formula (1)). A group (a is 1), R 2 is hydrogen, and in general formula (1), R 1 is hydrogen and R 2 is a mixture of functional groups (a is 1) represented by general formula (2). It was.
１Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ3、δ（ｐｐｍ））：１．１５、６．０７、０．９４、３．８５、４．３６、３．１８、２．６４、２．８３ 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 1.15, 6.07, 0.94, 3.85, 4.36, 3.18, 2.64, 2.83
１３Ｃ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ3、δ（ｐｐｍ））１３３．１８−１３９．４３、１７５．２０、１７５．３２、６４．３０−６４．６１ 13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) 133.18-139.43, 175.20, 175.32, 64.30-64.61
ＩＲ（ｎｅａｔ）：１１５０、１７３６、１０３６（ｃｍ-1） IR (neat): 1150, 1736, 1036 (cm −1 )
本発明の化合物および重合体は、電子材料、光学材料として有用である。また、不飽和脂環構造および二重結合またはエポキシ基を有するといった特異な構造を有することから、各種化合物の誘導前駆体として使用することもできると考えられる。
The compounds and polymers of the present invention are useful as electronic materials and optical materials. Moreover, since it has a specific structure such as an unsaturated alicyclic structure and a double bond or an epoxy group, it can be used as a derivative precursor for various compounds.
Claims (3)
（式中、Ｒ4、Ｒ５、Ｒ４´およびＲ５´は、一般式（５）：−ＣＯＲ6（式中、Ｒ6は水酸基、炭素数１〜４のアルコキシ基を表す。）、メチル基または水素原子を表し、それぞれ同一でも、異なっていてもよい。ただし、Ｒ４、Ｒ５、Ｒ４´およびＲ５´の少なくとも一つは水素原子およびメチル基以外の基である。）で表される化合物に、一般式（６）：
(Wherein, R 4, R 5, R 4' and R 5'are general formula (5): - COR 6 (wherein, R 6 represents a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms). It represents a methyl group or a hydrogen atom, in each identical or different. However, R 4, R 5, at least one of R 4'and R 5'are groups other than a hydrogen atom and a methyl group.) In the compound represented by general formula (6):
A polymer obtained by polymerizing the compound according to claim 1.
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